Organoboron compounds and methods of making same
10301328 ยท 2019-05-28
Assignee
Inventors
- Jiasheng Lu (Kingston, CA)
- Suning Wang (Kingston, CA)
- Soo-Byung Ko (Kingston, CA)
- Sean Michael McDonald (Kingston, CA)
- Dengtao Yang (Kingston, CA)
Cpc classification
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C09K2211/1044
CHEMISTRY; METALLURGY
H10K85/6572
ELECTRICITY
C09K2211/185
CHEMISTRY; METALLURGY
C09K11/025
CHEMISTRY; METALLURGY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C09K11/02
CHEMISTRY; METALLURGY
C07F15/00
CHEMISTRY; METALLURGY
G03G5/06
PHYSICS
Abstract
The invention provides organoboron precursors and facile photoirradiation and/or heating methods of making corresponding elimination products. Some elimination products are polycyclic aromatic molecules wherein a number of aromatic CC moieties have been replaced by a BN moiety to form azaborine compounds with interesting properties such as electronic, photophysical, luminescent, as well as chemical properties. Examples of polymer films that were doped with such compounds are shown wherein irradiated portions of the polymer film luminesce. The invention further provides methods of producing photoluminescence and electroluminescence, and uses of the compounds of the invention in luminescent probes, sensors, electroluminescent devices, hydrogen storage materials, optoelectronic materials, and bioactive molecules.
Claims
1. A method of making aromatic azaborine compounds, comprising: photoirradiating a reactant; and obtaining an elimination product; wherein the reactant comprises: (i) a boron atom that is bonded at least to a first moiety and a second moiety, the first moiety being a terminal moiety, and the second moiety being a Lewis base comprising an aryl, heteroaryl, N-heterocyclic carbene, or a heteroatom; (ii) a carbon atom that is proximal to the boron and that is bonded to at least one hydrogen atom; wherein the elimination product differs from the reactant such that the elimination product: (a) has a bond between the boron and the carbon, which may be a single bond or an additional bond between the boron and the carbon; and (b) does not include the first moiety.
2. The method of claim 1, comprising a reaction: ##STR00174## wherein G is independently carbon or a heteroatom; X and Y are independently carbon or nitrogen; T is a terminal moiety; R is hydrogen, a linear, branched or cyclic aliphatic moiety, or an aryl (which includes heteroaryl) moiety, and may be further substituted; R is hydrogen, a linear, branched or cyclic aliphatic moiety, or an aryl (which includes heteroaryl) moiety, and may be further substituted, and is optionally a fused ring(s); t is independently 0 or 1; p is independently 0 to 10; and a dotted circle represents optional aromaticity; with the proviso that at least one moiety bonded to B, excluding the terminal moiety, is a Lewis base, wherein each ring has 0-2 ring atoms that are heteroatoms, and at least one ring of the product is an aryl ring.
3. The method of claim 1, wherein the elimination product is photoluminescent or electroluminescent.
4. The method of claim 1, wherein the elimination product is an electron transport material.
5. The method of claim 2, wherein the reactant is: BN-1, BN-2, BN-3, BN-4, BN-7, (BN2)-1, (BN2)-2, BC-1, BC-2, BC-3, BC-4, BN-bpy1, SM1, DT1, or BN-Bpy-Pt1 ##STR00175## ##STR00176##
6. The method of claim 1, wherein the elimination product is: BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, SM1-aza, DT1-aza, or BN-5b ##STR00177##
7. The method of claim 1, wherein a final product is a triboron compound or a conjugated polycyclic compound comprising BN moieties.
8. The method of claim 7, wherein the triboron compound is BN-5b, (BN)2-2a, BN-5c, BN-6c, BC-1b, BN-7b, BN-bpyB1a, BN-bpy-Pt1a, or BC-1 ##STR00178## ##STR00179##
9. An electroluminescent device for use with an applied voltage, comprising: a first electrode, an emitter which is an electroluminescent elimination product of claim 1, optionally in a host layer, and a second, transparent electrode, wherein voltage is applied to the two electrodes to produce an electric field across the emitter so that the emitter electroluminesces.
10. A compound of general formula: ##STR00180## wherein G is independently carbon or a heteroatom (e.g., N, S, O, P); X and Y are independently carbon or nitrogen; R is an aliphatic or aryl (which includes heteroaryl) moiety that may be further substituted; R is an aliphatic or aryl (which includes heteroaryl) moiety that may be further substituted and is optionally a fused ring(s); t is independently 0 or 1; p is independently 0 to 10; and a dotted circle represents optional aromaticity; wherein each ring has 0-2 ring atoms that are heteroatoms, and at least one ring of the product is an aryl ring.
11. The compound of claim 10, wherein for the ring comprising X, t is zero and at least one ring atom is a heteroatom, so that ring is a five-membered heterocycle.
12. The compound of claim 10, wherein X is nitrogen and Y is carbon.
13. The compound of claim 10, wherein the ring comprising Y is substituted phenyl.
14. The compound claim 10, wherein the R substituent on B is mesityl.
15. The compound of claim 10, wherein the compound is BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, BN-5b, SM1-aza, or DT1-aza ##STR00181##
16. A compound which comprises a structure of general formula: ##STR00182## ##STR00183## wherein G is independently carbon or a heteroatom (e.g., N, S, O, P; X and Y are independently carbon or nitrogen; T is a terminal moiety; R is hydrogen, a linear, branched or cyclic aliphatic moiety, or an aryl (which includes heteroaryl) moiety, and may be further substituted; R is hydrogen, a linear, branched or cyclic aliphatic moiety, or an aryl (which includes heteroaryl) moiety, and may be further substituted, and is optionally a fused ring(s); t is independently 0 or 1; p is independently 0 to 10; and a dotted circle represents optional aromaticity; wherein each ring has 0-2 ring atoms that are heteroatoms, and at least one ring of the product is an aryl ring, and with the proviso that at least one moiety bonded to B, excluding the terminal moiety, is a Lewis base, and wherein rings may be substituted or unsubstituted.
17. The compound of claim 16, wherein the compound is (BN)2-2, BN-5b, (BN)2-2a, BN-5c, BN-6c, BC-1b, BN-7b, BN-bpyB1a, BN-bpy-Pt1a, BC-1, BN-5, BN-6, BN-1a, BN-2a, BN-3a, BN-4a, (BN2)-1a, BN-5b, SM1-aza, or DT1-aza ##STR00184## ##STR00185## ##STR00186##
18. The method of claim 1, wherein the elimination product's boron atom can undergo one or more subsequent elimination reaction(s) involving the same carbon atom or a different carbon atom.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) For a better understanding of the present invention and to show more clearly how it may be carried into effect, reference will now be made by way of example to the accompanying drawings, which illustrate aspects and features according to preferred embodiments of the present invention, and in which:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
DETAILED DESCRIPTION OF THE INVENTION
Definitions
(28) As used herein, the term azaborine refers to a compound comprising at least one boron atom and at least one nitrogen atom. Although not meant to be limiting, azaborine may describe a compound that comprises a BN moiety.
(29) As used herein, the term TfOH means trifluoromethanesulfonic acid, which is also known as triflic acid or CF.sub.3SO.sub.3H. The term TsOH means p-toluenesulfonic acid. The term TFA means trifluoroacetic acid. The term PA means picolinic acid.
(30) As used herein, the terms N^C chelate, P^C chelate and C^C chelate indicate chelation ligands wherein the atoms indicated are those that are bonded to the central atom. As used herein the term aliphatic includes alkanyl, alkenyl and alkynyl moieties. An aliphatic group may be substituted or unsubstituted. It may be straight chain, branched chain or cyclic.
(31) As used herein the term Mes means mesityl, which is also known as 2,4,6-trimethylphenyl.
(32) As used herein the term aryl includes aromatic carbocycles and aromatic heterocycles, and aryl moieties may be substituted or unsubstituted.
(33) As used herein, the term unsubstituted refers to any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified then it is hydrogen.
(34) As used herein substituted refers to the structure having one or more substituents.
(35) As used herein heteroatom means a non-carbon, non-hydrogen atom. In some cases, a heteroatom may have a lone pair of electrons available to form dative or coordinate bonds (e.g., N, O, S, P).
(36) As used herein, the term HSQC refers to Heteronuclear Single Quantum Coherence, which is a Nuclear Magnetic Resonance (NMR) method to determine chemical shifts that are difficult to determine by typical NMR.
(37) As used herein, the term dative bond refers to a coordination bond formed when one molecular species serves as a donor and the other as an acceptor of an electron pair to be shared.
(38) As used herein, the term Lewis base refers to a molecular entity able to provide a pair of electrons (IUPAC Gold Book).
(39) As used herein, the term isoelectronic means two or more molecular entities that have the same number of valence electrons and the same structure, i.e. number and connectivity of atoms, but differ in some of the elements involved (IUPAC Gold Book).
(40) As used herein, the term ligand refers to a chemical species or moiety that is capable of bonding an atom of interest (e.g., boron).
(41) As used herein, the term moiety refers to an indefinite portion (i.e., a segment or part of a whole) of a molecule.
(42) As used herein, the term terminal ligand describes an atom or group of atoms (charged or uncharged) that is non-bridging, i.e., does not connect to another part of the molecule, but rather ends. In this context, in specified reactions described herein, the terminal ligand of a reactant leaves and is absent from the consequent product. Also as used herein, the term terminal moiety describes an atom or group of atoms (charged or uncharged) that is non-bridging, i.e., does not connect to another part of the molecule, but rather ends. In this context, in specified reactions described herein, the terminal moiety of a reactant leaves and is absent from the consequent product.
(43) As used herein, the term proximal when used in relation to chemical reactivity, means that chemical moieties that are proximal are close enough to one another to influence each other's reactivity. Although not strictly required, in some instances, proximal groups are three bonds away from one another. In other instances, proximal groups are bonded to one another. In certain embodiments, proximal groups are several bonds from one another (e.g., 5 bonds), but they can be positioned close enough in space to influence each other's reactivity.
