ROOM TEMPERATURE AMBIENT SYNTHESIS OF METAL-DOPED HALIDE PEROVSKITE NANOCRYSTALS
20250171686 ยท 2025-05-29
Inventors
Cpc classification
C01P2006/60
CHEMISTRY; METALLURGY
C01G21/006
CHEMISTRY; METALLURGY
International classification
Abstract
A method of preparing a composition including crystalline particles of a halide perovskite, a composition and a perovskite-based device including the same. The halide perovskite has a chemical formula ABX.sub.3, wherein A is a monocation, B is selected from a combination of lead (II) and a dopant and X is selected from a halide.
Claims
1. A method of preparing a composition comprising crystalline particles of a first halide perovskite, the method comprising the steps of: combining an A-site stock solution comprising: an A-site complex comprising an A-site precursor and an A-site complexing agent; and a first non-polar solvent; with a B-site stock solution comprising: a B-site complex comprising a lead (II) halide, a dopant halide, a B-site complexing agent; and a second non-polar solvent; in a third non-polar solvent, under conditions suitable for the formation of a first product mixture, comprising the crystalline particles of a first halide perovskite, the first halide perovskite having a chemical formula according to Formula I:
ABX.sub.3(I); wherein: A is a monocation selected from a metallic element and a monocationic organic group; B is selected from a combination of Pb.sup.2+ and a dopant; X, independently at each occurrence, is a halide; and further wherein: the A-site precursor is a salt of A, which is soluble in the first non-polar solvent; the A-site complexing agent and the B-site complexing agent are each selected from a molecule comprising at least one non-polar hydrocarbyl group and at least one polar group; the dopant is a dication of a metallic element or a trication of a metallic element.
2. The method of any one of claim 1, wherein A is selected from the group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, and Cs.sup.+ or from the group consisting of methylammonium [(CH.sub.3NH.sub.3).sup.+], formamidinium [(HC(NH.sub.2).sub.2.sup.+], ethylammonium [(H.sub.5C.sub.2NH.sub.3).sup.+], butylammonium [(H.sub.9C.sub.4NH.sub.3).sup.+], and guanidinium [C(NH.sub.2).sub.3.sup.+].
3. The method of claim 1, wherein the dopant is selected from the group consisting of Sn.sup.2+, Cd.sup.2+, Zn.sup.2+, Mn.sup.2+, Sr.sup.2+, Ni.sup.2+, Fe.sup.2+, Mn.sup.2+, Zn.sup.2+, Ni.sup.2+, Sr.sup.2+, Ca.sup.2+, Sm.sup.2+, Eu.sup.2+, and Co.sup.2+ or from the group consisting of Eu.sup.3+, Bi.sup.3+, In.sup.3+, Yb.sup.3+, Ce.sup.3+, Er.sup.3+, Sm.sup.3+, Eu.sup.3+, Tb.sup.3+, and Dy.sup.3+.
4. The method of claim 1, wherein the B-site stock solution comprises a combination of Pb.sup.2+ and a dopant in a molar ratio of Pb.sup.2+ relative to dopant of from about 95:5 to about 50:50.
5. The method of claim 1, wherein the halide perovskite comprises the dopant in an atomic ratio of from about 1:10000 to about 1:100 relative to Pb.sup.2+.
6. The method of claim 1, wherein X, independently at each occurrence, is selected from Cl, Br, and I.
7. The method of claim 1, wherein X, independently at each occurrence, is selected from Cl and Br.
8. The method of claim 1, wherein the first non-polar solvent, second non-polar solvent, and third non-polar solvent are each independently selected from a C.sub.5-C.sub.10 hydrocarbon, or is a mixture thereof.
9. The method of claim 1, wherein the method is carried out at room temperature.
10. The method of claim 1, further comprising: contacting the first product mixture with a halide exchange solution; wherein the halide exchange solution comprises: a halide exchange reagent, the halide exchange reagent comprising an additional halide; and a fourth non-polar solvent; under conditions suitable to exchange at least one halide ion of the first halide perovskite with the additional halide; thereby forming a second product mixture comprising crystalline particles of a second halide perovskite, wherein the second halide perovskite has a chemical formula according to Formula (I), and further wherein, each occurrence of X is the same halide.
11. The method of claim 10, wherein the halide exchange reagent is selected from an oleylammonium halide and WCl.sub.6.
12. The method of claim 10, wherein the halide exchange reagent is selected from oleylammonium chloride, oleylammonium bromide, oleylammonium iodide and WCl.sub.6.
13. The method of claim 10, wherein the fourth non-polar solvent is independently selected from a C.sub.5-C.sub.10 hydrocarbon, or is a mixture thereof.
14. The method of claim 10, wherein the second product mixture comprises the A-site complexing agent, the B-site complexing agent, and the second halide perovskite; and the method further comprises: contacting the second product mixture with a ligand exchange solution, the ligand exchange solution comprising: at least one ligand; and a fifth non-polar solvent; under conditions suitable to exchange the A-site complexing agent and/or the B-site complexing agent with the at least one ligand, thereby forming a third product mixture comprising ligated crystalline particles of the second halide perovskite; wherein the ligated crystalline particles each have an outer surface, and each of the ligated crystalline particles further comprises at least one ligand bonded to the outer surface of the ligated crystalline particle.
15. The method of claim 14, wherein the at least one ligand is a molecule comprising at least one non-polar hydrocarbyl group and at least one zwitterionic group.
16. The method of claim 14, wherein the at least one ligand is selected from the group consisting of long chain sulfobetaines, phosphocholines, phospholipids, long-chain alkylamines, and long-chain alkylacids.
17. The method of claim 14, wherein the at least one ligand is lecithin.
18. The method of claim 14, wherein the fifth non-polar solvent is independently selected from a C.sub.5-C.sub.10 hydrocarbon, or is a mixture thereof.
19. The method of claim 14, wherein the method further comprises isolating the ligated crystalline particles from the third product mixture.
20. A composition comprising ligated crystalline particles of a halide perovskite obtained according to the method of claim 19 having an edge length of less than about 9 nm.
21. A perovskite-based device comprising ligated crystalline particles of a halide perovskite obtained according to the method of claim 19 and being selected from an optoelectronic device, a photoelectrochemical device, a sensor, a nanoscale magnet and a quantum material-based spintronic device.
22. The perovskite-based device according to claim 21, wherein the ligated crystalline particles of a halide perovskite have an edge length of less than about 9 nm.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0065] Interesting magneto-optical properties have been observed in other semiconductor nanocrystal systems (e.g., ZnSc or CdSc quantum dots) doped with Mn, but only when the nanocrystals are very small (quantum confined), e.g., from about 3 to about 7 nm edge length in halide perovskite nanocrystals (HP NCs). Smaller, more quantum confined perovskite nanocrystals doped with Mn could be crucial for the control of electron spin, useful for spintronics.
[0066] Typical Mn-doped perovskite nanocrystals are too large to see unique magneto-optical effects that are observed in other nanocrystal material classes, due to the synthetic limitations imposed by traditional hot synthesis methods. Taking the widely studied CsPbBr.sub.3 as an example, undoped CsPbBr.sub.3 NCs are formed upon the injection of Cs-oleate into a PbBr.sub.2 precursor containing oleylamine and oleic acid ligands. In this case, the reaction occurs to completion within seconds, meaning that NC nucleation and growth processes cannot be significantly separated temporally. Therefore, only temperature can be used as a handle to modify NC size using hot injection approaches, and narrow size dispersions are difficult to obtain without post-synthetic separation methods.
[0067] Recently, a new synthesis approach of HP NCs has been achieved using a complexation agent or complexing agent, trioctylphosphine oxide (TOPO) to weakly bind to the reaction precursors, i.e. the mixture of halide salts PbBr.sub.2 and Cs.sub.2CO.sub.3, resulting in a slower reaction that yielded monodisperse HP NCs, whose size is tunable from 3 to 13 nm in edge length. Importantly, this synthetic approach can occur at room temperature, and contains multiple convenient handles to control the NC size, and therefore quantum confinement. In short, this NC synthesis route occurs according to the equilibrium shown in eq II. Cs.sup.+ cations are introduced into the reaction mixture in the form of a Cs-diisooctylphosphinate (DOPA) complex, which reacts with the PbBr.sub.2-TOPO complex to form a Cs.sup.+/haloplumbate PbBr.sub.3.sup. intermediate ion pair. This Cs[PbBr.sub.3] serves as a monomer species, resulting in the formation and subsequent growth of CsPbBr.sub.3 NCs. All perovskite NCs produced by this synthetic approach are undoped HP NCs.
[0068] As this reaction mechanism occurs in the order of minutes rather than seconds, size can be controlled temporally, in contrast to hot injection methods. Further, as guided by the reaction equilibrium, the concentration of TOPO in the solution is a convenient handle to control the size of the resultant CsPbBr.sub.3 NCs, as a higher TOPO concentration shifts the equilibrium balance toward the reactants, as it limits the formation of Cs[PbBr.sub.3] monomer species, resulting in larger NCs being formed.
[0069] While this method is successful in synthesizing pristine, undoped HP NCs, there is currently a large, outstanding gap of work where small size pure doped HP NCs can be successfully synthesized. Despite the appealing optical properties of HP NCs as described previously, HP NCs face issues due to their low stability in ambient conditions. Strongly confined HP NCs cannot be synthesized by simply lowering the temperature; mixtures of cubic NCs and nanoplatelets can be observed. Confined undoped NCs have been reported and obtained either directly through precursors modification or through post-synthetic purification processes. Doping or alloying the B-site cation in HP NCs could also help to mediate this issue, as the stability could be increased due to more favorable lattice parameters. Further, the doping of semiconductor HP NCs can modulate the electronic, optical, and magnetic properties of the resultant NCs. Mn.sup.2+ is commonly the workhorse dopant in semiconductor NCs, due in part to its five unpaired d-electrons, which can impart interesting magneto-optical properties in confined HP NCs, most notably in II-VI HP NCs. Beyond these magneto-optical effects, Mn-doped HP NCs feature emission from a Mn.sup.2+ spin-forbidden transition (.sup.4T.sub.1.fwdarw..sup.6A.sub.1) upon energy transfer from the host NC. Interestingly, despite the additional decay pathway of Mn emission in Mn-doped CsPbCl.sub.3 NCs, the PL QY of the HP band-edge emission increased upon Mn-doping. This phenomenon has been recently explained by dopant-induced charge carrier localization effects, which concomitantly enhances the radiative recombination rate, potentially paving the way for more efficient blue-emitting LEDs.
[0070] However, there is no generalizable synthesis method of doped HP NCs that allows for the same size control and NC monodispersity as their undoped counterparts. Thus, dopant effects on the electronic properties of the host NC cannot be disentangled from quantum confinement effects.
[0071] The methods and compositions of the present disclosure meet the existing need in synthesizing small, size pure doped HP NCs, since the methods of the present disclosure result in size-tunable HP NCs doped with highly controlled dopant concentrations of various metals, working under ambient conditions at room temperature. The methods of the present disclosure are simple, scalable, and may be performed at room temperature.
Methods of Preparing Crystalline Halide Perovskite Particles
[0072] In particular embodiments, the methods provide herein can dope HP NCs from 5-10 nm in size, i.e. edge length with Mn, Ni, and Zn. This is notable, as interesting magneto-optical properties of Mn-doped NCs have only been able to be unlocked in very small, quantum confined nanocrystals. In certain embodiments, MnCl.sub.2 is added to the reaction mixture, resulting in Mn-doped HP NCs with varied halide content, depending on the ratio of PbBr.sub.2 to MnCl.sub.2 in the precursor solution or the B-site stock solution. In certain such embodiments, the final halide composition of the Mn-doped HP NCs synthesized using this synthetic approach may be adjusted with a halide exchange reagent. In some embodiments, this is done by adding 1 mL of a 10 mg/mL oleylammonium chloride solution, resulting in CsPb.sub.xMn.sub.1-xCl.sub.3 NCs being a particular second halide perovskite of the present disclosure having, at each occurrence, a halide X selected from Cl, said particular second halide perovskite being doped by Mn. According to existing methods, ZnCl.sub.2 is used to exchange halide in CsPbBr.sub.3 HP NCs. However, divalent metal salts used as halide exchange agents are known for uncontrolled cation exchange in B-site of non-doped HP NCs. To avoid displacing Pb or other divalent dopants present in doped HP NCs, organic cations paired with halide or large metal salts with higher valencies are preferably used as halide exchange reagents in the methods of this disclosure.
[0073] The absorption and photoluminescence (PL) emission of differently sized NCs, doped with various amounts of Mn were measured, where the absorption and emission both redshift with increasing size, in accordance with the quantum confinement effect. The blueshift of absorption and emission is evidence of Mn incorporation, along with a strong spin-forbidden Mn emission, centered at 600 nm as illustrated in
[0074] Further, using transmission electron microscopy (TEM), it was determined that the size corresponding to the edge length of the HP NCs does not change significantly upon Mn-doping, even in the smaller NCs. Representative pristine and Mn-doped CsPbCl.sub.3 NCs are shown in the TEM micrographs in
[0075] Additionally, the doping approaches provided herein can be generalized to used other metal as dopants. For example, Zn and Ni were successfully used as dopants in the methods described herein to dope HP NCs. Upon the addition of Zn and Ni into the HP NCs, characteristic blue shifting of the perovskite excitonic absorption is observed such as illustrated in
[0076] In certain embodiments, a complexing agent selected from a molecule comprising at least one non-polar hydrocarbyl group and at least one polar group is added to the combination of the A-site stock solution with the B-site stock solution. Said complexing agent may be selected from the group consisting of long-chain alkylsulfobetaines, phosphocholines, phospholipids, long-chain alkylamines, and long-chain alkylacids. In some embodiments, said complexing agent is selected from trioctylphosphine oxide (TOPO), diisooctylphosphinate (DOPA), oleylamine (OAm), and oleic acid (OA). In preferred embodiments, the complexing agent is a B-site complexing agent. The complexing agent is selected from trioctylphosphine oxide (TOPO).
[0077] In certain embodiments, methods of the disclosure further comprise: [0078] contacting the first product mixture with a halide exchange solution; [0079] wherein the halide exchange solution comprises: [0080] a halide exchange reagent, the halide exchange reagent comprising an additional halide; and [0081] a fourth non-polar solvent; [0082] under conditions suitable to exchange at least one halide ion of the first halide perovskite with the additional halide; [0083] thereby forming a second product mixture comprising crystalline particles of a second halide perovskite, wherein the second halide perovskite has a chemical formula according to Formula (I), and further wherein each X is the same.
[0084] In some embodiments, the halide exchange reagent is selected from a halide salt. The halide salt is selected from an inorganic halide and an organic halide. The halide salt for the halide exchange solution is selected to have the same halide at each occurrence of X. In certain embodiments, the halide exchange reagent is an oleylammonium halide and WCl.sub.6 or a combination thereof, when halide is Cl. In certain preferred embodiments, the halide exchange reagent is selected from oleylammonium chloride, oleylammonium bromide, oleylammonium iodide, and WCl.sub.6.
[0085] In certain embodiments, each occurrence of X is Cl, Br or I after submitting the first halide perovskite of the disclosure to the step of the halide exchange. In some preferred embodiments, each occurrence of X is Br or Cl. In certain embodiments, each occurrence of X is I.
[0086] In certain embodiments, the second product mixture comprises the A-site complexing agent, the B-site complexing agent, and the second halide perovskite; and the method further comprises: [0087] contacting the second product mixture with a ligand exchange solution, the ligand exchange solution comprising: [0088] at least one ligand; and [0089] a fifth non-polar solvent; [0090] under conditions suitable to exchange the A-site complexing agent and/or the B-site complexing agent with the at least one ligand, thereby forming a third product mixture comprising ligated crystalline particles of the second halide perovskite; [0091] wherein the ligated crystalline particles each have an outer surface, and each of the ligated crystalline particles further comprises at least one ligand bonded to the outer surface of the ligated crystalline particle.
[0092] In some embodiments, the A-site complexing agent and the B-site complexing agent are each, independently, selected from a molecule comprising at least one non-polar hydrocarbyl group and at least one polar group. Said A-site and/or B-site complexing agents are selected from chemical compounds enabling the formation of complexes with the cation and/or the anion of the A and/or B elements in the synthesis methods of the disclosure. the A-site complexing agent and the B-site complexing agent are each, independently, selected from coordinating agent a compound having at least one non-polar hydrocarbyl group and at least one polar group. In certain embodiments, the A-site complexing agents and B-site complexing agents are independently selected from trioctylphosphine oxide (TOPO), diisooctylphosphinate (DOPA), oleylamine (OAm), and oleic acid (OA). They may bind to the outer surface of the crystalline particles in the first and/or second product mixture, wherein the halide is or is not exchanged. They may also be present on the outer surface to the crystalline particles of the third product mixture and/or they may be partially exchanged for at least one ligand. They are present on the outer surface of the crystalline particles of the product mixture before to be exchanged by a ligand being a compound having at least one non-polar hydrocarbyl group and at least one zwitterionic group.
[0093] In certain embodiments, the method further comprises isolating the ligated crystalline particles from the third product mixture.
[0094] In some embodiments, the at least one ligand is a molecule comprising at least one non-polar hydrocarbyl group and at least one zwitterionic group.
[0095] In certain embodiments, the at least one ligand is selected from the group consisting of long chain sulfobetaines, phosphocholines, phospholipids, long-chain alkylamines, and long-chain alkylacids. In certain preferred embodiments, the at least one ligand is lecithin.
[0096] In some embodiments, the first non-polar solvent, second non-polar solvent, third non-polar solvent, fourth non-polar solvent, and fifth non-polar solvent are each independently selected from a C.sub.5-C.sub.10 hydrocarbon, or is a mixture thereof. In certain preferred embodiments, the first non-polar solvent, second non-polar solvent, third non-polar solvent, fourth non-polar solvent, and fifth non-polar solvent are each independently selected from pentanes, petroleum ether, hexanes, heptanes, octanes, toluene, and xylene, or a mixture thereof.
[0097] In certain embodiments, each of the first non-polar solvent, second non-polar solvent, third non-polar solvent, fourth non-polar solvent, and fifth non-polar solvent are the same.
[0098] In some embodiments, each of the first non-polar solvent, second non-polar solvent, third non-polar solvent, fourth non-polar solvent, and fifth non-polar solvent are different.
Compositions Comprising Crystalline Particles of a Halide Perovskite
[0099] In certain embodiments, provided herein are compositions, comprising crystalline particles of a halide perovskite, the halide perovskite having a chemical formula according to Formula I:
ABX.sub.3(I); [0100] wherein: [0101] A is a monocation; [0102] B is selected from Pb.sup.2+, a dopant and a combination thereof; [0103] X, independently at each occurrence, is a halide; [0104] wherein the dopant is a dication or trication of a metallic element; and [0105] further wherein the crystalline particles have an edge length distribution characterized by a d(0.9) of less than about 8.5 nm.
[0106] d(0.9) corresponds to a point along a distribution curve of the NCs sizes that fall below 90%. For example, d(0.9) of less than about 8.5 nm is defined as the point on a distribution curve of the measured edge lengths of the HP NCs on TEM images which 90% of the particles have an edge length of less than about 8.5 nm.
[0107] In another aspect, the invention provides a composition comprising ligated crystalline particles of a halide perovskite obtained according to the methods of the disclosure and having an edge length of less than about 9 nm. In some embodiments, the edge length of the crystalline particles is in the range from about 2 nm to about 10 nm, preferably from about 3 nm to 9 nm.
[0108] As will be appreciated by one of ordinary skill in the art, the identities of A, B, and X, are defined in part by size limitations of the perovskite structure. For example, halide perovskites, i.e. metal doped HP NCs, described herein may have a Goldschmidt tolerance factor (t) of about 1 as calculated by formula (III):
[0109] wherein r.sub.A is the ionic radius of A, r.sub.B is the atomic radius of B, and r.sub.X is the atomic radius of X. Accordingly, suitable combinations of A, B, and X, as defined herein, will be apparent to one of skill in the art upon reading this disclosure.
[0110] In certain embodiments, A is a monocation of a metallic element or a monocationic organic group. In some embodiments, A is a monocation of a metallic element selected from Group 1 of the periodic table. In further embodiments, A is selected from Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, and Cs.sup.+. In certain preferred embodiments, A is Cs.sup.+.
[0111] In some embodiments, A is a monocationic organic group. In certain such embodiments, A is selected from methylammonium [(CH.sub.3NH.sub.3).sup.+], formamidinium [(HC(NH.sub.2).sub.2.sup.+], ethylammonium [(H.sub.5C.sub.2NH.sub.3).sup.+], butylammonium [(H.sub.9C.sub.4NH.sub.3).sup.+], and guanidinium [C(NH.sub.2).sub.3.sup.+]. In certain preferred embodiments, A is methylammonium [(CH.sub.3NH.sub.3).sup.+] or formamidinium [(HC(NH.sub.2).sub.2.sup.+].
[0112] In certain embodiments, the dopant is a dication of a metallic element. In further embodiments, the dopant is a dication of a metallic element selected from Group 2, Group 3, Group 7, Group 8, Group 9, Group 10, Group 12, and Group 14 of the periodic table. In yet further embodiments, the dopant is selected from Sn.sup.2+, Cd.sup.2+, Zn.sup.2+, Mn.sup.2+, Sr.sup.2+, Ni.sup.2+, Fe.sup.2+, Mn.sup.2+, Zn.sup.2+, Ni.sup.2+, Sr.sup.2+, Ca.sup.2+, Sm.sup.2+, Eu.sup.2+, and Co.sup.2+. In certain preferred embodiments, the dopant is Mn.sup.2+. In other preferred embodiments, the dopant is Zn.sup.2+. In some preferred embodiments, the dopant is Ni.sup.2+.
[0113] In certain embodiments, the dopant is a trication of a metallic element. In further embodiments, the dopant is a trication of a metallic element selected from Group 2, Group 3, Group 8, Group 9, Group 13, and Group 15. In yet further embodiments, the dopant is selected from Eu.sup.3+, Bi.sup.3+, In.sup.3+, Yb.sup.3+, Ce.sup.3+, Er.sup.3+, Sm.sup.3+, Eu.sup.3+, Th.sup.3+, and Dy.sup.3+.