(44) As used herein, the term main group metal refers to elements in groups whose lightest members are helium, lithium, beryllium, boron, carbon, nitrogen, oxygen, and fluorine as arranged in columns of the periodic table of the elements. Main group elements include elements (except hydrogen) in groups 1 and 2 (s-block), and groups 13 to 18 (p-block).
(45) As used herein, the term rare earth metal refers to a set of seventeen chemical elements in the periodic table, specifically, fifteen lanthanides plus scandium and yttrium.
(46) As used herein, the term luminescence refers to emission of light by a substance not resulting from heat; it is thus a form of cold body radiation. Electroluminescence refers to luminescence as a result of an electric current passing through a substance. Photoluminescence refers to luminescence as a result of absorption of photons. Fluorescence refers to photoluminescence as a result of singlet-singlet electronic relaxation (typical lifetime: nanoseconds). Phosphorescence refers to photoluminescence as a result of triplet-singlet electronic relaxation (typical lifetime: milliseconds to hours).
(47) As used herein, the term optoelectronics refers to study and application of electronic devices that source, detect and control light. Optoelectronic devices are electrical-to-optical or optical-to-electrical transducers, or instruments that use such devices in their operation.
Embodiments
(48) A new and facile photoelimination synthetic method has been discovered. This method provides a synthesis for forming one or more bonds between carbon and boron. In certain embodiments, a reactant compound that is suitable for this synthetic method comprises a boron that is bonded to a terminal ligand and that is also bonded to a Lewis base (i.e., a moiety having a lone pair of electrons) through a dative bond. Such suitable compound also includes a carbon located proximal to the boron, wherein the carbon is bonded to at least one hydrogen atom. Upon irradiation with light, the reactant undergoes an elimination reaction. After this elimination reaction, the hydrogen and the terminal ligand are no longer bonded to the carbon and boron, respectively, and may be bonded to one another. Also after this elimination reaction, the product has a newly-formed bond between the carbon and the boron. In some embodiments, the newly-formed bond is a single bond between the carbon and the boron. In other embodiments, the newly-formed bond is an additional bond between these two atoms that were previously bonded by a lesser number of bonds (e.g., a double bond where previously there had been a single bond).
(49) In some embodiments, the boron is bonded to a carbon atom or nitrogen atom that is a ring atom of an aromatic ring. In some embodiments, the boron is a substituent of a fused aromatic ring system. In certain embodiments, the boron is a substituent of a carbocycle that may be aromatic or non-aromatic. In certain embodiments, the boron is a substituent of a heterocycle that may be aromatic or non-aromatic. In certain embodiments, the boron is a substituent of a heterocycle and is bonded to the heterocycle through at least one of its heteroatom(s). In other embodiments, the boron is a substituent of a heterocycle and is bonded to the heterocycle through a carbon ring atom.
(50) A schematic is provided below as a simplified example of this new synthetic method.
(51) ##STR00008##
(52) wherein X and Y are independently carbon or nitrogen;
(53) T is a terminal ligand (e.g., H, aliphatic, aryl, CH.sub.3, mesityl);
(54) R is a aliphatic or aryl moiety that may be further substituted;
(55) a circular moiety represents an aromatic, non-aromatic, saturated, or unsaturated cyclic moiety.
(56) Acceptable substituents include any chemical moiety that does not interfere with the desired reaction and may include, for example: a non-aromatic carbocycle or heterocycle, an aryl group (which includes a heteroaryl) that is attached as a fused ring or as a substituent, a hydroxy group, alkoxo, nitro, amino, halo, BR.sub.2, B(aryl).sub.2, aryl-B(aryl).sub.2, O, NR.sub.2, OR, a nitrile group, C(halo).sub.3 which includes CF.sub.3, and R, where R is a substituted or unsubstituted aliphatic group having 1-24 carbon atoms which may be straight, branched or cyclic (e.g., adamantyl). A substituent may be further substituted.
(57) In addition, through this new synthetic method, new organoboron (aromatic and non-aromatic) compounds have been prepared and characterized. In certain embodiments, such compounds have a BN moiety as a replacement for a CC unit in an aromatic molecule. This is possible because a BN moiety is isoelectronic to CC (see Campbell, P. G. et al., Angew. Chem. Int. Ed. 2012, 51, 6074-6092). Such replacements lead to new compounds with interesting new properties. Hence, such compounds may be useful in a variety of fields such as: hydrogen storage materials (P. G. Campbell, et al., J. Am. Chem. Soc. 2010, 132, 18048), optoelectronic materials (T. Agou, et al., Org. Lett. 2006, 8, 2241; R. Kwong, G. Kottas, International Patent, WO 2011/143563 A2), sensors (T. Agou, et al., Chem. Commun. 2009, 1894; M. Lepeltier, et al., Chem. Commun. 2010, 46, 7007), and bioactive molecules (L. Liu, et al., Angew. Chem. Int. Ed. 2009, 48, 6817). Examples of organoboron compounds that display photochemical reactivity are known previously (W. H. Saunders, et al., Mechanisms of Elimination Reactions, John Wiley & Sons, New York, 1973; A. Gilbert, et al., in Photochemistry, 1995, 26, 326; A. Pelter, et al., Tetrahedron, 2000, 56, 7339; Y. L. Rao, et al., Coord. Chem. Rev. 2012, 256, 759; R. L. Rao, et al., J. Am. Chem. Soc. 2008, 130, 12898; K. Ansorg, et al. Angew. Chem. Int. Ed. 2011, 50, 2833; J. D. Wilkey, et al., J. Am. Chem. Soc. 1988, 110, 7569).
(58) However, the present photoelimination reaction is unusual. In certain embodiments, a CH bond is cleaved and a BC bond is formed. Furthermore, the present photoelimination method provides a general method to produce N-heterocyclic compounds, where ring heteroatoms comprise B and N, optionally bonded to each other. Such compounds may be, for example, fused ring systems. (One might imagine a graphene in which one or more CC moiety is replaced by a corresponding one or more BN moiety). The photoelimination reaction product may comprise, for example, a pyridyl, pyrimidinyl, benzothiazolyl, or imidazolyl moiety. In addition, the present photoelimination reaction also applies to N-heterocyclic carbenes (NHCs) functioning as the Lewis base that forms a dative bond with boron (see Scheme 4), enabling generation of boron-substituted aromatic compounds. Furthermore, the present photoelimination method can be applied in the synthesis of polycyclic aromatic compounds such as BN replaced graphenes and related extended ?-conjugated materials, which are an important class of materials for organic electronics and organic optoelectronic devices (Geim, A. K. et al. Nature Materials, 2007, 6, 183).
(59) Importantly, it has been shown that this photoelimination reaction may also occur readily in a polymer matrix or in solid state. As described herein, initial studies have shown that precursor compounds (i.e., reactants from which there will be elimination) BN-1, BN-2, BN-3 and BN-4 can undergo quantitative photoelimination in a polymer film (e.g. PMMA) in the same manner as seen in solution. Such polymer films studies generated luminescent aromatic azaborine compounds (see UV-Vis spectra and fluorescence spectra in
(60) Precursors suitable as reactants for this photoelimination or thermoelimination reaction include compounds that comprise a structure of one or more formulae set forth below. Their corresponding elimination products are provided as the products of the reactions set forth below.
(61) ##STR00009##
(62) wherein G is independently carbon or a heteroatom (e.g., N, S, O, P)
(63) X and Y are independently carbon or nitrogen;
(64) T is a terminal ligand;
(65) R is hydrogen, an aliphatic, or aryl (which includes heteroaryl) moiety that may be further substituted;
(66) R is hydrogen, an aliphatic or aryl (which includes heteroaryl) moiety that may be further substituted and is optionally a fused ring(s);
(67) t is independently 0 or 1;
(68) p is independently 0 to 10;
(69) a dotted circle represents optional aromaticity,
(70) with the proviso that at least one moiety bonded to B, excluding the terminal ligand T, is a Lewis base that has donated a lone pair of electrons and is bonded to boron through a dative bond.
(71) Examples of several reactants having the above general formulas, known herein as precursors, are provided herein. Structural formulae for specific examples are provided in Tables 1 and 2 and Schemes 1-8d, photophysical properties of selected elimination products are shown in Table 3, and synthetic information and characterization are provided in the Working Examples. In addition, details of successful elimination reactions of many exemplary precursors are provided. Structural formulae for the elimination products are also provided in Table 1, and synthetic information and characterization are provided in the Working Examples.
(72) A person of skill in the art of the invention will recognize that in certain embodiments, elimination products can themselves be precursors, and photoelimination can continue if the conditions (e.g., substituents) are suitable. Accordingly, the inventors provide below general structures for monomer (i.e., monoboron), dimer (i.e., diboron) and trimer compound (i.e., triboron) compounds that may be formed by photoelimination reactions described herein. The inventors have demonstrated formation of dimer and trimer compounds by photoelimination of appropriate precursors, and have confirmed the products by high resolution mass spectroscopic methods.
(73) Furthermore, dimer or trimer compounds formed by photoelimination can undergo further reactions to form tetramer and greater compounds, such as polycyclic molecules (e.g., aromatic polycycles, polycyclic ?-conjugated azaborine molecules). Thus, it is appropriate to state that certain compounds according to the invention comprise the general monomer, dimer, or trimer structures set forth below, meaning that such a compound includes the selected structure, but is not limited to it, and may include additional structure(s). For example, certain compounds according to the invention may include multiple such dimer structures, or multiple such trimer structures. Monomer, dimer, trimer and other multimer compounds may be useful in the creation of films, particularly photo-patterned films. Such compounds may additionally or alternatively be useful for hydrogen storage, reversible hydrogenation applications, and/or conductive/charge transport/luminescent materials for optoelectronic devices.