[0114] In certain embodiments, the halide perovskite comprises the dopant in an atomic ratio of from about 1:10000 to about 1:100 relative to Pb.sup.2+. In example embodiments, the halide perovskite comprises the dopant in an atomic ratio of about 1:10000, about 2:10000, about 3:10000, about 4:10000, about 5:10000, about 6:10000, about 7:10000, about 8:10000, about 9:10000, or about 1:1000. In other example embodiments, the halide perovskite comprises the dopant in an atomic ratio of about 1:1000, about 2:1000, about 3:1000, about 4:1000, about 5:1000, about 6:1000, about 7:1000, about 8:1000, about 9:1000, or about 1:100.
[0115] In certain embodiments, the edge length distribution is characterized by a d(0.9) of about 5.5 nm to about 8 nm. In some embodiments, the edge length distribution is characterized by a d(0.9) of about 8 nm. In certain embodiments, the edge length distribution is characterized by a d(0.9) of about 7.5 nm. In some embodiments, the edge length distribution is characterized by a d(0.9) of about 6.5 nm. In certain preferred embodiments, the edge length distribution is characterized by a d(0.9) of about 6 nm.
[0116] In certain embodiments, the crystalline particles each has an outer surface, at least one crystalline particle further comprises at least one ligand bonded to the outer surface of the at least one crystalline particle. In further embodiments, the at least one ligand is a molecule comprising at least one non-polar hydrocarbyl group and at least one polar group. In yet further embodiments, the at least one ligand is selected from the group consisting of long-chain alkylsulfobetaines, phosphocholines, phospholipids, long-chain alkylamines, and long-chain alkylacids. In some embodiments, the at least one ligand is selected from trioctylphosphine oxide (TOPO), lecithin, oleylamine (OAm), and oleic acid (OA). In preferred embodiments, the at least one ligand is lecithin.
[0117] Metal doped HP NCs of this disclosure are promising materials for optoelectronic applications. Metal doping improves the performance of such crystalline particles of the disclosure, e.g., by enhancing light emission, or to provide additional functionalities, such as nanoscale magnetism and polarization control.
[0118] In a further aspect, the invention proposes a perovskite-based device comprising ligated crystalline particles of a halide perovskite obtained according to the methods of the disclosures and being selected from an optoelectronic device, a photoelectrochemical device, a sensor, a nanoscale magnet and a quantum material-based spintronic device.
[0119] In certain embodiments, the perovskite-based device comprises the ligated crystalline particles of a halide perovskite having an edge length of less than about 9 nm.
[0120] The disclosure provides a generalizable synthesis method for metal-doped halide perovskite NCs, which enables full size- and composition tunability, which is scalable and operates under ambient conditions at room temperature. This method allows the incorporation of metal dopants into the lattice during synthesis, and for unprecedented synthetic control across multiple NC sizes and dopant level regimes. This synthetic method for doping HP NCs will provide additional leverage to further shift the bandgap while maintaining stability. Importantly, controlled metal doping can also enable new functionalities, such as magnetic exchange interactions in the case of magnetic dopants, for unexplored applications in spin-photonic interfaces and quantum information processing, or improving device performance in the deep blue to UV spectral range for the technical fields of light-emitting diodes (LEDs) and water disinfection.
Definitions
[0121] Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry, cell and tissue culture, molecular biology, cell and cancer biology, neurobiology, neurochemistry, virology, immunology, microbiology, pharmacology, genetics and protein and nucleic acid chemistry, described herein, are those well known and commonly used in the art.
[0122] Definitions of specific functional groups and chemical terms are described in more detail below. The chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75.sup.th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March, March's Advanced Organic Chemistry, 5.sup.th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; and Carruthers, Some Modern Methods of Organic Synthesis, 3.sup.rd Edition, Cambridge University Press, Cambridge, 1987.
[0123] When a range of values is listed, it is intended to encompass each value and sub-range within the range. For example, C.sub.1-6 alkyl is intended to encompass C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5, C.sub.6, C.sub.1-6, C.sub.1-5, C.sub.1-4, C.sub.1-3, C.sub.1-2, C.sub.2-6, C.sub.2-5, C.sub.2-4, C.sub.2-3, C.sub.3-6, C.sub.3-5, C.sub.3-4, C.sub.4-6, C.sub.4-5, and C.sub.5-6 alkyl.
[0124] The term aliphatic refers to alkyl, alkenyl, alkynyl, and carbocyclic groups. Likewise, the term heteroaliphatic refers to heteroalkyl, heteroalkenyl, heteroalkynyl, and heterocyclic groups.
[0125] The term hydrocarbyl as used herein refers to an alkyl or alkenyl group.
[0126] The term alkyl as used herein refers to a radical of a straight-chain or branched saturated hydrocarbon group having from 1 to 10 carbon atoms (C.sub.1-10 alkyl). In some embodiments, an alkyl group has 1 to 9 carbon atoms (C.sub.1-9 alkyl). In some embodiments, an alkyl group has 1 to 8 carbon atoms (C.sub.1-8 alkyl). In some embodiments, an alkyl group has 1 to 7 carbon atoms (C.sub.1-7 alkyl). In some embodiments, an alkyl group has 1 to 6 carbon atoms (C.sub.1-6 alkyl). In some embodiments, an alkyl group has 1 to 5 carbon atoms (C.sub.1-5 alkyl). In some embodiments, an alkyl group has 1 to 4 carbon atoms (C.sub.1-4 alkyl). In some embodiments, an alkyl group has 1 to 3 carbon atoms (C.sub.1-3 alkyl). In some embodiments, an alkyl group has 1 to 2 carbon atoms (C.sub.1-2 alkyl). In some embodiments, an alkyl group has 1 carbon atom (C.sub.1 alkyl). In some embodiments, an alkyl group has 2 to 6 carbon atoms (C.sub.2-6 alkyl). Examples of C.sub.1-6 alkyl groups include methyl (C.sub.1), ethyl (C.sub.2), propyl (C.sub.3) (e.g., n-propyl, isopropyl), butyl (C.sub.4) (e.g., n-butyl, tert-butyl, sec-butyl, iso-butyl), pentyl (C.sub.5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tertiary amyl), and hexyl (C.sub.6) (e.g., n-hexyl). Additional examples of alkyl groups include n-heptyl (C.sub.7), n-octyl (C.sub.8), and the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted (an unsubstituted alkyl) or substituted (a substituted alkyl) with one or more substituents (e.g., halogen, such as F). In certain embodiments, the alkyl group is an unsubstituted C.sub.1-10 alkyl (such as unsubstituted C.sub.1-6 alkyl, e.g., CH.sub.3 (Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, e.g., unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), unsubstituted butyl (Bu, e.g., unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu), unsubstituted isobutyl (i-Bu)). In certain embodiments, the alkyl group is a substituted C.sub.1-10 alkyl (such as substituted C.sub.1-6 alkyl, e.g., CF.sub.3, Bn).
[0127] The term polar group as used herein refers to an organic functional group or molecule, which may be overall neutral or charged, and which carries a net dipole moment. As a non-limiting example, a polar group may refer to optionally substituted groups selected from: phosphate, phosphate diester, amine, ammonium, alkoxy, carboxylate, aldehyde, or a zwitterionic group (a functional group comprising a positively charged site and a negatively charged site) comprising, e.g., a positively charged ammonium group and a negatively charged phosphate or carboxylate group. Non-limiting examples of molecules comprising polar groups include trioctylphosphine oxide (TOPO), diisooctylphosphinate (DOPA), lecithin, oleylamine (OAm), and oleic acid (OA).
[0128] The term hydroxyalkyl is a substituted alkyl group, wherein one or more of the hydrogen atoms are independently replaced by a hydroxyl. In some embodiments, the hydroxyalkyl moiety has 1 to 8 carbon atoms (C.sub.1-8 hydroxyalkyl). In some embodiments, the hydroxyalkyl moiety has 1 to 6 carbon atoms (C.sub.1-6 hydroxyalkyl). In some embodiments, the hydroxyalkyl moiety has 1 to 4 carbon atoms (C.sub.1-4 hydroxyalkyl). In some embodiments, the hydroxyalkyl moiety has 1 to 3 carbon atoms (C.sub.1-3 hydroxyalkyl). In some embodiments, the hydroxyalkyl moiety has 1 to 2 carbon atoms (C.sub.1-2 hydroxyalkyl).
[0129] The term alkoxy refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. In some embodiments, the alkoxy moiety has 1 to 8 carbon atoms (C.sub.1-8 alkoxy). In some embodiments, the alkoxy moiety has 1 to 6 carbon atoms (C.sub.1-6 alkoxy). In some embodiments, the alkoxy moiety has 1 to 4 carbon atoms (C.sub.1-4 alkoxy). In some embodiments, the alkoxy moiety has 1 to 3 carbon atoms (C.sub.1-3 alkoxy). In some embodiments, the alkoxy moiety has 1 to 2 carbon atoms (C.sub.1-2 alkoxy). Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy and tert-butoxy.
[0130] The term alkoxyalkyl is a substituted alkyl group, wherein one or more of the hydrogen atoms are independently replaced by an alkoxy group, as defined herein. In some embodiments, the alkoxyalkyl moiety has 1 to 8 carbon atoms (C.sub.1-8 alkoxyalkyl). In some embodiments, the alkoxyalkyl moiety has 1 to 6 carbon atoms (C.sub.1-6 alkoxyalkyl). In some embodiments, the alkoxyalkyl moiety has 1 to 4 carbon atoms (C.sub.1-4 alkoxyalkyl). In some embodiments, the alkoxyalkyl moiety has 1 to 3 carbon atoms (C.sub.1-3 alkoxyalkyl). In some embodiments, the alkoxyalkyl moiety has 1 to 2 carbon atoms (C.sub.1-2 alkoxyalkyl).
[0131] The term heteroalkyl refers to an alkyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (i.e., inserted between adjacent carbon atoms of) and/or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkyl group refers to a saturated group having from 1 to 20 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-20 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 18 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-18 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 16 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-16 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 14 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-14 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 12 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-12 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 10 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-10 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 8 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-8 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 6 carbon atoms and 1 or more heteroatoms within the parent chain (heteroC.sub.1-6 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 4 carbon atoms and 1 or 2 heteroatoms within the parent chain (heteroC.sub.1-4 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 3 carbon atoms and 1 heteroatom within the parent chain (heteroC.sub.1-3 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 to 2 carbon atoms and 1 heteroatom within the parent chain (heteroC.sub.1-2 alkyl). In some embodiments, a heteroalkyl group is a saturated group having 1 carbon atom and 1 heteroatom (heteroC.sub.1 alkyl). In some embodiments, the heteroalkyl group defined herein is a partially unsaturated group having 1 or more heteroatoms within the parent chain and at least one unsaturated carbon, such as a carbonyl group. For example, a heteroalkyl group may comprise an amide or ester functionality in its parent chain such that one or more carbon atoms are unsaturated carbonyl groups. Unless otherwise specified, each instance of a heteroalkyl group is independently unsubstituted (an unsubstituted heteroalkyl) or substituted (a substituted heteroalkyl) with one or more substituents. In certain embodiments, the heteroalkyl group is an unsubstituted heteroC.sub.1-20 alkyl. In certain embodiments, the heteroalkyl group is an unsubstituted heteroC.sub.1-10 alkyl. In certain embodiments, the heteroalkyl group is a substituted heteroC.sub.1-20 alkyl. In certain embodiments, the heteroalkyl group is an unsubstituted heteroC.sub.1-10 alkyl.
[0132] The term alkenyl refers to a radical of a straight-chain or branched hydrocarbon group having from 2 to 10 carbon atoms and one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 double bonds). In some embodiments, an alkenyl group has 2 to 9 carbon atoms (C.sub.2-9 alkenyl). In some embodiments, an alkenyl group has 2 to 8 carbon atoms (C.sub.2-8 alkenyl). In some embodiments, an alkenyl group has 2 to 7 carbon atoms (C.sub.2-7 alkenyl). In some embodiments, an alkenyl group has 2 to 6 carbon atoms (C.sub.2-6 alkenyl). In some embodiments, an alkenyl group has 2 to 5 carbon atoms (C.sub.2-5 alkenyl). In some embodiments, an alkenyl group has 2 to 4 carbon atoms (C.sub.2-4 alkenyl). In some embodiments, an alkenyl group has 2 to 3 carbon atoms (C.sub.2-3 alkenyl). In some embodiments, an alkenyl group has 2 carbon atoms (C.sub.2 alkenyl). The one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl). Examples of C.sub.2-4 alkenyl groups include ethenyl (C.sub.2), 1-propenyl (C.sub.3), 2-propenyl (C.sub.3), 1-butenyl (C.sub.4), 2-butenyl (C.sub.4), butadienyl (C.sub.4), and the like. Examples of C.sub.2-6 alkenyl groups include the aforementioned C.sub.2-4 alkenyl groups as well as pentenyl (C.sub.5), pentadienyl (C.sub.5), hexenyl (C.sub.6), and the like. Additional examples of alkenyl include heptenyl (C.sub.7), octenyl (C.sub.8), octatrienyl (C.sub.8), and the like. Unless otherwise specified, each instance of an alkenyl group is independently unsubstituted (an unsubstituted alkenyl) or substituted (a substituted alkenyl) with one or more substituents. In certain embodiments, the alkenyl group is an unsubstituted C.sub.2-10 alkenyl. In certain embodiments, the alkenyl group is a substituted C.sub.2-10 alkenyl. In an alkenyl group, a CC double bond for which the stereochemistry is not specified
##STR00001##
may be an (E)- or (Z)-double bond.
[0133] The term heteroalkenyl refers to an alkenyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (i.e., inserted between adjacent carbon atoms of) and/or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkenyl group refers to a group having from 2 to 10 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-10 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 9 carbon atoms at least one double bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-9 alkenyl).
[0134] In some embodiments, a heteroalkenyl group has 2 to 8 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-8 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 7 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-7 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 6 carbon atoms, at least one double bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-6 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 5 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-5 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 4 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-4 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 3 carbon atoms, at least one double bond, and 1 heteroatom within the parent chain (heteroC.sub.2-3 alkenyl). In some embodiments, a heteroalkenyl group has 2 to 6 carbon atoms, at least one double bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-6 alkenyl). Unless otherwise specified, each instance of a heteroalkenyl group is independently unsubstituted (an unsubstituted heteroalkenyl) or substituted (a substituted heteroalkenyl) with one or more substituents. In certain embodiments, the heteroalkenyl group is an unsubstituted heteroC.sub.2-10 alkenyl. In certain embodiments, the heteroalkenyl group is a substituted heteroC.sub.2-10 alkenyl.
[0135] The term alkynyl refers to a radical of a straight-chain or branched hydrocarbon group having from 2 to 10 carbon atoms and one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 triple bonds) (C2_10 alkynyl). In some embodiments, an alkynyl group has 2 to 9 carbon atoms (C.sub.2-9 alkynyl). In some embodiments, an alkynyl group has 2 to 8 carbon atoms (C.sub.2-8 alkynyl). In some embodiments, an alkynyl group has 2 to 7 carbon atoms (C.sub.2-7 alkynyl). In some embodiments, an alkynyl group has 2 to 6 carbon atoms (C.sub.2-6 alkynyl). In some embodiments, an alkynyl group has 2 to 5 carbon atoms (C.sub.2-5 alkynyl). In some embodiments, an alkynyl group has 2 to 4 carbon atoms (C.sub.2-4 alkynyl). In some embodiments, an alkynyl group has 2 to 3 carbon atoms (C.sub.2-3 alkynyl). In some embodiments, an alkynyl group has 2 carbon atoms (C.sub.2 alkynyl). The one or more carbon-carbon triple bonds can be internal (such as in 2-butynyl) or terminal (such as in 1-butynyl). Examples of C.sub.2_4 alkynyl groups include, without limitation, ethynyl (C.sub.2), 1-propynyl (C.sub.3), 2-propynyl (C.sub.3), 1-butynyl (C.sub.4), 2-butynyl (C.sub.4), and the like. Examples of C.sub.2-6 alkenyl groups include the aforementioned C.sub.2-4 alkynyl groups as well as pentynyl (C.sub.5), hexynyl (C.sub.6), and the like. Additional examples of alkynyl include heptynyl (C.sub.7), octynyl (C.sub.8), and the like. Unless otherwise specified, each instance of an alkynyl group is independently unsubstituted (an unsubstituted alkynyl) or substituted (a substituted alkynyl) with one or more substituents. In certain embodiments, the alkynyl group is an unsubstituted C.sub.2-10 alkynyl. In certain embodiments, the alkynyl group is a substituted C.sub.2-10 alkynyl.
[0136] The term heteroalkynyl refers to an alkynyl group, which further includes at least one heteroatom (e.g., 1, 2, 3, or 4 heteroatoms) selected from oxygen, nitrogen, or sulfur within (i.e., inserted between adjacent carbon atoms of) and/or placed at one or more terminal position(s) of the parent chain. In certain embodiments, a heteroalkynyl group refers to a group having from 2 to 10 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-10 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 9 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-9 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 8 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-8 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 7 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-7 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 6 carbon atoms, at least one triple bond, and 1 or more heteroatoms within the parent chain (heteroC.sub.2-6 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 5 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-5 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 4 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-4 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 3 carbon atoms, at least one triple bond, and 1 heteroatom within the parent chain (heteroC.sub.2-3 alkynyl). In some embodiments, a heteroalkynyl group has 2 to 6 carbon atoms, at least one triple bond, and 1 or 2 heteroatoms within the parent chain (heteroC.sub.2-6 alkynyl). Unless otherwise specified, each instance of a heteroalkynyl group is independently unsubstituted (an unsubstituted heteroalkynyl) or substituted (a substituted heteroalkynyl) with one or more substituents. In certain embodiments, the heteroalkynyl group is an unsubstituted heteroC.sub.2-10 alkynyl. In certain embodiments, the heteroalkynyl group is a substituted heteroC.sub.2-10 alkynyl.
[0137] The term unsaturated bond refers to a double or triple bond.
[0138] The term unsaturated or partially unsaturated refers to a moiety that includes at least one double or triple bond.
[0139] The term saturated refers to a moiety that does not contain a double or triple bond, i.e., the moiety only contains single bonds.
[0140] Affixing the suffix -ene to a group indicates the group is a divalent moiety, e.g., alkylene is the divalent moiety of alkyl, alkenylene is the divalent moiety of alkenyl, alkynylene is the divalent moiety of alkynyl, heteroalkylene is the divalent moiety of heteroalkyl, heteroalkenylene is the divalent moiety of heteroalkenyl, heteroalkynylene is the divalent moiety of heteroalkynyl, carbocyclylene is the divalent moiety of carbocyclyl, heterocyclylene is the divalent moiety of heterocyclyl, arylene is the divalent moiety of aryl, and heteroarylene is the divalent moiety of heteroaryl.
[0141] A group is optionally substituted unless expressly provided otherwise. The term optionally substituted refers to being substituted or unsubstituted. In certain embodiments, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl groups are optionally substituted. Optionally substituted refers to a group which may be substituted or unsubstituted (e.g., substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heteroalkenyl, substituted or unsubstituted heteroalkynyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl group). In general, the term substituted means that at least one hydrogen present on a group is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction. Unless otherwise indicated, a substituted group has a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position. The term substituted is contemplated to include substitution with all permissible substituents of organic compounds, and includes any of the substituents described herein that results in the formation of a stable compound. The present invention contemplates any and all such combinations in order to arrive at a stable compound. For purposes of this invention, heteroatoms such as nitrogen may have hydrogen substituents and/or any suitable substituent as described herein which satisfy the valencies of the heteroatoms and results in the formation of a stable moiety. The invention is not intended to be limited in any manner by the exemplary substituents described herein.