(74) ##STR00010##
Monomer, where G, Y, X, t, p and R are as described above.
(75) ##STR00011##
Dimer A
(76) ##STR00012##
Dimer B
(77) ##STR00013##
Dimer C.
(78) For clarity, the top general formula of each pair depicted hereinabove has been shown in a simplified form with six-membered aromatic rings, and unsubstituted, but a person of skill in the art of the invention will recognize that five-membered rings, substituents, and/or larger numbers of heteroatoms are encompassed by aspects of the invention. This is more apparent from the bottom general formula of each pair.
(79) ##STR00014##
Dimer D
(80) For clarity, the top general formula of each pair depicted hereinabove has been shown in a simplified form with six-membered aromatic rings, and unsubstituted, but a person of skill in the art of the invention will recognize that five-membered rings, substituents, and/or larger numbers of heteroatoms are encompassed by aspects of the invention. This is more apparent from the bottom general formula of each pair.
(81) ##STR00015##
Trimer.
(82) For clarity, the top general formula of each pair depicted hereinabove has been shown in a simplified form with six-membered aromatic rings, and unsubstituted, but a person of skill in the art of the invention will recognize that five-membered rings, substituents, and/or larger numbers of heteroatoms are encompassed by aspects of the invention. This is more apparent from the bottom general formula of each pair.
(83) ##STR00016##
Fully Conjugated Trimer.
(84) For clarity, the top general formula of each pair depicted hereinabove has been shown in a simplified form with six-membered aromatic rings, and unsubstituted, but a person of skill in the art of the invention will recognize that five-membered rings, substituents, and/or larger numbers of heteroatoms are encompassed by aspects of the invention. This is more apparent from the bottom general formula of each pair. Notably, Dimers A-D can also trimerize, forming 2D conjugated boron-containing polyaromatic systems.
(85) Precursor compounds that were prepared as described herein were observed to be colourless except for BN-3 and BN-bpy-Pt1, which were light yellow in solution and in the solid state. They were air and thermally stable and did not show any appreciable change in toluene, when heated to 110? C. They were fully characterized by .sup.1H, .sup.13C, and .sup.11B NMR, and high resolution mass spectra (HRMS) and/or elemental analysis data as described in the Working Examples. Crystal structures of BN-1, BN-3, BN-4, BN-4a, BN-bpy1, BC-1, SM1-aza, and DT1-aza were determined by single-crystal X-ray diffraction analysis as shown in
(86) The synthesized precursors underwent elimination reactions either via the photoirradiation method described herein or via the pyrolysis method described herein and their corresponding elimination products were characterized as described in the Working Examples. Structural formulae of certain compounds of the invention are shown in the Schemes and Tables.
(87) All of the precursor compounds are not fluorescent in the visible region of the spectra while their corresponding new azaborine analogues display bright green or yellow-green fluorescence in both solution and solid state (see
(88) BN-1a, BN-2a, BN-3a and (BN)2-1a are stable for days in the solid state and slowly degrade in solution upon exposure to air. In contrast, BN-4a decomposes rapidly in solution and in the solid state under air, presumably because of the reaction with oxygen (A. N. Lamm, et al., Mol. BioSyst. 2009, 5, 1303). The greater chemical stability of BN-1a to BN-3a and (BN)2-1a is clearly provided by the bulky mesityl group. Compounds BN-1a, BN-2a and BN-4a are previously unknown isomers of BN-phenanthrenes while compound (BN)2-1a is a new BN-replaced pyrene. Three other isomers of BN-phenanthrene and their derivatives (1-3) (R. Kwong, G. Kottas, International Patent, WO 2011/143563 A2; M. J. D. Bosdet, et al., Org. Lett. 2007, 9, 1395; M. J. S. Dewar, et al., J. Am. Chem. Soc. 1962, 84, 4884; M. J. S. Dewar, V. P. Kubba, R. Pettit, J. Chem. Soc. 1958, 3073; and M. J. D. Bosdet, et al., Angew. Chem. Int. Ed. 2007, 46, 4960) and one isomer of BN-pyrene (4) (M. J. D. Bosdet, et al., Angew. Chem. Int. Ed. 2007, 46, 4960) were reported previously and are shown below.
(89) ##STR00017##
Structures of Previously Known BN-Phenanthrene and BN-Pyrene Compounds
(90) Solution Phase Conversion of Precursors of Scheme 1 and 3 to Form Corresponding Azaborine Compounds by Photoelimination
(91) The precursor compounds shown in Scheme 1 Scheme 2a and Scheme 3 were converted to their corresponding aromatic azaborine monomer compounds by photoelimination reaction as illustrated by examples in Scheme 3. For example, when excited at 300 nm in dry toluene or benzene under nitrogen, the solutions of BN-1, BN-2 and BN-4 changed from colourless to bright yellow. In the UV-Vis spectra, a distinct new absorption band appeared at the 360 to 520 nm region and grew in intensity with increasing irradiation time, which accounts for the solution colour change (
(92) Diboron compound (BN)2-1 underwent a similar photoelimination reaction, forming the diboron azaborine compound (BN)2-1a as shown in Scheme 3a. (BN)2-1a displays a red color and was characterized by HRMS spectroscopy.
(93) Solid Phase Conversion of Precursors in Scheme 1 and 3 to the Corresponding Azaborine Compounds by Photoelimination in a Polymer Matrix.
(94) As described above, in certain embodiments, precursor compounds may readily undergo the photoelimination reaction described herein in the solid state or in a polymer film such as, for example, poly(methyl methacrylate) (PMMA) or poly(N-vinylcarbazole) (PVK). UV-Vis spectra of the precursor compounds in PMMA films undergo similar changes upon irradiation by UV light to those recorded for the same compounds in solution (e.g., in toluene), supporting that the same azaborine species were formed. UV-Vis spectra showing conversion of BN-2 to BN-2a, and BN-4 to BN-4a in PMMA film (10 wt %) with UV irradiation are shown in
(95) Patterned fluorescent films can be prepared using compounds of the embodiments of the invention. This patterning is possible because of the contrasting non-emissive and emissive properties of the precursor compounds relative to their corresponding elimination products. Some examples were prepared of patterned fluorescent films and the resultant films had high contrast. Such films can be made by casting a precursor doped PMMA film on a glass substrate, positioning a mask between the film and a light source (e.g., covering the film with a mask), and exposing it to UV light. The masked areas remained non-luminescent, and the areas that were exposed to UV light were glowing a yellowing-green colour. Examples of such patterned films are shown in
(96) A prototype electroluminescent device with the structure of ITO/PVK:3 wt % of BN-3/Ca has been fabricated. BN-3 was converted to BN-3a, after BN-3/PVK was spin-cast to the ITO substrate, by irradiation at 265 nm. This device emitted a yellow-green color after it was turned on, see photograph in
(97) Absorption and fluorescence spectra of BN-1a, BN-2a and BN-4a are similar, despite the different substituent groups. This similarity is an indication that the low energy electronic transitions in these molecules are most likely dictated by the BN-phenanthrene unit. This idea has been confirmed by computational studies. HOMO and LUMO levels of BN-1a, BN-2a, BN-4a and BN-5a are localized on the BN-phenanthrene ring with no or little contributions from substituent groups. Similarly, for the benzothiazolyl BN-3a compound, the HOMO and LUMO levels are localized at the BN-substituted arene ring. Thus, the fluorescence of the new azaborine compounds can be attributed to a ?.fwdarw.?* transition of the ?-conjugated azaborine unit. An impact of BN replacement in phenanthrene was narrowing the HOMO-LUMO gap and decreasing the ?.fwdarw.?* transition energy. This finding is in agreement with the general trend observed previously for azaborine compounds (M. J. D. Bosdet, et al., Org. Lett. 2007, 9, 1395; A. Chrostowska, et al., J. Am. Chem. Soc. 2012, 134, 10279; M. J. D. Bosdet, et al., Angew. Chem. Int. Ed. 2007, 46, 4940), with the exception of BN-phenanthrene 1 (R=R=H) that has a higher HOMO-LUMO transition energy than phenanthrene (M. J. D. Bosdet, et al., Org. Lett. 2007, 9, 1395; M. J. S. Dewar, et al., J. Chem. Soc. 1958, 3073).
(98) Conversion of the Precursors in Scheme 4 to the Corresponding Azaborine Trimer Compounds by Photoelimination According to Scheme 2.
(99) Precursor compounds that comprise a BH.sub.3 moiety are shown in Schemes 2 and 4. Such precursors can undergo quantitative photoelimination of hydrogen molecules, forming trimer compounds. Presumably, the monomer shown in Scheme 2 was formed first, which subsequently converted to the trimer by eliminating 3 more equivalents of hydrogen molecules per trimer. Several such trimer products have been synthesized, and characterized by HRMS spectroscopy (
(100) A calculated structure of BN-5b optimized by DFT (discrete Fourier transform) computation is shown in
(101) Conversion of Azaborine Trimers to Fully Conjugated BN- or B-Substituted Polyaromatic Molecules
(102) Some of the azaborine trimer compounds (e.g. BN-5b in Scheme 5 and (BN)2-2a in Scheme 5a can undergo oxidative dehydrogenation reactions readily forming a fully conjugated species such as BN-5c and BN-6c shown in Scheme 6. Oxidative dehydrogenation is a well-established synthetic method for converting hexa-phenyl substituted benzene and its derivatives to fully conjugated graphenes (M. D. Watson, et al., Chem. Rev. 2001, 101, 1207; and A. Stabel, et al., Angew. Chem. Int. Ed., 1995, 34, 1609). The same procedure has been shown to work well for the BN-replaced molecules. Other potential BN-replaced graphenes or B-replaced fully conjugated polyaromatic molecules are provided in Table 2.