[0142] Exemplary carbon atom substituents include, but are not limited to, halogen, CN, NO.sub.2, N.sub.3, SO.sub.2H, SO.sub.3H, OH, OR.sup.aa, ON(R.sup.bb).sub.2, N(R.sup.bb).sub.2, N(R.sup.bb).sub.3.sup.+X.sup., N(OR)R.sup.bb, SH, SR.sup.aa, SSR.sup.cc, C(O)R.sup.aa, CO.sub.2H, CHO, C(OR).sub.3, CO.sub.2R.sup.aa, OC(O)R.sup.aa, OCO.sub.2R.sup.aa, C(O)N(R.sup.bb).sub.2, OC(O)N(R.sup.bb).sub.2, NR.sup.bbC(O)R.sup.aa, NR.sup.bbCO.sub.2R.sup.aa, NR.sup.bbC(O)N(R.sup.bb).sub.2, C(NR.sup.bb)R.sup.aa, C(NR.sup.bb)OR.sup.aa, OC(NR.sup.bb)R.sup.aa, OC(NR.sup.bb)OR.sup.aa, C(NR.sup.bb)N(R.sup.bb).sub.2, OC(NR.sup.bb)N(R.sup.bb).sub.2, NR.sup.bbC(NR.sup.bb)N(R.sup.bb).sub.2, C(O)NR.sup.bbSO.sub.2R.sup.aa, NR.sup.bbSO.sub.2R.sup.aa, SO.sub.2N(R.sup.bb).sub.2, SO.sub.2R.sup.aa, SO.sub.2OR.sup.aa, OSOR.sup.aa, S(O)R.sup.aa, OS(O)R.sup.aa, Si(R.sup.aa).sub.3, OSi(R.sup.aa).sub.3, C(S)N(R.sup.bb).sub.2, C(O)SR.sup.aa, C(S)SR.sup.aa, SC(S)SR.sup.aa, SC(O)SR.sup.aa, OC(O)SR.sup.aa, SC(O)OR.sup.aa, SC(O)R.sup.aa, P(O)(R.sup.aa).sub.2, P(O)(OR.sup.cc).sub.2, OP(O)(R.sup.aa).sub.2, OP(O)(OR.sup.cc).sub.2, P(O)(N(R.sup.bb).sub.2).sub.2, OP(O)(N(R.sup.bb).sub.2).sub.2, NR.sup.bbP(O)(R.sup.aa).sub.2, NR.sup.bbP(O)(OR.sup.cc).sub.2, NR.sup.bbP(O)(N(R.sup.bb).sub.2).sub.2, P(R.sup.cc).sub.2, P(OR.sup.cc).sub.2, P(R.sup.cc).sub.3.sup.+X.sup., P(OR.sup.cc).sub.3.sup.+X.sup., P(R.sup.cc).sub.4, P(OR.sup.cc).sub.2, OP(R).sub.2, OP(R.sup.cc).sub.3.sup.+X.sup., OP(OR.sup.cc).sub.2, OP(OR.sup.cc).sub.3.sup.+X.sup., OP(R.sup.cc).sub.4, OP(OR.sup.cc).sub.4, B(R.sup.aa).sub.2, B(OR.sup.cc).sub.2, BR.sup.aa(OR.sup.cc), C.sub.1-10 alkyl, C.sub.1-10 perhaloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, heteroC.sub.1-10 alkyl, heteroC.sub.2-10 alkenyl, heteroC.sub.2-10 alkynyl, C.sub.3-10 carbocyclyl, 3-14 membered heterocyclyl, C.sub.6-14 aryl, and 5-14 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.dd groups; wherein X is a counterion; or two geminal hydrogens on a carbon atom are replaced with the group O, S, NN(R.sup.bb).sub.2, NNR.sup.bbC(O)R.sup.aa, NNR.sup.bbC(O)OR.sup.aa, NNR.sup.bbS(O).sub.2R.sup.aa, NR.sup.bb or NOR.sup.cc; each instance of R.sup.aa is, independently, selected from C.sub.1-10 alkyl, C.sub.1-10 perhaloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, heteroC.sub.1-10 alkyl, heteroC.sub.2-10 alkenyl, heteroC.sub.2-10 alkynyl, C.sub.3-10 carbocyclyl, 3-14 membered heterocyclyl, C.sub.6-14 aryl, and 5-14 membered heteroaryl, or two R.sup.aa groups are joined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.dd groups; each instance of R.sup.bb is, independently, selected from hydrogen, OH, OR.sup.aa, N(R).sub.2, CN, C(O)R.sup.aa, C(O)N(R).sub.2, CO.sub.2R.sup.aa, SO.sub.2R.sup.aa, C(NR.sup.cc)OR.sup.aa, C(NR.sup.cc)N(R).sub.2, SO.sub.2N(R).sub.2, SO.sub.2R.sup.aa, SO.sub.2OR.sup.cc, SOR.sup.aa, C(S)N(R).sub.2, C(O)SR.sup.cc, C(S)SR.sup.cc, P(O)(R.sup.aa).sub.2, P(O)(OR.sup.cc).sub.2, P(O)(N(R).sub.2).sub.2, C.sub.1-10 alkyl, C.sub.1-10 perhaloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, heteroC.sub.1-10 alkyl, heteroC.sub.2-10 alkenyl, heteroC.sub.2-10 alkynyl, C.sub.3-10 carbocyclyl, 3-14 membered heterocyclyl, C.sub.6-14 aryl, and 5-14 membered heteroaryl, or two R.sup.bb groups are joined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.dd groups; wherein X is a counterion; each instance of R.sup.cc is, independently, selected from hydrogen, C.sub.1-10 alkyl, C.sub.1-10 perhaloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, heteroC.sub.1-10 alkyl, heteroC.sub.2-10 alkenyl, heteroC.sub.2-10 alkynyl, C.sub.3-10 carbocyclyl, 3-14 membered heterocyclyl, C.sub.6-14 aryl, and 5-14 membered heteroaryl, or two Rec groups are joined to form a 3-14 membered heterocyclyl or 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.dd groups; each instance of R.sup.dd is, independently, selected from halogen, CN, NO.sub.2, N.sub.3, SO.sub.2H, SO.sub.3H, OH, OR.sup.ee, ON(R.sup.ff).sub.2, N(R.sup.ff).sub.2, N(R.sup.ff).sub.3.sup.+X.sup., N(OR)R.sup.ff, SH, SR.sup.ee, SSR.sup.ee, C(O)R.sup.ee, CO.sub.2H, CO.sub.2R.sup.ee, OC(O)R.sup.ee, OCO.sub.2R.sup.ee, C(O)N(R.sup.ff).sub.2, OC(O)N(R.sup.ff).sub.2, NR.sup.ffC(O)R.sup.ee, NR.sup.ffCO.sub.2R.sup.ee, NR.sup.ffC(O)N(R.sup.ff).sub.2, C(NR.sup.ff)OR.sup.ee, OC(NR.sup.ff)R.sup.ee, OC(NR.sup.ff)OR.sup.ee, C(NR.sup.ff)N(R.sup.ff).sub.2, OC(NR.sup.ff)N(R.sup.ff).sub.2, NR.sup.ffC(NR.sup.ff)N(R.sup.ff).sub.2, NR.sup.ffSO.sub.2R.sup.ee, SO.sub.2N(R.sup.ff).sub.2, SO.sub.2R.sup.ee, SO.sub.2OR.sup.ee, OSO.sub.2R.sup.ee, S(O)R.sup.ee, Si(R.sup.ee).sub.3, OSi(R.sup.ee).sub.3, C(S)N(R.sup.ff).sub.2, C(O)SR.sup.ee, C(S)SR.sup.ee, SC(S)SR.sup.ee, P(O)(OR.sup.ee).sub.2, P(O)(R.sup.ee).sub.2, OP(O)(R.sup.ee).sub.2,
[0143] OP(O)(OR.sup.ee).sub.2, C.sub.1-6 alkyl, C.sub.1-6 perhaloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, heteroC.sub.1-6 alkyl, heteroC.sub.2-6 alkenyl, heteroC.sub.2-6 alkynyl, C.sub.3-10 carbocyclyl, 3-10 membered heterocyclyl, C.sub.6-10 aryl, 5-10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.gg groups, or two geminal R.sup.dd substituents can be joined to form O or S; wherein X is a counterion; each instance of R.sup.ee is, independently, selected from C.sub.1-6 alkyl, C.sub.1-6 perhaloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, heteroC.sub.1-6 alkyl, heteroC.sub.2-6 alkenyl, heteroC.sub.2-6 alkynyl, C.sub.3-10 carbocyclyl, C.sub.6-10 aryl, 3-10 membered heterocyclyl, and 3-10 membered heteroaryl, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.gg groups; each instance of R.sup.ff is, independently, selected from hydrogen, C.sub.1-6 alkyl, C.sub.1-6 perhaloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, heteroC.sub.1-6 alkyl, heteroC.sub.2-6 alkenyl, heteroC.sub.2-6 alkynyl, C.sub.3-10 carbocyclyl, 3-10 membered heterocyclyl, C.sub.6-10 aryl and 5-10 membered heteroaryl, or two R.sup.ff groups are joined to form a 3-10 membered heterocyclyl or 5-10 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.gg groups; and each instance of R.sup.gg is, independently, halogen, CN, NO.sub.2, N.sub.3, SO.sub.2H, SO.sub.3H, OH, OC.sub.1-6 alkyl, ON(C.sub.1-6 alkyl).sub.2, N(C.sub.1-6 alkyl).sub.2, N(C.sub.1-6 alkyl).sub.3.sup.+X.sup., NH(C.sub.1-6 alkyl).sub.2.sup.+X.sup., NH.sub.2(C.sub.1-6 alkyl).sub.3.sup.+X.sup., NH.sub.3.sup.+X.sup., N(OC.sub.1-6 alkyl) (C.sub.1-6 alkyl), N(OH)(C.sub.1-6 alkyl), NH(OH), SH, SC.sub.1-6 alkyl, SS(C.sub.1-6 alkyl), C(O)(C.sub.1-6 alkyl), CO.sub.2H, CO.sub.2(C.sub.1-6 alkyl), OC(O)(C.sub.1-6 alkyl), OCO.sub.2(C.sub.1-6 alkyl), C(O)NH.sub.2, C(O)N(C.sub.1-6 alkyl).sub.2, OC(O)NH(C.sub.1-6 alkyl), NHC(O)(C.sub.1-6 alkyl), N(C.sub.1-6 alkyl)C(O)(C.sub.1-6 alkyl), NHCO.sub.2(C.sub.1-6 alkyl), NHC(O)N(C.sub.1-6 alkyl).sub.2, NHC(O)NH(C.sub.1-6 alkyl), NHC(O)NH.sub.2, C(NH)O(C.sub.1-6 alkyl), OC(NH)(C.sub.1-6 alkyl), OC(NH)OC.sub.1-6 alkyl, C(NH)N(C.sub.1-6 alkyl).sub.2, C(NH)NH(C.sub.1-6 alkyl), C(NH)NH.sub.2, OC(NH)N(C.sub.1-6 alkyl).sub.2, OC(NH)NH(C.sub.1-6 alkyl), OC(NH)NH.sub.2, NHC(NH)N(C.sub.1-6 alkyl).sub.2, NHC(NH)NH.sub.2, NHSO.sub.2(C.sub.1-6 alkyl), SO.sub.2N(C.sub.1-6 alkyl).sub.2, SO.sub.2NH(C.sub.1-6 alkyl), SO.sub.2NH.sub.2, SO.sub.2(C.sub.1-6 alkyl), SO.sub.2O(C.sub.1-6 alkyl), OSO.sub.2(C.sub.1-6 alkyl), SO(C.sub.1-6 alkyl), Si(C.sub.1-6 alkyl).sub.3, OSi(C.sub.1-6 alkyl).sub.3, C(S)N(C.sub.1-6 alkyl).sub.2, C(S)NH(C.sub.1-6 alkyl), C(S)NH.sub.2, C(O)S(C.sub.1-6 alkyl), C(S)SC.sub.1-6 alkyl, SC(S)SC.sub.1-6 alkyl, P(O)(OC.sub.1-6 alkyl).sub.2, P(O)(C.sub.1-6 alkyl).sub.2, OP(O)(C.sub.1-6 alkyl).sub.2, OP(O)(OC.sub.1-6 alkyl).sub.2, C.sub.1-6 alkyl, C.sub.1-6 perhaloalkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, heteroC.sub.1-6 alkyl, heteroC.sub.2-6 alkenyl, heteroC.sub.2-6 alkynyl, C.sub.3-10 carbocyclyl, C.sub.6-10 aryl, 3-10 membered heterocyclyl, 5-10 membered heteroaryl; or two geminal R.sup.gg substituents can be joined to form O or S; wherein X is a counterion.
[0144] The term halo or halogen refers to fluorine (fluoro, F), chlorine (chloro, Cl), bromine (bromo, Br), or iodine (iodo, I).
[0145] The term hydroxyl or hydroxy refers to the group-OH. The term substituted hydroxyl or substituted hydroxyl, by extension, refers to a hydroxyl group wherein the oxygen atom directly attached to the parent molecule is substituted with a group other than hydrogen, and includes groups selected from OR.sup.aa, ON(R.sup.bb).sub.2, OC(O)SR.sup.aa, OC(O)R.sup.aa, OCO.sub.2R.sup.aa, OC(O)N(R.sup.bb).sub.2, OC(NR.sup.bb)R.sup.aa, OC(NR.sup.bb)OR.sup.aa, OC(NR.sup.bb)N(R.sup.bb).sub.2, OS(O)R.sup.aa, OSO.sub.2R.sup.aa, OSi(R.sup.aa).sub.3, OP(R.sup.cc).sub.2, OP(R.sup.cc).sub.3.sup.+X.sup., OP(OR.sup.cc).sub.2, OP(OR.sup.cc).sub.3.sup.+X.sup., OP(O)(R.sup.aa).sub.2, OP(O)(OR.sup.cc).sub.2, and OP(O)(N(R.sup.bb).sub.2).sub.2, wherein X, R.sup.aa, R.sup.bb and Rec are as defined herein.
[0146] The term amino refers to the group NH.sub.2. The term substituted amino, by extension, refers to a monosubstituted amino, a disubstituted amino, or a trisubstituted amino. In certain embodiments, the substituted amino is a monosubstituted amino or a disubstituted amino group.
[0147] The term monosubstituted amino refers to an amino group wherein the nitrogen atom directly attached to the parent molecule is substituted with one hydrogen and one group other than hydrogen, and includes groups selected from NH(R.sup.bb), NHC(O)R.sup.aa, NHCO.sub.2R.sup.aa, NHC(O)N(R.sup.bb).sub.2, NHC(NR.sup.bb)N(R.sup.bb).sub.2, NHSO.sub.2R.sup.aa, NHP(O)(OR.sup.cc).sub.2, and NHP(O)(N(R.sup.bb).sub.2).sub.2, wherein R.sup.aa, R.sup.bb, and Rec are as defined herein, and wherein R.sup.bb of the group NH(R.sup.bb) is not hydrogen.
[0148] The term disubstituted amino refers to an amino group wherein the nitrogen atom directly attached to the parent molecule is substituted with two groups other than hydrogen, and includes groups selected from N(R.sup.bb).sub.2, NR.sup.bbC(O)R.sup.aa, NR.sup.bbCO.sub.2R.sup.aa, NR.sup.bbC(O)N(R.sup.bb).sub.2, NR.sup.bbC(NR.sup.bb)N(R.sup.bb).sub.2, NR.sup.bbSO.sub.2R.sup.aa, NR.sup.bbP(O)(OR).sub.2, and NR.sup.bbP(O)(N(R.sup.bb).sub.2).sub.2, wherein R.sup.aa, R.sup.bb, and Re are as defined herein, with the proviso that the nitrogen atom directly attached to the parent molecule is not substituted with hydrogen.
[0149] The term trisubstituted amino refers to an amino group wherein the nitrogen atom directly attached to the parent molecule is substituted with three groups, and includes groups selected from N(R.sup.bb).sub.2 and N(R.sup.bb).sub.3.sup.+X.sup., wherein R.sup.bb and X are as defined herein.
[0150] The term sulfonyl refers to a group selected from SO.sub.2N(R.sup.bb).sub.2, SO.sub.2R.sup.aa, and SO.sub.2OR.sup.aa, wherein R.sup.aa and R.sup.bb are as defined herein.
[0151] The term sulfinyl refers to the group S(O)R.sup.aa, wherein R.sup.aa is as defined herein.
[0152] The term acyl refers to a group having the general formula C(O)R.sup.X1, C(O)OR.sup.X1, C(O)OC(O)R.sup.X1, C(O)SR.sup.X1, C(O)N(R.sup.X1).sub.2, C(S)R.sup.X1, C(S)N(R.sup.X1).sub.2, C(S)O(R.sup.X1), C(S)S(R.sup.X1), C(NR.sup.X1)R.sup.X1, C(NR.sup.X1)OR.sup.X1, C(NR.sup.X1) SR.sup.X1, and C(NR.sup.X1)N(R.sup.X1).sub.2, wherein R.sup.X1 is hydrogen; halogen; substituted or unsubstituted hydroxyl; substituted or unsubstituted thiol; substituted or unsubstituted amino; substituted or unsubstituted acyl, cyclic or acyclic, substituted or unsubstituted, branched or unbranched aliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched heteroaliphatic; cyclic or acyclic, substituted or unsubstituted, branched or unbranched alkyl; cyclic or acyclic, substituted or unsubstituted, branched or unbranched alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, mono- or di-aliphaticamino, mono- or di-heteroaliphaticamino, mono- or di-alkylamino, mono- or di-heteroalkylamino, mono- or di-arylamino, or mono- or di-heteroarylamino; or two R.sup.X1 groups taken together form a 5- to 6-membered heterocyclic ring.
[0153] Exemplary acyl groups include aldehydes (CHO), carboxylic acids (CO.sub.2H), ketones, acyl halides, esters, amides, imines, carbonates, carbamates, and ureas. Acyl substituents include, butare not limited to, any of the substituents described herein, that result in the formation of a stable moiety (e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, oxo, imino, thiooxo, cyano, isocyano, amino, azido, nitro, hydroxyl, thiol, halo, aliphaticamino, heteroaliphaticamino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphaticoxy, heteroaliphaticoxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphaticthioxy, heteroaliphaticthioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, acyloxy, and the like, each of which may or may not be further substituted).
[0154] The term carbonyl refers a group wherein the carbon directly attached to the parent molecule is sp.sup.2 hybridized, and is substituted with an oxygen, nitrogen or sulfur atom, e.g., a group selected from ketones (e.g., C(O)R.sup.aa), carboxylic acids (e.g., CO.sub.2H), aldehydes (CHO), esters (e.g., CO.sub.2R.sup.aa, C(O)SR.sup.aa, C(S)SR.sup.aa), amides (e.g., C(O)N(R.sup.bb).sub.2, C(O)NR.sup.bbSO.sub.2R.sup.aa, C(S)N(R.sup.bb).sub.2, and imines (e.g., C(NR.sup.bb)R.sup.aa, C(NR.sup.bb)OR.sup.aa), C(NR.sup.bb)N(R.sup.bb).sub.2, wherein R.sup.aa and R.sup.bb are as defined herein.
[0155] The term oxo refers to the group O, and the term thiooxo refers to the group S.
[0156] Nitrogen atoms can be substituted or unsubstituted as valency permits, and include primary, secondary, tertiary, and quaternary nitrogen atoms. Exemplary nitrogen atom substituents include, but are not limited to, hydrogen, OH, OR.sup.aa, N(R).sub.2, CN, C(O)R.sup.aa, C(O)N(R).sub.2, CO.sub.2R.sup.aa, SO.sub.2R.sup.aa, C(NR.sup.bb)R.sup.aa, C(NR.sup.cc)OR.sup.aa, C(NR)N(R).sub.2, SO.sub.2N(R).sub.2, SO.sub.2R.sup.cc, SO.sub.2OR.sup.cc, SOR.sup.aa, C(S)N(R).sub.2, C(O)SR.sup.cc, C(S)SR.sup.cc, P(O)(OR).sub.2, P(O)(R.sup.aa).sub.2, P(O)(N(R.sup.cc).sub.2).sub.2, C.sub.1-10 alkyl, C.sub.1-10 perhaloalkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl, heteroC.sub.1-10 alkyl, heteroC.sub.2-10 alkenyl, heteroC.sub.2-10 alkynyl, C.sub.3-10 carbocyclyl, 3-14 membered heterocyclyl, C.sub.6-14 aryl, and 5-14 membered heteroaryl, or two Rec groups attached to an N atom are joined to form a 3-14 membered heterocyclyl or a 5-14 membered heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, carbocyclyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5 R.sup.dd groups, and wherein R.sup.aa, R.sup.bb, Roc and R.sup.dd are as defined herein.
[0157] An anionic counterion is a negatively charged group associated with a positively charged group in order to maintain electronic neutrality. An anionic counterion may be monovalent (i.e., including one formal negative charge). An anionic counterion may also be multivalent (i.e., including more than one formal negative charge), such as divalent or trivalent. Exemplary counterions include halide ions (e.g., F.sup., Cl.sup., Br.sup., I.sup.), NO.sub.3.sup., ClO.sub.4.sup., OH.sup., H.sub.2PO.sub.4.sup., HCO.sub.3.sup., HSO.sub.4.sup., sulfonate ions (e.g., methansulfonate, trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, 10-camphor sulfonate, naphthalene-2-sulfonate,
[0158] naphthalene-1-sulfonic acid-5-sulfonate, ethan-1-sulfonic acid-2-sulfonate, and the like), carboxylate ions (e.g., acetate, propanoate, benzoate, glycerate, lactate, tartrate, glycolate, gluconate, and the like), BF.sub.4.sup., PF.sub.4.sup., PF.sub.6.sup., AsF.sub.6.sup., SbF.sub.6.sup., B[3,5-(CF.sub.3).sub.2C.sub.6H.sub.3].sub.4.sup., B(C.sub.6F.sub.5).sub.4.sup., BPh.sub.4, Al(OC(CF.sub.3).sub.3).sub.4.sup., and carborane anions (e.g., CB.sub.11H.sub.12.sup. or (HCB.sub.11Me.sub.5Br.sub.6).sup.). Exemplary counterions which may be multivalent include CO.sub.3.sup.2, HPO.sub.4.sup.2, PO.sub.4.sup.3, B.sub.4O.sub.7.sup.2, SO.sub.4.sup.2, S.sub.2O.sub.3.sup.2, carboxylate anions (e.g., tartrate, citrate, fumarate, maleate, malate, malonate, gluconate, succinate, glutarate, adipate, pimelate, suberate, azelate, sebacate, salicylate, phthalates, aspartate, glutamate, and the like), and carboranes.
[0159] The term bonded or bound as used herein refers to two species (e.g., a crystalline particle and a ligand, or a cation and an anion) that are interconnected via chemical bonds, the nature of which will be understood by one of ordinary skill the art. For example, chemical bonds involved in the compositions and methods of the present disclosure include but are not limited to dative bonds, covalent, bonds, ionic bonds, hydrogen bonds, and halogen bonds, which themselves are common terms of art and well understood by ordinarily skilled artisans thereof.
[0160] A salt as used herein refers to a compound comprising at least one positively charged ion (cation) and at least one negatively charged ion (anion), the compound itself being overall neutral in charge. As a non-limiting example, a salt may comprise: a metal monocation and a nonmetal anion (e.g., PbBr.sub.2, MnCl.sub.2, and CsCO.sub.3); or a cation of an organic molecule and a nonmetal anion, e.g. formamidinium chloride, [CH(NH.sub.2).sub.2].sup.+Cl.sup...
[0161] The term long-chain alkyl as used herein refers to an alkyl group as defined above, having a carbon chain of at least about 5 carbons in length, e.g., from about 5 to about 25 carbons in length, or from about 8 to about 18 carbons in length. Long-chain alkyl groups may have one or more sites of unsaturation in the chain, e.g. one or more double bond. As a non-limiting example, long chain alkyl may refer to hexyl, heptyl, octyl, nonyl, stearyl, oleyl, and/or decyl groups. The term long-chain alkyl may be used to refer to lipids and vice versa.