(103) Embodiments Having Metal-Functionalized Azaborine Compounds
(104) The backbone of BN-azaborine compounds may be modified by attaching metal-chelate units (e.g., main-group metal chelate units, transition metal chelate units, or rare earth metal chelate units). Two examples are illustrated in Scheme 7. Modification of the backbone by such metal chelates can effectively tune the colors of the precursor molecules. In some embodiments, the presence of metal-substituents shifts the excitation energy of the precursor to the visible region, making it possible to drive the photoelimination reaction using visible light. In addition, the presence of metal-substituents introduces properties such as phosphorescence and electron transport to the molecule. Oxidative dehydrogenation of the metal modified compounds could lead to the formation of fully conjugated metal-functionalized molecules such as the one example shown in Scheme 7b. Additional examples of such compounds with metal chelate units can be found in Table 2.
(105) In summary, an unprecedented photoelimination reaction has been discovered, which can be used effectively in constructing, for example, ?-conjugated polycyclic azaborine compounds. In some embodiments this is done by eliminating a RH molecule from a BR.sub.2CH.sub.2 unit. This photoelimination is applicable to solid substrates such as, for example, B,N-heterocycle doped PMMA or PVK films. This solid phase reaction makes possible a simple and convenient method for in-situ generation of polycyclic azaborine compounds in polymer substrates and for creating patterned fluorescent polymer films by light, which may find applications in fabrication of optoelectronic devices.
(106) In some embodiments of the invention, an EL device includes one or more charge transport layers interposed between an emitter comprising a luminescent compound as described herein and one or both of the electrodes. Such charge transport layer(s) are employed in prior art systems with inorganic salt emitters to reduce the voltage drop across the emitter. In a first example of such a device, layers are arranged in a sandwich in the following order: first electrode, charge transport layer, emitter and host, second charge transport layer, and second transparent electrode. In an embodiment of this type, a substrate of glass, quartz or the like is employed. A reflective metal layer (corresponding to the first electrode) is deposited on one side of the substrate, and an insulating charge transport layer is deposited on the other side. The emitter layer including a compound of the invention is deposited on the charge transport layer, preferably by vacuum vapor deposition, though other methods may be equally effective. A transparent conducting electrode (e.g., ITO) is then deposited on the emitter layer. An effective voltage is applied to produce electroluminescence of the emitter.
(107) In a second example of an EL device of the invention, a second charge transport layer is employed, and the sandwich layers are arranged in the following order: first electrode, first charge transport layer, emitter and host, second charge transport layer and second, transparent electrode.
(108) Electroluminescent devices of the invention may include one or more of the emitting compounds described herein. In some embodiments of the invention, an electroluminescent device such as a flat panel display device may include not only an emitting compound as described herein, but may be a multiple-color display device including one or more other emitters. The other emitters may emit in other light ranges, e.g., red, green, and/or be stacked relative to each other. Convenient materials, structures and uses of electroluminescent display devices are described in Rack, P. D. et al., Materials used in electroluminescent displays MRS Bulletin (1996) 21(3): 49-58.
(109) The invention further provides methods employing compounds of the invention to harvest photons, and corresponding devices for such use. Spectroscopic studies have demonstrated that compounds of the invention have high efficiency to harvest photons and produce luminescence. In general, when such compounds are excited by light, a charge separation occurs within the molecule; a first portion of the molecule has a negative charge and a second portion has a positive charge. Thus the first portion acts as an electron donor and the second portion as an electron acceptor. If recombination of the charge separation occurs, a photon is produced and luminescence is observed. In photovoltaic devices, recombination of the charge separation does not occur; instead the charges move toward an anode and a cathode to produce a potential difference, from which current can be produced.
(110) Molecules with the ability to separate charges upon light initiation are useful for applications such as photocopiers, photovoltaic devices and photoreceptors. Photoconductors provided by the present invention are expected to be useful in such applications, due to their stability and ability to be spread into thin films. Related methods are encompassed by the invention.
(111) Organic semiconducting materials can be used in the manufacture of photovoltaic cells that harvest light by photo-induced charge separation. To realize an efficient photovoltaic device, a large interfacial area at which effective dissociation of excitons occurs must be created; thus an electron donor material is mixed with an electron acceptor material. (Here, an exciton is a mobile combination of an electron and a hole in an excited crystal, e.g., a semiconductor.) Luminescent compounds as semiconductors are advantageous due to their long lifetime, efficiency, low operating voltage and low cost. Photocopiers use a light-initiated charge separation to attract positively-charged molecules of toner powder onto a drum that is negatively charged.
(112) Certain embodiments of the invention provide compounds suitable for use in biological and/or medical imaging. For example, the compounds' luminescent properties may be useful in vivo or in vitro in visualizing cell substructures or tissue superstructures, such as tumours or other anomalies.
(113) Referring to
(114) The following working examples further illustrate embodiments of the present invention and are not intended to be limiting in any respect.
WORKING EXAMPLES
(115) All experiments were performed under a nitrogen atmosphere unless otherwise noted. Toluene, THF, diethyl ether, hexanes and benzene-d.sub.6 were dried using sodium and benzophenone (as an indicator) and were freshly distilled. CH.sub.2Cl.sub.2 was distilled over P.sub.2O.sub.5. .sup.1H, .sup.13C, .sup.11B 2D-COSY, 2D-NOESY, 2D-HSQC and 2D-HMBC NMR spectra were recorded on Bruker Avance 500 or 600 MHz spectrometers. Excitation and emission spectra were recorded using a Photon Technologies International QuantaMaster Model 2 spectrometer. HRMS were measured by Micromass/Waters GCT Time of Flight (TOF) mass spectrometer (MS) and Thermo Scientific Orbitrap Velos Pro mass spectrometer. Elemental analyses were performed at an elemental analysis laboratory, University of Montreal, Montreal, Quebec, Canada. UV-Visible spectra were recorded using a Varian Cary 50 UV-visible absorbance spectrophotometer (available from Varian, Inc. of Agilent Technologies, Mississauga, ON, Canada). Cyclic voltammetry experiments were performed using a BAS CV-50W analyzer. The electrochemical cell was a standard three-compartment cell composed of a Pt working electrode, a Pt auxiliary electrode, and an Ag/AgCl reference electrode. CV measurements were carried out at room temperature with ?0.1 M tetrabutylammonium hexafluorophosphate (TBAP) as the supporting electrolyte, with ferrocene/ferrocenium as internal standard (E?=0.55 V). A solvent mixture of CH.sub.3CN and THF was used for CV measurements. Fluorescence quantum efficiencies were measured using Ir(ppy).sub.3 as a standard in toluene (T. Sajoto, et al., J. Am. Chem. Soc. 2009, 131, 9813). Photoelimination quantum efficiency was determined using a ferrioxalate as a standard chemical actinometer using previously reported procedures (C. G. Hatchard, et al., Proc. R. Soc. Lond. A, 1956, 235, 518).
Example 1. Synthesis and Characterization of Reactants for Photoirradiation
(116) Synthesis of 2-(2-methylphenyl)-pyridine
(117) 2-(2-methylphenyl)-pyridine was prepared using Pd(PPh.sub.3).sub.4 (5 mol %) and K.sub.2CO.sub.3 (3 equiv) at 80? C. as typical conditions for Suzuki-coupling reactions. After completion, the reaction mixture was purified by column chromatography on silica gel using CH.sub.2Cl.sub.2 and hexane as eluent. .sup.1H NMR and .sup.13C NMR data for the product agrees with that previously reported for 2-(2-methylphenyl)-pyridine (C. Liu, et al., Eur. J. Org. Chem. 2010, 29, 5548).
(118) Synthesis of 2-(2,5-dimethylphenyl)-4-methylpyridine
(119) 2,5-Dimethylbenzenboronic acid (1.0 g, 6.6 mmol), 4-methyl-2-Bromopyridine (1.1 g, 6.6 mmol), Pd(PPh.sub.3).sub.4 (0.38 g, 0.33 mmol) and K.sub.3PO.sub.4 (4.2 g, 19.8 mmol) were dissolved in degassed THF and water (3:1) mixture (250 mL). The mixture was refluxed under N.sub.2 for 18 hours. After removal of the solvent, the residue was extracted with CH.sub.2Cl.sub.2 and water. The organic phase was dried over magnesium sulfate and filtered. The filtrate was purified by column chromatography on silica gel to afford 2-(2,5-dimethylphenyl)-4-methylpyridine as a white solid (0.99 g, 75% yield). .sup.1H NMR (CDCl.sub.3, 600 MHz): ? 8.53 (d, J=5.0 Hz, 1H), 7.20 (s, 1H), 7.19 (s, 1H), 7.14 (d, J=7.6 Hz, 1H), 7.09 (d, J=7.6 Hz, 1H), 7.05 (d, J=5.0 Hz, 1H), 2.39 (s, 3H), 2.34 (s, 3H), 2.30 (s, 3H).
(120) Synthesis of Precursor Compounds of Scheme 1 and Scheme 2a.
(121) The precursor compounds shown in Scheme 1 were prepared by the general procedure shown in Scheme 3. Representative examples of BN-1, BN-2, BN-3 and BN-4 are also shown in Scheme 3. The starting materials or ligands 2-(2-methylphenyl)-pyridine for BN-1, 2-(2,5-dimethylphenyl)-4-methylpyridine for BN-2 and BN-4, and 2-(2,5-dimethylphenyl)-benzothiazole for BN-3 were prepared using Suzuki-Miyaura coupling methods with Pd(PPh.sub.3).sub.4 as the catalyst and K.sub.2CO.sub.3 as the base. Compound BN-1 was synthesized in good yield by the reaction of n-BuLi with 2-(2-methylphenyl)pyridine at ?78? C., followed by the addition of BMes.sub.2F. The dimethyl analogue BN-2 and the benzothiazolyl B,N-heterocyclic compound BN-3 were obtained using the same procedure in good yields. For BN-4, BMes.sub.2F was replaced by BMe.sub.2Br in the synthesis. The presence of tetramethylethylenediamine (TMEDA) in the lithiation step is necessary to ensure that the lithiation takes place mostly at the methyl site and not at the ortho-H atom of the phenyl ring, which can lead to the formation of the undesired N^C-chelate BMes.sub.2 compounds that are analogues of B(ppy)Mes.sub.2 (ppy=phenylpyridine) (R. L. Rao, et al., J. Am. Chem. Soc. 2008, 130, 12898) with a five-membered B,N-heterocycle as side product. The yield of BN-4 was poor, which may be caused by the reaction of BMe.sub.2Br with TMEDA.