[0162] The term sulfobetaines refers to functional groups or molecules comprising a positively charged quaternary ammonium and a negatively charged sulfonate group separated by a C3 alkyl group, or suitable salts thereof. A long-chain sulfobetaine is a molecule comprising a sulfobetaine group as defined above, and a long-chain alky group as defined above.
[0163] The term phosphocholines refers to functional groups or molecules having a quaternary ammonium group and a phosphate group separated by a C2 alkyl group, or suitable salts thereof. The phosphate group and/or the ammonium group may be substituted with one or more alkyl groups, e.g., a long-chain alkyl group as defined above. As a non-limiting example, lecithin may be referred to herein as a phosphocholine.
[0164] The term phospholipids as used herein refers to functional groups or molecules having a phosphate group and at least one long-chain alkyl, group. For example, phopholipids include lecithin.
[0165] The term long-chain alkylamines as used herein refers to functional groups or molecules having an amine group and at least one long-chain alkyl group, or suitable salts thereof. For example, oleylamine is a long-chain alkylamine of the disclosure.
[0166] The term long-chain alkylacids as used herein refers to functional groups or molecules having a carboxylate group and at least one long-chain alkyl group, or suitable salts thereof. For example, oleic acid, and suitable salts thereof, are long-chain alkylacids of the disclosure.
EXAMPLES
[0167] The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of certain aspects and embodiments of the present invention, and are not intended to limit the invention.
Example 1: Exemplary Synthetic Methods
Materials:
[0168] PbBr2 (99.99%), MnCl2 (99.99%), ZnCl2 (98%), NiCl2 (98%), trioctylphosphine oxide (TOPO, 90%), Cs.sub.2CO.sub.3 (99%), Diisooctylphosphinic acid (DOPA, 90%), oleylamine (98%), and hydrochloric acid (37%) were ordered from Sigma-Aldrich. Hexane (97%, HPLC grade), acetone (99.5%) were ordered from VWR. Lecithin (97%, from soy), diethyl ether (99%, stabilized) were ordered from ThermoFisher. Octane (98%) was ordered from Beantown Chemicals. All reagents were used without further purification.
Stock Solution Preparation
[0169] The XCl:PbBr2 stock solutions were prepared with different molar ratios (100:0, 95:5, 90:10, 80:20, 75:25, and 50:50) of XCl:PbBr.sub.2 (X=Mn, Ni, and Zn). In general, W 1.25 mmol of TOPO, 0.2 mmol (total) of XCl:PbBr.sub.2 were added to 1.25 ml of octane, where the temperature was raised to 120 C. for 1 hour. Upon cooling, 5 mL of hexanes were added. The trioctylphosphine oxide (TOPO) stock solution was prepared by dissolving 6 mmol of TOPO in 30 ml of hexane. The Cs.sub.2CO.sub.3 stock solution was prepared by adding 100 mg of Cs.sub.2CO.sub.3 to a vial with 1 ml of diisooctylphosphinate (DOPA) and 2 ml octane before heating for 60 min. at 120 C. Upon cooling, 27 ml hexane were added. The lecithin stock solution was prepared by dissolving lecithin in hexane in 50 mg/mL. All stock solutions were syringe filtered (13 mm diameter, 0.45 m pore size) before NC synthesis.
Oleylammonium Chloride Synthesis
[0170] 12.5 mL of oleylamine and 100 mL were added to a flask and placed in an ice bath. 9.6 mL of HCl was added dropwise, and allowed to stir overnight. The oleylammonium chloride (OleyCl) salt was purified by washing with diethyl ether 3 times, and dried under vacuum overnight, yielding a white powder.
[0171] The OleyCl stock solution was prepared by dissolving OleyCl in toluene at a concentration of 10 mg/mL in toluene.
General Nanocrystalline Halide Perovskite Synthesis
[0172] In a glass vial with a ml of hexane, l of a PbBr.sub.2:X.sub.DOPANTCl.sub.2 stock solution was added (where X.sub.DOPANT=Mn, Zn, Ni) with a certain ratio (=100:0, 95:5, 90:10, 80:20, 75:25, 50:50, 25:75, or 0:100) and L of the TOPO stock solution together with a small stirring bar. All stock solutions are agitated directly before usage for 10 s. at 2,500 rpm. The synthesis was started directly after adding the stock solutions into the glass vial filled with hexane. Up to six samples are placed on a stirring plate approx. 5 cm from the middle such that they are all stirred with the same intensity at 500 rpm. After 20 s. of mixing, l of Cs.sub.2CO.sub.3 is added to start the synthesis. After a certain time T, the synthesis is ended by adding l of lecithin solution. For chloride and bromide shifting (halide exchange), 1 ml of chloride or bromide salt (chosen depending on the halide desired in the resulting HP NC) was dissolved toluene or non-polar solvent solution 30 s. prior to adding lecithin.
[0173] The typical volumes used for each synthesis parameter are shown below in Table S1.
TABLE-US-00001 TABLE S1 Parameter Typical Range Hexane Volume, 1-12 mL Volume of PbBr.sub.2 stock solution, 20-200 L Ratio of Pb:X.sub.DOPANT doping, 100:0-50:50 TOPO stock solution volume added, 0-360 L Volume of Cs.sub.2CO.sub.3 stock solution, 10-100 L Reaction time, T 1-30 min
[0174] Most syntheses performed fell into these typical ranges, but this synthesis works for higher quantities. For example, Mn-doped NCs scaled up by 50-100 typical quantities were successfully synthesized via this method, resulting in NCs synthesized on the 100-1000 mg scales with no change in their optical properties (indicating similar size characteristics).
NC Purification
[0175] The synthesized NCs were added to a centrifuge tube, where 18 ml of acetone (approx. 3-fold excess) were added into the centrifuge tube. All tubes were centrifuged for 5 min. at 7480 rpm, corresponding to 5,500 g. After acetone was dispensed, the vials were dried for 4 min. Then, 1 ml of hexane was added to each centrifuge tube and agitated for 10 s to dissolve the nanocrystals. The NC solutions were finally passed through hydrophobic PTFE syringe filters (0.45 m pore size with 13 mm in diameter). The final solution of nanocrystals dissolved in 1 ml of hexane was stored in small glass vials for later measurement.
Steady-State Optical Characterization
[0176] UV-visible absorption spectra were collected using a Cary 5000 UV-Vis-NIR spectrophotometer using a spectral bandwidth of 2 nm. Steady-state PL spectra were collected using a CCS200/M spectrometer (ThorLabs) using a 365 nm LED (ThorLabs Solis365C) equipped with a 365 nm bandpass filter (Newport) to excite the samples. A 385 nm long pass filter (Newport) was placed after the sample to remove excess scatter from the excitation source. The 1 mL hexane redispersed samples were measured optically without further modification.
Elemental Analysis
[0177] As-synthesized Mn-doped or metal-doped halide perovskite nanocrystals were first purified as normal, and then dried under vacuum for 1 hour to remove residual hexane. For elemental analysis via ICP-MS, the nanocrystals were digested in aqueous HNO.sub.3 before the % Mn/Pb was determined using an ICP-MS:Agilent 7800.
Transient Absorption (TA) Spectroscopy
[0178] TA was measured using a setup based on a 1030 nm seed laser (PHAROS, Light Conversion, Yb:KGW lasing medium, 400 J pulse energy, 150 fs duration, 50 kHz repetition rate). The 343 nm pump beam (800 m in diameter) was generated from the first and second harmonics of the 1030 nm seed laser using a harmonic generation unit equipped with nonlinear crystals (beta-barium borate, lithium triborate). (HIRO, Light Conversion). The residual first and second harmonics were removed by dichroic mirrors. The third harmonic (343 nm) pump was passed through an optical chopper (100 Hz), where a portion of the pump was routed to a photodiode using a beam splitter in order to sort generated probe measurements into pumped and unpumped. The probe beam (200 m in diameter) was generated from the second harmonic of the seed laser using quasi-supercontinuum generation in a sapphire crystal. The probe beam was passed into a grating spectrograph (Andor Kymera 193i) and recorded using a Si NMOS photodiode array detector (256 pixels). All TA experiments were conducted at pump fluences 3 J/cm2. NC samples were measured in a 1 mm path-length quartz cuvette (Hellma) at concentrations 0.5 M.
Time-Resolved Photoluminescence Measurements
[0179] Time-resolved photoluminescence was measured using time-correlated single photon counting (TCSPC). The 343 nm excitation sources were generated from a 1030 nm seed laser (PHAROS, Light Conversion, Yb:KGW lasing medium, 400 J pulse energy, 150 fs duration, 50 kHz repetition rate) using a harmonic generation unit equipped with beta-barium borate and lithium triborate nonlinear crystals (HIRO, Light Conversion). Upon photoexcitation, fluorescence from the sample was focused on a photomultiplier tube (Becker & Hickl HPM-100-07) positioned behind the exit slit of a monochromator, where photon counting occurred using the single photon counting module provided by Light Conversion. Nanocrystal Size Quantification
[0180] After purification and redispersal in hexane, the HP NCs were drop-casted onto a TEM grid. Micrographs were measured using a JEOL 2100 TEM. Edge lengths were determined using line profiles using ImageJ.
[0181] Further structural characterization was performed and the morphologies of samples with histogrammed sizes were collected using a JEOL ARM 200F TEM at 200 kV using a single tilt holder.
Electron Paramagnetic Resonance (EPR)
[0182] X-band continuous-wave (CW) EPR spectra were recorded on a Bruker ElexSys E500 spectrometer. All spectra were recorded at room temperature as suspensions in hexane. Spectrometer settings were as follows: frequency=9.86 GHz, power=0.6325 mW, gain=20 dB, modulation amplitude=8.0 G, modulation frequency=100 kHz, 32 sweeps. All spectra were simulated using EasySpin to obtain effective g values and hyperfine coupling constants.