(122) Diboron precursor compounds shown in Scheme 2a with R=Aryl or aliphatic (alkyl) can be obtained by double-lithiation of the appropriate ligands. An example, (BN)2-1, is shown in Scheme 3a.
(123) Synthesis of Precursor Compounds of Scheme 2.
(124) The precursor compounds shown in Scheme 2 were synthesized by the general procedure shown in Scheme 4. Representative examples of the precursor compounds obtained by this procedure are also shown in Scheme 4. For BC-1 and BC-3, the R group can be an aliphatic, aryl, (CH.sub.2O).sub.nR (n=1-24, R=alkyl), silyl (e.g. SiR.sub.3) groups. Selected examples of the precursor compounds in Scheme 4 have been fully characterized by NMR spectroscopy. The crystal structure of BC-1 (R=Me) has been determined by X-ray diffraction analysis and is shown in
(125) Synthesis of BN-1
(126) n-BuLi (0.41 mL, 0.66 mmol) was added to a mixture solution of 2-(2-methylphenyl)-pyridine (100 mg, 0.59 mmol) and TMEDA (0.18 mL, 1.18 mmol) in THF (50 mL) at ?78? C. After stirring at this temperature for 2 h, BMes.sub.2F (190 mg, 0.71 mmol) was added. The mixture was stirred for another hour at ?78? C., then allowed to warm slowly to room temperature and stirred for 16 hrs. After removal of the solvent, the residue was extracted with CH.sub.2Cl.sub.2 and water. The hydrophobic phase was dried over magnesium sulfate and filtered. The resultant filtrate was purified by column chromatography on silica gel to afford BN-1 as a white solid (111 mg, 45% yield). .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): ? 8.60 (d, J=6.0 Hz, 1H), 7.20 (d, J=7.3 Hz, 1H), 7.09 (d, J=8.1 Hz, 1H), 6.94 (m, 1H), 6.91 (m, 2H), 6.88 (s, 4H), 6.17 (m, 1H), 3.08 (s, 2H), 2.26 (s, 6H), 2.22 (s, 12H); .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): ? 156.31, 147.73, 147.70, 146.79, 141.70, 141.09, 133.44, 130.77, 130.46, 129.67, 128.39, 126.14, 124.31, 123.56, 123.04, 77.50, 24.61, 20.24; .sup.11B NMR (CD.sub.2Cl.sub.2, 160 MHz): ? 1.62; HR-EIMS (m/z): [M.sup.+] calcd. for C.sub.30H.sub.32BN, 417.2633; found 417.2614. Elemental analysis, calcd: C, 86.33, H, 87.73, N, 3.36; found: C, 86.33, H, 7.78, N, 3.38.
(127) Synthesis of BN-2
(128) n-BuLi (0.35 mL, 0.56 mmol) was added to a mixture solution of 2-(2,5-dimethylphenyl)-4-methylpyridine (100 mg, 0.51 mmol) and TMEDA (0.14 mL, 1.02 mmol) in THF (50 mL) at ?78? C. After stirring at this temperature for 2 hrs, BMes.sub.2F (164 mg, 0.61 mmol) was added. The mixture was stirred for 1 hour at ?78? C., then allowed to warm slowly to room temperature and was stirred for 16 hrs. After removal of the solvent, the residue was extracted with CH.sub.2Cl.sub.2 and water. The hydrophobic phase was dried over magnesium sulfate and filtered. The resultant filtrate was purified by column chromatography on silica gel to afford BN-2 as a white solid (124 mg, 55% yield). .sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): ? 8.44 (d, J=6.2 Hz, 1H), 7.81 (s, 1H), 7.48 (s, 1H), 7.14 (d, J=6.2 Hz, 1H), 6.97 (d, J=7.6 Hz, 1H), 6.80 (d, J=7.6 Hz, 1H), 6.60 (s, 4H), 2.76 (s, 2H), 2.58 (s, 3H), 2.36 (s, 3H), 2.18 (s, 6H), 1.87 (s, 12H); .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): ? 155.64, 153.50, 147.57, 147.23, 144.42, 141.75, 133.56, 133.26, 131.42, 130.29, 129.61, 128.52, 126.56, 124.03, 123.79, 77.50, 24.65, 21.25, 20.73, 20.24; .sup.11B NMR (CD.sub.2Cl.sub.2, 160 MHz): ? 1.15; HR-EIMS (m/z): [M.sup.t] calcd. for C.sub.32H.sub.36BN, 445.2946; found 445.2953. Elemental analysis, calcd: C, 86.28, H, 8.15, N, 3.14; found: C, 86.24, H, 8.26, N, 3.15.
(129) Synthesis of BN-3
(130) Starting material 2-(2,5-dimethylphenyl)-benzothiazole was prepared by the reaction of 1-chlorobenzothiazole with 2,5-dimethylphenylboronic acid using Suzuki-Miyaura coupling methods with Pd(PPh.sub.3).sub.4 (5 mol %) as the catalyst and K.sub.2CO.sub.3 (3 equiv) as the base in degassed THF and water (3:1) mixture. .sup.1H NMR and .sup.13C NMR data agreed with those previously reported for this compound (H. Hachiva, et al. Org. Lett. 2009, 11, 1737). n-BuLi (0.57 mL, 0.92 mmol) was added to a mixture solution of 2-(2,5-dimethylphenyl)benzothiazole (200 mg, 0.84 mmol) and TMEDA (0.25 mL, 1.67 mmol) in THF (50 mL) at ?78? C. After stirring the mixture at ?78? C. for 2 hrs, BMes.sub.2F (268 mg, 1.00 mmol) was added. After being stirred for 1 hr at ?78? C., the mixture was allowed to warm up to room temperature and stirred for another 16 hrs. After the removal of the solvent, the residue was washed with water and extracted with CH.sub.2Cl.sub.2. After the hydrophobic phase was dried over MgSO.sub.4 and filtered, it was purified by column chromatography on silica gel to afford BN-3 as a white solid (285 mg, 70% yield). .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): ? 8.17 (d, J=8.2 Hz, 1H), 7.34 (s, 1H), 7.16 (m, 1H), 7.00 (d, J=7.7 Hz, 1H), 6.92 (s, 4H), 6.86 (m, 2H), 6.75 (d, J=7.8 Hz 1H), 3.29 (s, 2H), 2.31 (s, 12H), 2.28 (s, 6H), 1.94 (s, 3H). .sup.13C NMR (CD.sub.2Cl.sub.2, 125 MHz): ? 172.31, 149.66, 147.93, 144.67, 141.87, 134.44, 134.25, 133.45, 130.56, 129.88, 129.64, 128.08, 127.25, 126.86, 126.08, 122.00, 121.98, 77.51, 24.65, 20.50, 20.30. .sup.11B NMR (CD.sub.2Cl.sub.2, 160 MHz): ? 2.09; HR-EIMS (m/z): [MH.sup.+] calcd. for C.sub.33H.sub.34BNS, 488.25778; found 488.25654. Elemental analysis, calcd: C, 81.30, H, 7.03, N, 2.87, S, 6.58; found: C, 81.29, H, 7.13, N, 2.87, S, 6.57.
(131) Synthesis of BN-4:
(132) n-BuLi (0.35 mL, 0.56 mmol) was added to a mixture solution of 2-(2,5-dimethylphenyl)-4-methylpyridine (100 mg, 0.51 mmol) and TMEDA (0.14 mL, 1.02 mmol) in THF (50 mL) at ?78? C. After stirring at this temperature for 2 hrs, BMe.sub.2Br (0.60 mL, 0.61 mmol) was added. The mixture was stirred for 3 hours at ?78? C., then allowed to warm slowly to room temperature and stirred for another 16 hrs. After removal of the solvent, the residue was extracted with CH.sub.2Cl.sub.2 and water. The hydrophobic phase was dried over magnesium sulfate and filtered. The resultant filtrate was purified via column chromatography on silica gel to afford BN-4 as a white solid (12 mg, 10% yield). .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): ? 8.33 (d, J=6.0 Hz, 1H), 7.42 (d, J=7.6 Hz, 1H), 7.29 (s, 1H), 7.14 (d, J=7.6 Hz, 1H), 7.13 (s, 1H), 6.28 (d, J=7.6 Hz, 1H), 2.34 (s, 2H), 2.30 (s, 3H), 1.73 (s, 3H), 0.56 (s, 6H); .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): ? 153.06, 150.41, 144.61, 143.04, 133.23, 131.82, 131.06, 130.27, 128.07, 127.18, 123.12, 122.70, 20.92, 20.46; .sup.11B NMR (C.sub.6D.sub.6, 160 MHz): ? ?2.65. HR-EIMS (m/z): [MH.sup.+] calcd. for C.sub.16H.sub.20BN, 238.17616; found 238.17557.
(133) Synthesis of (BN)2-1.
(134) n-BuLi (1.6 mL, 2.5 mmol) was added to a mixture solution of 3,3-Dimethyl-2,2-bipyridine (184 mg, 1 mmol) and TMEDA (0.57 mL, 4.0 mmol) in THF (250 mL) at ?78? C. After stirring at this temperature for 2 hrs, BMes.sub.2F (590 mg, 2.2 mmol) was added. The mixture was stirred for 1 hour at ?78? C., then allowed to warm slowly to room temperature and stirred for 16 hrs. After removal of the solvent, the residue was extracted with CH.sub.3Cl and water. The hydrophobic phase was dried over magnesium sulfate and filtered. The resultant filtrate was purified by column chromatography on silica gel to afford the product as a white solid (136 mg, 20% yield). .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): ? 8.35 (d, 1H), 6.94 (d, 1H), 6.60 (s, 4H), 5.78 (t, 1H), 3.06 (s, 2H), 2.26 (s, 6H), 2.02 (s, 12H) HR-EIMS (m/z): [M+] calcd. for C.sub.48H.sub.54B.sub.2N.sub.2, 680.4489; found 680.4457.
(135) Synthesis of BC-1.
Preparation of 3-methyl-1-(2,5-dimethyl)phenyl-2,3-dihydro-H1-imidazol-2-ylidene.BH3 (BC-1)
(136) BC-1 was prepared according to the Scheme 8a. 0.785 g (2.50 mmol) of 3-methyl-1-(2,5-dimethyl)phenylimidazolium iodide was loaded into a 50 mL Schlenk flask with 30 mL of dry degassed THF. The solution was cooled to 0? C. and 2.5 mL of KOtBu (1.0 M in THF) was added dropwise, and the solution was allowed to stir for 45 minutes then 45 more minutes at room temperature, resulting in the slurry turning orange. The reaction mixture was re-cooled to 0? C. and 2.5 mL of BH.sub.3.THF (1.0 M in THF) was then added dropwise, resulting in the slurry turning pale peach. The mixture was stirred for 30 minutes, then allowed to warm to room temperature and stirred for 2 hours further. Volatiles were then removed under vacuum and the resultant residue was extracted in CH.sub.2Cl.sub.2 and filtered. Slow evaporation of the resultant filtrate resulted in 0.23 g (46%) of pale yellow crystals which was identified as the target compound. .sup.1H NMR (400.3 MHz, CDCl.sub.3): ?=7.20 (d, .sup.3J.sub.HH=8.0 Hz, 1H, ArH), 7.17 (d, .sup.3J.sub.HH=8.0 Hz, 1H, ArH), 7.00 (br. s, 1H, ArH), 6.96 (d, .sup.3J.sub.HH=8.0 Hz, 1H, NCH?CHN), 6.86 (d, .sup.3J.sub.HH=8.0 Hz, 1H, NCH?CHN), 3.83 (s, 3H, NCH.sub.3), 2.53 (s, 3H, ArCH.sub.3), 2.05 (s, 3H, ArCH.sub.3), 0.83 (1:1:1:1 q, .sup.2J.sub.HB=88.1 Hz, 3H, BH.sub.3). .sup.13C{.sup.1H} NMR (100.7 MHz, CDCl.sub.3): ?=?174 (NCN located via HMBC), 137.7 (ArC), 136.4 (ArC), 131.9 (ArC), 130.6 (ArC), 130.0 (ArC), 127.7 (ArC), 120.3 (NCH?CHN), 120.1 (NCH?CHN), 36.0 (NCH.sub.3), 20.7 (ArCH.sub.3), 17.2 (ArCH.sub.3). .sup.11B{.sup.1H} NMR (128.4 MHz, CDCl.sub.3): ?=?37.1 (q, .sup.2J.sub.BH=84.7 Hz).
Synthesis of 3-butyl-1-(2,5-dimethyl)phenyl-2,3-dihydro-H1-benzimidazol-2-ylidene.BH3 (BC-3-Bu) (see Scheme 8b)
(137) 0.450 g (1.33 mmol) of N-2,5-dimethylphenyl-N-butyl-benzimidazolium iodide was loaded into a 50 mL Schlenk flask with 25 mL of dry degassed THF. The resulting solution was cooled to 0? C. and 1.6 mL of KOtBu (1.0 M in THF) was added dropwise. During this addition, a green colour was present which ceased once a full equivalent was added, and a yellow slurry was observed. The mixture was allowed to stir for 45 minutes, then 45 more minutes at room temperature. The reaction mixture was cooled again to 0? C. and 1.6 mL of BH.sub.3.THF (1.0 M in THF) was then added dropwise, no visual change occurred. The mixture was stirred for 30 minutes, then allowed to warm to room temperature and stirred for 2 hours further. The volatiles were then removed under vacuum and the residue was extracted in CH.sub.2Cl.sub.2 and filtered. The remaining residue was purified by column chromatography, eluting with 50:50 CH.sub.2Cl.sub.2:hexanes. The combined fractions gave 0.276 g (71%) of a clear, colourless oil, identified as the desired compound by NMR spectra. .sup.1H NMR (400.3 MHz, CDCl.sub.3): ?=7.50 (d, .sup.3J.sub.HH=4.0 Hz, 1H, ArH), 7.38 (t, .sup.3J.sub.HH=4.0 Hz, 1H, ArH), 7.28-7.23 (m, 3H, ArH), 7.06 (s, 1H, ArH), 6.98 (d, .sup.3J.sub.HH=4.0 Hz, 1H, ArH), 4.50 (t, 2H, .sup.3J.sub.HH=8.0 Hz, NCH.sub.2), 2.37 (s, 3H, ArCH.sub.3), 1.95 (tt, 2H, .sup.3J.sub.HH=8.0 Hz, NCH.sub.2CH.sub.2), 1.94 (s, 3H, ArCH.sub.3), 1.49 (qt, 2H, .sup.3J.sub.HH=8.0 Hz, NCH.sub.2CH.sub.2CH.sub.2), 1.01 (t, 3H, .sup.3J.sub.HH=8.0 Hz, NCH.sub.2CH.sub.2CH.sub.2CH.sub.3), 1.00 (1:1:1:1 q, .sup.2J.sub.HB=88.1 Hz, 3H, BH.sub.3). .sup.13C{.sup.1H} NMR (100.7 MHz, CDCl.sub.3): ?=(NCN not located), 136.8 (ArC), 135.0 (ArC), 133.8 (ArC), 132.8 (ArC), 132.4 (ArC), 130.9 (ArC), 130.4 (ArC), 128.5 (ArC), 123.9 (ArC), 123.9 (ArC), 111.7 (ArC), 110.7 (ArC), 45.8 (NCH.sub.2), 31.0 (NCH.sub.2CH.sub.2), 20.8 (ArCH.sub.3), 20.1 (NCH.sub.2CH.sub.2CH.sub.2), 17.0 (ArCH.sub.3), 13.8 (NCH.sub.2CH.sub.2CH.sub.2CH.sub.3). .sup.11B[.sup.1H] NMR (128.4 MHz, CDCl.sub.3): ?=?36.7 (q, .sup.2J.sub.BH=86.9 Hz).
(138) Synthesis of BN-5
(139) BH.sub.3SMe.sub.2 (5.9 ml, 11.8 mmol, 2 eq) was added to a solution of 2-(2-methylphenyl)-pyridine (1 g, 5.9 mmol) in 20 mL of toluene. The mixture was stirred overnight. After removal of solvent and excess BH.sub.3SMe.sub.2 under vacuum, white solid of pure product was obtained in 99% yield. .sup.1H NMR (THF-d8, 600 MHz): ? 8.85 (d, 1H), 8.05 (dd, 1H), 7.59 (dd, 1H), 7.44 (d, 1H), 7.29 (dd, 1H), 7.28 (m, 2H), 7.17 (d, 1H), 2.48 (s, 3H, broad), 2.06 (s, 3H).
(140) Synthesis of BN-7
(141) 2-(2,5-dimethylphenyl)-benzothiazole (1.013 g, 4.23 mmol) was dissolved in dry toluene and the mixture was reduced to ?78? C. in a dry ice/acetone bath. To the mixture was added (CH.sub.3).sub.2S.BH.sub.3 in THF (4 mL, 8.0 mmol) dropwise over a period of 30 min. After stirring for 1 hr, the mixture was allowed to warm to room temperature and was stirred for an additional 10 hrs. The solvent was removed under vacuum and the product mixture was washed by dry hexanes (3?5 mL) to afford a colorless solid of BN-7. .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): ? 8.81 (d, 1H), 7.14 (m, 1H), 6.99 (d, 1H), 6.94 (m, 1H), 6.93 (m, 2H), 6.84 (s, 1H), 2.18 (s, 3H), 2.02 (s, 3H). HRMS: C15H16BNS: Calc: 253.1099; observed: 253.1105.
(142) Synthesis of BN-bpy1
(143) n-BuLi (0.41 mL, 0.66 mmol) was added to a mixture solution of 3-methyl-2,2-bipyridine (472 mg, 2.77 mmol) and TMEDA (830 ?L, 5.54 mmol) in diethyl ether (15 mL) at ?78? C. under N.sub.2 atmosphere. After stirring at this temperature for 1 h, BMes.sub.2F (800 mg, 2.98 mmol) was added. The mixture was stirred for a further one hour at ?78? C., then allowed to warm slowly to room temperature and stirred for 18 h. After removal of the solvent, the residue was extracted with ethyl acetate and water. The hydrophobic phase was dried over magnesium sulfate and filtered. The filtrate was purified by column chromatography on silica gel to obtain BN-bpy1 as a white solid (92 mg, 8% yield). .sup.1H NMR (CDCl.sub.3, 400 MHz): ? 8.62 (d, .sup.3J=8.0 Hz, 1H), 8.58 (d, .sup.3J=6.0 Hz, 1H), 8.29 (d, .sup.3J=4.4 Hz, 1H), 8.09 (t, .sup.3J=7.6 Hz, 1H), 7.39 (t, .sup.3J=6.4 Hz, 1H), 7.12 (d, .sup.3J=7.6 Hz, 1H), 6.95 (dd, .sup.3J=7.2 Hz, .sup.4J=4.4 Hz, 1H), 6.59 (s, 4H), 2.81 (s, 2H), 2.16 (s, 6H), 1.86 (s, 12H). .sup.13C NMR (CDCl.sub.3, 100 MHz): ? 155.70, 147.71, 147.50, 145.72, 143.26, 141.78, 141.22, 136.68, 133.94, 129.96, 125.48, 124.67, 124.52, 77.55, 24.95, 20.80. .sup.11B NMR (CDCl.sub.3, 128 MHz): ? 1.75. HR-EIMS (m/z): [M.sup.+] calcd. for C.sub.29H.sub.31BN.sub.2, 418.2580; found 418.2597.