Example 2: Exemplary Nanocrystalline Mn-Doped CsPbCl.SUB.3 .Halide Perovskites Selected for TEM Imaging
TABLE-US-00002 TABLE S2 Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 X X Added 320 (L) 280 240 X X X 200 160 X X X X X 120 X X X X X
Example 3: Absorbance Peak Maxima (.SUB.max .in nm) for Exemplary Halide Shifted (X=Cl.SUP..) Nanocrystals
TABLE-US-00003 TABLE S3 Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 402.25 399.25 386.75 387.5 386.75 388.25 Added 320 402.5 398.0 385.25 387.75 388 388.25 (L) 280 404 396 395.5 390.25 389 392 240 399.25 395.25 392.75 392.5 391.5 390.25 200 397.5 394.25 392.75 392.5 397 391 160 395.25 392.75 392.5 392.5 395.25 390.5 120 393.25 390.75 388.75 389.0 390.75 390.5
Example 4: Absorbance Peak Maxima (.SUB.max .in nm) for Exemplary Non-Halide Shifted (X=Mixture of Cl/Br) Nanocrystals
TABLE-US-00004 TABLE S4 Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 501.5 489.75 475.25 445.5 440.5 430.25 Added 320 501.5 484.5 473 455.25 442.25 417.5 (L) 280 497.5 482.25 470 459.5 447.25 418.75 240 496 480.5 467.5 453.25 446.25 418.75 200 489 472.5 463.25 451.5 445.74 424 160 484.25 484.5 461.75 465.5 451.5 445.25 120 473 469.25 472 466 450.5 429.25
Example 5: Emission Peak Maxima (.SUB.max .in nm) for Exemplary Halide Shifted (X=Cl.SUP..) Nanocrystals
TABLE-US-00005 TABLE S5 Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 405.25 404.28 403.72 403.72 403.07 403.07 Added 320 406.34 404.16 403.07 403.94 403.07 401.98 (L) 280 410.5 403.07 403.72 403.07 403.07 405.47 240 404.38 403.07 401.98 401.98 403.07 401.98 200 403.07 401.98 401.98 401.98 404.38 401.98 160 403.07 401.1 403.07 403.07 404.38 401.98 120 401.98 398.92 397.18 398.98 401.1 401.1
Example 6: Emission Peak Maxima (.SUB.max .in nm) for Exemplary Non-Halide Shifted (X=Mixture of Cl/Br) Nanocrystals
TABLE-US-00006 TABLE S6 Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 508.75 499.62 489.17 470.55 459.94 439.44 Added 320 508.31 494.5 485.62 469.66 459.94 431.75 (L) 280 504.07 491.84 481.63 472.32 459.94 431.52 240 503.18 490.5 480.96 464.8 458.39 431.53 200 496.95 484.95 477.64 464.58 457.95 421.88 160 494.06 496.51 480.96 466.13 458.39 431.75 120 490.06 486.06 487.4 478.08 463.92 438.12
Example 7: Absorbance and Emission Peak Maxima (.SUB.max .in nm) for Exemplary Zn-Doped CsPbCl.SUB.3 .Perovskite Nanocrystals
TABLE-US-00007 TABLE S7a Absorbance Peak Maxima (.sub.max in nm). Molar Ratio of Pb:Zn in Stock Solution 100:0 90:10 80:20 50:50 TOPO 360 402.25 401.25 394.75 392.75 Added 240 400.25 401.25 394.75 396.75 (L) 120 392.25 395.25 393.25 396.25
TABLE-US-00008 TABLE S7b Emission Peak Maxima (.sub.max in nm). Molar Ratio of Pb:Zn in Stock Solution 100:0 90:10 80:20 50:50 TOPO 360 412.8 413.9 415.5 408.9 Added 240 411.8 411 410.2 409.6 (L) 120 408.1 406.2 406.2 410.7
Example 8: Absorbance and Emission Peak Maxima (.SUB.max .in nm) for Exemplary Ni-Doped CsPbCl.SUB.3 .Perovskite Nanocrystals
TABLE-US-00009 TABLE S8a Absorbance Peak Maxima (.sub.max in nm). Molar Ratio of Pb:Ni in Stock Solution 100:0 90:10 80:20 50:50 TOPO 360 404.25 404.25 397.25 389.25 Added 240 404.25 404.25 399.5 395.5 (L) 120 397.5 394.5 393.5 396.25
TABLE-US-00010 TABLE S8b Emission Peak Maxima (.sub.max in nm). Molar Ratio of Pb:Ni in Stock Solution 100:0 90:10 80:20 50:50 TOPO 360 412.3 411.8 407.5 406.7 Added 240 408.9 410.2 407 410.7 (L) 120 406.7 408.1 407.5 407
Example 9: Inductively Coupled Plasma-Mass Spectrometry Analysis of Exemplary Nanocrystalline Mn-doped CsPbCl.SUB.3 .Halide Perovskites
TABLE-US-00011 TABLE S9a Exemplary Nanocrystalline Mn-doped CsPbCl.sub.3 Halide Perovskites Selected for Inductively Coupled Plasma-Mass Spectrometry Analysis Molar Ratio of Pb:Mn in Stock Solution 100:0 95:5 90:10 80:20 75:25 50:50 TOPO 360 X X X X Added 320 (L) 280 240 X X X 200 160 120 X X X X X
TABLE-US-00012 TABLE S9b Results of Inductively Coupled Plasma-Mass Spectrometry Analysis of Exemplary Nanocrystalline Mn-doped CsPbCl.sub.3 Halide Perovskites TOPO Vol. Pb:Mn Ratio (L) (pre-synthesis) % Mn (relative to Pb) 120 95:5 0.062% 360 95:5 0.103% 120 90:10 0.111% 240 90:10 0.189% 360 90:10 0.187% 120 75:25 0.297% 360 75:25 0.298% 120 50:50 0.477% 240 50:50 0.502% 360 50:50 0.468%
Example 10: Edge Length Characterization of Exemplary Mn-Doped Halide Perovskite Nanocrystal Compositions
120 L TOPO Stock Solution
TABLE-US-00013 TABLE S10a Pb:Mn Ratio (pre- Std. synthesis) D90 D70 D50 Mean Dev. 100:0 6.53 5.88 5.42 5.51 0.87 95:5 7.20 5.77 5.12 5.31 1.24 80:20 7.18 6.21 5.66 5.64 1.17 75:25 6.96 6.26 5.78 5.85 0.95 50:50 8.61 7.20 6.60 6.76 1.27
160 L TOPO Stock Solution
TABLE-US-00014 TABLE S10b Pb:Mn Ratio Std. (pre-synthesis) D90 D70 D50 Mean Dev. 100:0 7.24 6.28 5.76 5.92 0.95 95:5 6.84 5.97 5.49 5.58 1.06 90:10 6.91 6.40 6.03 6.00 0.73 80:20 6.04 5.43 5.03 5.03 0.80 50:50 6.75 6.04 5.60 5.64 0.92
240 L TOPO Stock Solution
TABLE-US-00015 TABLE S10c Pb:Mn Ratio Std. (pre-synthesis) D90 D70 D50 Mean Dev. 100:0 7.39 6.56 6.22 6.23 0.83 80:20 6.98 6.10 5.46 5.53 1.15 50:50 7.39 6.65 6.034 6.06 1.08
360 L TOPO Stock Solution
TABLE-US-00016 TABLE S10d Pb:Mn Ratio Std. (pre-synthesis) D90 D70 D50 Mean Dev. 100:0 12.12 10.97 9.95 9.91 1.76 50:50 13.35 11.35 10.23 10.66 2.18
Example 11: Results and Discussion of a Mn-Doped as an Example Case
[0183] At first, it has to be emphasized that the methods of the disclosure can be generalized to other metallic dopant such as Ni or Zn. Mn-doped NCs, which are an exemplary case, are examined more specifically below. Size-tunable doped nanocrystals were synthesized according to the methods of the disclosure, using the above-described mole ratios and various amounts of TOPO added to precisely tune the Mn concentration and NC size, respectively. Upon the addition of Mn, the pure-chloride-doped NCs feature the expected pronounced blue shift in their excitonic absorption (
[0184] When the halide anion is not shifted during synthesis, the host excitonic absorption and emission blue shift with higher Mn doping ratios due to a higher chloride content brought in, rather than the impact of the metal dopant. In the not fully halide-shifted case (i.e., largely bromide-rich Mn-doped CsPbX.sub.3 with only small amounts of chloride content), no Mn significant emission is observed.
[0185] The NC size and shape remain again largely unchanged upon doping, as shown by TEM (
[0186] The ability to precisely synthesize size- and doping-level-tunable NCs allows for the elucidation of their photophysical properties in a systematical manner allowing decoupling effects due to dopant incorporation or halide composition from those of quantum confinement. Accordingly, the dynamics of charge recombination and energy transfer to Mn centers in Mn-doped CsPbX.sub.3 NCs have been studied through a combination of time-resolved optical spectroscopies, providing insights on carrier trapping, radiative recombination, energy/charge transfer to Mn, and Auger-like processes.
[0187]
[0188] In all spectra, three dominant features can be observed: i) a negative feature corresponding to the excitonic ground state bleach (GSB), attributed to carrier filling upon excitation, ii) a positive photoinduced absorption (PIA) feature blue-shifted from the GSB, and iii) another PIA red-shifted from the GSB. The positive feature red-shifted from the GSB is commonly attributed to the presence of biexcitons. In our analysis, we focus on the ground-state exciton bleach and plot the kinetics at the respective maximum for each undoped NC size in
[0189] We observe largely multi-exponential appearing kinetics for all cases, which can be understood from the ensemble character of the nanocrystals having a distribution of respective sizes and trap densities (e.g. a different propensity of surface traps between two NCs in the solution). Therefore, we refrain here from the unphysical assignment of lifetimes from multi-exponential fits to specific processes but note that generally charge trapping has been assigned to occur often on few-ps timescales, energy-transfer from host to dopant on a few-hundred ps timescale, radiative recombination on the sub-ns to few-ns timescale, and delayed trap-assisted recombination on the order of hundreds of ns. Following this, the initially similar drop within the first few ps for all sizes of undoped NCs (
[0190] Further, we use TA to elucidate differences in the surface dynamics to monitor the effects of the different chloride-shifting agents. We measured TA kinetics taken from the GSB maxima for undoped and 1.8% Mn-doped CsPbCl.sub.3 NCs chloride shifted with oleylammonium chloride or WCl6/TOPO. In both cases, the recovery lessened in the first 5 ps, the timescale typically attributed to rapid carrier trapping in CsPbCl.sub.3 NCs. Therefore, we attribute the slower bleach recovery to a higher degree of surface passivation when oleylammonium chloride is used. The excess amines allow for tighter cationic ligand binding. It is important to note though, that the injection of oleylammonium chloride also forms additional species present in solution, which can be visible in the UV-Vis absorbance. These species probably are 2D layered Pb-halide species formed under an excess of oleylamine. These species can be separated by employing slightly longer mixing times (after ligand addition) and by syringe filtering the NC solution. Therefore, the anion-shifting agent can be chosen to reflect the priority for ease in synthesis (WCl6/TOPO), or for a higher degree of surface passivation (oleylammonium chloride), based on application requirements.
[0191] As the methods of this disclosure can be generalized, HP NCs were doped with Ni.sup.2+ or Zn.sup.2+ dopants.
[0192] The synthetic method of the disclosure allows for photophysical investigations into doped perovskite nanocrystals at size and dopant concentration ranges that have not been able to be reached previously. We observed a difference in the optical properties over time in undoped and doped nanocrystals with different sizes across multiple timescales, for example. First, using time-resolved photoluminescence (PL) measurements in the form of time-correlated single photon counting, we observed the PL decay rapidly in the presence of Mn-dopants, where we attributed this to energy transfer to Mn d-d states upon nanocrystal excitation. Importantly, the rates of energy transfer change depending on the nanocrystal size as it can be observed from the comparison between
[0193] Additionally, the ultrafast photophysical phenomena of doped and undoped perovskite nanocrystals have been observed using ultrafast transient absorption. Transient absorption allows for the elucidation of spectral and temporal dynamics in the excited states of both undoped and doped perovskite nanocrystals. We observed a larger difference in the ground state bleach kinetics of smaller perovskite nanocrystals, when the undoped nanocrystals are compared directly to Mn-doped perovskite nanocrystals with a 50:50 Pb:Mn doping ratio (
INCORPORATION BY REFERENCE
[0194] All publications and patents mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control.
EQUIVALENTS
[0195] While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims below. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.