(144) Synthesis of BN-bpy-Pt1 and Others
(145) Boron and Pt functionalized compounds BN-bpy-Pt1, BN-bpy-Pt2 and BN-bpy-B1 can be obtained by previously established procedures as shown in Scheme 8c (R. L. Rao, et al., J. Am. Chem. Soc. 2008, 130, 12898; Z. M. Hudson, et al., Org. Lett., 2012, 14, 1700). Details for BN-bpy-Pt1 are provided below as a representative example.
(146) Synthesis of BN-bpy-Pt1
(147) [PtMe.sub.2(SMe.sub.2).sub.2] (62 mg, 0.108 mmol) and BN-bpy1 (90 mg, 0.215 mmol) were dissolved in THF (3 mL) under N.sub.2 atmosphere. The reaction mixture is allowed to stir 1 h at room temperature, then a solution of p-toluenesulfonic acid (41 mh, 0.215 mmol) in THF (1 mL) was slowly added dropwise. After 0.5 h, a solution of sodium acetylacetonate (52 mg, 0.430 mmol) in methanol (2 mL) was added to the mixture. The reaction was further stirred for 10 h. After removal of the solvent, the resulting mixture was extracted with dichloromethane and water. The hydrophobic phase was dried over magnesium sulfate, filtered, and concentrated. The residue was recrystallized by dichloromethane and n-hexane to obtain BN-bpy-Pt1 complex as yellow solid (125 mg, 0.176 mmol) in 82% yield. .sup.1H NMR (CDCl.sub.3, 400 MHz): ? 8.71 (d, .sup.3J=5.6 Hz, 1H), 8.17-8.15 (m, 2H), 7.53 (d, .sup.3J=7.2 Hz, 1H), 7.13 (t, .sup.3J=7.6 Hz, 2H), 6.65 (s, 4H), 5.54 (s, 1H), 2.83 (s, 2H), 2.19 (s, 6H), 2.05 (s, 3H), 2.03 (s, 3H), 1.83 (s, 12H); .sup.11B NMR (CDCl.sub.3, 128 MHz): ? 1.40.
(148) Synthesis of IMes-BMes.sub.2 Chelate SM1
(149) ##STR00018##
(150) IMesHCl (0.503 g, 1.47 mmol) was loaded into an oven-dried 100 mL Schlenk flask and placed under a nitrogen atmosphere. Dry degassed THF (50 mL) was added to the flask via cannula and a white slurry formed. The slurry was chilled to ?78? C. in a dry ice/acetone bath and 1.00 mL of 1.6M nBuLi in hexane (1.6 mmol) was added drop-wise. This reaction mixture was stirred for 30 minutes in the cold bath followed by 2 hours out of the bath to generate free carbene. The flask was then cooled a second time to ?78? C. followed by addition of freshly distilled TMEDA (0.97 mL; 6.47 mmol) and 1.00 mL of 1.6 M nBuLi. The reaction mixture was stirred for 2 hours at ?78? C. followed by addition of Mes.sub.2BF (0.473 g, 1.76 mmol). The reaction mixture was stirred for 3 hours while at ?78? C. before warming to room temperature and stirring overnight. The resulting mixture was quenched with water and extracted with diethyl ether. An organic extract was dried over MgSO.sub.4 followed by removal of volatiles in vaccuo. A resulting solid was dissolved in a minimum of diethyl ether and was precipitated by addition of hexane. The solid was collected by vacuum filtration and 0.723 g (89%) of the chelate product SM1 was collected. X-ray quality crystals were grown using a saturated solution of THF layered with hexanes. .sup.1H NMR (C.sub.6D.sub.6): ?=1.67 (s, 3H, ArCH.sub.3), 1.68 (s, 3H, ArCH.sub.3), 1.85 (s, 3H, ArCH.sub.3), 2.04 (s, 3H, ArCH.sub.3), 2.07 (s, 3H, ArCH.sub.3), 2.08 (s, 3H, ArCH.sub.3), 2.08 (s, 3H, ArCH.sub.3), 2.13 (s, 3H, ArCH.sub.3), 2.17 (s, 3H, ArCH.sub.3), 2.46 (s, 3H, ArCH.sub.3), 2.84 (d, 1H, .sup.3J.sub.HH=12.0 Hz, BCH.sub.2), 2.88 (s, 3H, ArCH.sub.3), 3.06 (d, 1H, .sup.3J.sub.HH=12.0 Hz, BCH.sub.2), 5.78 (d, 1H, .sup.3J.sub.HH=4.0 Hz, Imidazole-CH), 5.97 (s, 1H, ArH), 6.18 (s, 1H, ArH), 6.48 (s, 1H, ArH), 6.52 (s, 1H, ArH), 6.52 (s, 1H, ArH), 6.62 (d, 1H, .sup.3J.sub.HH=4.0 Hz, Imidazole-CH), 6.72 (s, 1H, ArH), 6.73 (s, 1H, ArH), 6.73 (s, 1H, ArH). .sup.11B[.sup.1H] NMR (C.sub.6D.sub.6): ?=?11.2. .sup.13C {.sup.1H} NMR (C.sub.6D.sub.6): ?=19.1 (ArCH.sub.3), 19.1 (ArCH.sub.3), 20.0 (ArCH.sub.3), 20.8 (ArCH.sub.3), 20.8 (ArCH.sub.3), 21.0 (ArCH.sub.3), 21.0 (ArCH.sub.3), 24.0 (ArCH.sub.3), 24.9 (ArCH.sub.3), 27.7 (ArCH.sub.3), 27.9 (ArCH.sub.3), 33.5 (located by HSQC, BCH.sub.2), 120.0 (Imidazole-CH), 121.3 (Imidazole-CH), 125.3 (ArC), 125.7 (ArC), 6 ArCH located under the solvent signal via HSQC, 129.0 (ArCH), 130.3 (ArC), 130.8 (ArCH), 131.5 (ArC), 131.9 (ArC), 133.0 (ArC), 133.1 (ArC), 134.4 (ArC), 135.9 (ArC), 137.0 (ArC), 138.3 (ArC), 138.7 (ArC), 141.3 (ArC), 141.9 (ArC), 143.1 (ArC), 145.4 (ArC), 207.4 (NCN). Anal. Calcd. for C.sub.39H.sub.45N.sub.2B: C, 84.77; H, 8.21; N, 5.07.
(151) Synthesis of DT1
(152) ##STR00019##
(153) To a stirred solution of (2-methyl)phenylpyridine (200 mg, 1.18 mmol), and TMEDA (0.35 mL, 2.36 mmol) in THF (10 mL) at ?78? C., a solution of .sup.nBuLi (2.5 M, 0.95 mL, 2.36 mmol) was added dropwise. After 1.5 hours at ?78? C., B(O.sup.iPr).sub.3 (0.44 mL, 1.9 mmol) was added dropwise and the solution stirred for 1 hour at this temperature. After this time the mixture was warmed to 0? C. and LiAlH.sub.4 (179 mg, 4.72 mmol) added in one portion and the resulting milky mixture stirred for 1 hour at 0? C. and warmed up to room temperature and stirred for overnight. Water was added dropwise to quench the reaction, ether was used to extract the reaction. The organic layers were combined and dried by MgSO.sub.4, the solvent was removed in vaccuo and the crude was purified by silica column chromatography, white solid DT1 was obtained (39 mg, 0.21 mmol, 18% yield).
(154) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=8.39 (d, J=5.6 Hz, 1H), 7.45 (d, J=7.8 Hz, 1H), 7.29 (m, 2H), 7.09 (m, 2H), 6.81 (t, J=7.8 Hz, 1H), 6.24 (t, J=5.6 Hz, 1H), 4.24-3.19 (m, 2H), 2.56 (t, J=5.2 Hz, 2H). .sup.11B NMR (128 MHz, C.sub.6D.sub.6) ?=?7.53 (J=94.6 Hz).
Example 2. Synthesis of Elimination Products Via Photoelimination
(155) General Procedure for the Generation of Elimination Products (e.g., Azaborine Compounds) by Photoelimination
(156) Photolysis was carried out in Norell quartz NMR tube using a Rayonet Photochemical Reactor. Samples were dissolved in freshly distilled C.sub.6D.sub.6 (0.5 mL) and sealed under N.sub.2. The reaction time was dependent on the concentration of the solution. For a sample concentration of about 1.0 mg in 0.5 mL solvent, precursor compounds were converted to elimination products under irradiation for 12 hrs. For a sample concentration at ?1.0?10.sup.?5 M, full conversion required about 30-40 minutes of UV irradiation, as established by UV-Vis and fluorescence data. After the removal of solvent, mesitylene was isolated from the elimination product by subjecting the residue to vacuum at 90? C. for a few days, or by column chromatograph. Conversion of precursor compounds to their corresponding products was monitored by .sup.1H NMR/.sup.11B NMR spectra. Details of this procedure are illustrated with BN-3a as a representative example.
(157) Representative Example of Solution State Conversion: Photoelimination of BN-3 to Form BN-3a
(158) Compound BN-3 was dissolved in freshly distilled C.sub.6D.sub.6 (0.5 mL) in a Norell quartz NMR tube and sealed under nitrogen. The NMR tube was placed inside a Rayonet Photochemical Reactor (available from Southern New England Ultraviolet Company, Branford, Conn., USA), and irradiated with 350 nm UV lamps. Progression of the elimination reaction was monitored by .sup.1H NMR spectroscopy. Photolysis time was dependent on the concentration of the solution. For a sample concentration of about 1.0 mg in 0.5 mL solvent, BN-3 was converted to BN-3a in ?70% yield with ?12 hrs irradiation. For a large preparative scale photolysis, this reaction may be carried out in a quartz flask. The photolysis can also be carried in a sealed quartz cuvette in toluene and monitored by UV-Vis and fluorescence spectroscopy. For a sample concentration of ?1.0?10.sup.?5 M, full conversion required about 30 minutes. Compound BN-3a can be isolated by first removing the solvent under vacuum at ambient temperature, then heating the residue under vacuum at 90? C. for 3 days to remove mesitylene. Recrystalization from hexane produced bright yellow crystals of BN-3a. .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): ? 7.82 (d, J=8.4 Hz, 1H), 7.69 (s, 1H), 7.59 (d, J=8.7 Hz, 1H), 7.26 (s, 1H), 7.20 (d, J=7.9 Hz 1H), 7.12 (s, 2H), 7.04 (m, 2H), 6.89 (m, 1H), 6.81 (m, 1H), 2.43 (s, 3H), 2.34 (s, 6H), 2.26 (s, 3H). .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): ? 148.25, 144.73, 144.04, 139.74, 137.08, 132.21, 129.96, 129.06, 128.56, 128.07, 127.88, 127.69, 126.44, 125.78, 124.42, 121.92, 118.78, 117.67, 22.93, 21.26, 21.22. .sup.11B NMR (C.sub.6D.sub.6, 160 MHz): ? 35.4; HR-EIMS (m/z): [M.sup.+] calcd. for C.sub.24H.sub.22BNS, 367.1577; found 367.1570. See Table 3 for photophysical properties of BN-3a.
(159) Representative Example of Solid State Conversion: Photoelimination of BN-3 to Form BN-3a in a PMMA Film
(160) PMMA (Poly(methyl methacrylate)) was purified by dissolving it in THF, followed by suspending it in water, then filtering and drying the polymer under vacuum for 3 days. About 10 mg of the purified PMMA powder and 1 mg of BN-3 were mixed and dissolved in 2 mL of dry THF in a glove box under a nitrogen atmosphere. This solution was used to cast a thin film on either a quartz glass slide or one side of a quartz cuvette. After the film was dried, it was subjected to UV irradiation by either a hand-held UV lamp at 365 nm or a UV reactor at 350 nm. To record the UV-Vis spectra, the cuvette was sealed under nitrogen. The formation of BN-3a was observed after a few minutes of exposure to UV light and the full conversion was achieved after about 1.0 hr exposure, based on UV-Vis spectra.
(161) The above solution state and solid state procedures can be used for other precursor compounds such as BN-1, BN-2, BN-4 etc.
(162) Characterization Data for Azaborine Compounds
(163) BN-1a
(164) .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): ? 8.39 (d, J=7.0 Hz, 1H), 8.21 (d, J=8.8 Hz, 1H), 8.15 (d, J=9.0 Hz, 1H), 7.80 (d, J=8.4 Hz, 1H), 7.39 (m, 1H), 7.36 (s, 1H), 7.12 (d, J=8.4 Hz, 1H), 7.11 (s, 2H), 6.81 (m, 1H), 6.28 (m, 1H), 2.42 (s, 3H), 2.30 (s, 6H); .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): ? 145.33, 142.48, 140.53, 137.35, 136.93, 136.46, 128.82, 128.72, 128.26, 127.10, 124.71, 121.78, 119.86, 118.99, 115.91, 22.56, 21.05; .sup.11B NMR (C.sub.6D.sub.6, 160 MHz): ? 35.52; HR-EIMS (m/z): [M.sup.+] calcd. C.sub.21H.sub.20BN, for 297.1693; found 297.1695. See Table 3 for photophysical properties of BN-1a.
(165) BN-2a
(166) .sup.1H NMR (C.sub.6D.sub.6, 600 MHz): ? 8.38 (d, J=7.0 Hz, 1H), 8.16 (s, 1H), 8.15 (s, 1H), 7.80 (d, J=8.5 Hz, 1H), 7.34 (s, 1H), 7.27 (d, J=8.5 Hz, 1H), 7.13 (s, 2H), 6.20 (d, J=7.0 Hz, 1H), 2.45 (s, 3H), 2.43 (s, 3H), 2.37 (s, 6H) 1.93 (s, 3H); .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): ? 144.17, 142.15, 140.60, 139.12, 137.35, 136.79, 136.19, 131.24, 128.86, 128.24, 127.10, 123.41, 120.81, 118.42, 118.15, 116.86, 22.66, 21.68, 21.20, 20.88; .sup.11B NMR (C.sub.6D.sub.6, 160 MHz): ? 34.97. HR-EIMS (m/z): [M.sup.+] calcd. for C.sub.23H.sub.24BN, 325.2006; found 325.1997. See Table 3 for photophysical properties of BN-2a.
(167) BN-4a
(168) .sup.1H NMR (C.sub.6D.sub.6, 500 MHz): ? 8.18 (d, J=7.0 Hz, 1H), 8.13 (s, 2H), 7.82 (d, J=8.5 Hz, 1H), 7.33 (s, 1H), 7.26 (d, J=8.5 Hz, 1H), 6.33 (d, J=7.0 Hz, 1H), 2.45 (s, 3H), 2.00 (s, 3H), 1.35 (s, 3H); .sup.13C NMR (C.sub.6D.sub.6, 125 MHz): ? 143.98, 143.41, 141.58, 135.05, 131.18, 128.99, 128.49, 123.40, 120.68, 117.66, 116.0, 29.97, 22.79, 21.71; .sup.11B NMR (C.sub.6D.sub.6, 160 MHz): ? 35.03; HR-ESIMS (m/z): [MH.sup.+] calcd. for C.sub.15H.sub.16BN, 222.14486; found 222.14420. See Table 3 for photophysical properties of BN-4a.
(169) (BN)2-1a
(170) This compound was obtained in the same manner as that of BN-1a. It was an insoluable solid and was characterized by HRMS. Calculated Mass for intermediate (one side reacted) (C.sub.39H.sub.42B.sub.2N.sub.2): 560.3547; Observed: 560.3352. Calculated Mass for (BN)2-1a the product (C.sub.30H.sub.30B.sub.2N.sub.2): 440.2606; observed: 440.2611.
(171) BN-bpy-Pt1a and BN-bpy-B1 can be obtained by the same procedure as that used for BN-1a. (See
(172) BN-5b
(173) 10 mg of BN-5 was dissolved in 0.5 mL of THF-d.sub.8 in a quartz NMR tube and sealed under N.sub.2. This tube was placed in the UV-chamber (300 nm) for 8 hours. White precipitate was observed and the clear solution was characterized by HRMS (EI) showing the formation of the trimer product. HR-ESIMS (m/z): C.sub.36H.sub.24B.sub.3N.sub.3, Calculated 531.2267; observed 531.2231. In addition, the patterns for both closely match one another.
(174) Procedure for Photoelimination of BC-1 to its Trimer BC-1b
(175) This procedure was done according to the Scheme 8a. BC-1 was loaded into a quartz NMR tube inside a glove box and dissolved in dry degassed C.sub.6D.sub.6. The NMR tube was brought out into the open environment with the cap tightly fastened and wrapped in many layers of PARAFILM?. The NMR tube was suspended in a UV reactor and 300 nm light irradiated the sample. The reaction was monitored by NMR over 2 weeks. The chemical shift of H.sub.2 at 4.47 ppm was observed and the intensity of BC-1 peaks decreased gradually with irradiation time. Inside the NMR tube a colorless precipitate began to accumulate which was believed to be the trimer BC-1b.
(176) Synthesis of Azaborine SM1-aza
(177) ##STR00020##
(178) BMes.sub.2 chelate (25 mg) was loaded into a quartz NMR tube in a nitrogen atmosphere glove box. Distilled C.sub.6D.sub.6 (0.7 mL) was added and the tube was capped and sealed with Teflon tape and Parafilm?. The tube was exposed to 300 nm UV light for 3 days with brief interruptions to monitor the NMR spectra. Once the starting material was present in equal amount to the product, by peak integration, the tube was reintroduced to the glovebox and the solution was allowed to slowly evaporate for about 24 hrs. A resulting residue was washed with a small amount of toluene and decanted to separate it from the remaining crystalline solid. 12 mg (48%) of the crystalline solid remained and was found to be the pure SM1-aza azaborine product. Single crystals were grown from a concentrated solution of THF which was allowed to evaporate slowly to half volume then chilled to ?35? C. Synthesis of SM1-aza may also be performed on a large scale using freshly distilled THF as the solvent in a sealed flask Yields were near 50%, in line with expectations. The new azaborine compound SM1-aza was determined to be a blue fluorescent emitter with emission quantum efficiency=0.60.
(179) .sup.1H NMR (C.sub.6D.sub.6): ?=1.77 (s, 6H, ArCH.sub.3), 2.04 (s, 3H, ArCH.sub.3), 2.26 (s, 3H, ArCH.sub.3), 2.30 (s, 6H, ArCH.sub.3), 2.31 (s, 3H, ArCH.sub.3), 2.54 (s, 3H, ArCH.sub.3), 6.22 (d, 1H, .sup.3J.sub.HH=4.0 Hz, Imidazole-CH), 6.43 (s, 2H, ArH), 6.66 (s, 2H, ArH), 6.71 (s, 1H, ArH), 7.46 (s, 1H, BCH), 7.60 (s, 1H, ArH), 8.04 (d, 1H, .sup.3J.sub.HH=4.0 Hz, Imidazole-CH). .sup.11B [.sup.1H] NMR (C.sub.6D.sub.6): ?=28.3.
(180) Synthesis of DT1-aza
(181) ##STR00021##
(182) Photolysis was carried out in quartz J-Young NMR tube using a Rayonet Photochemical Reactor. Samples were dissolved in freshly distilled C.sub.6D.sub.6 (0.5 mL) and sealed under N.sub.2. The reaction time was dependent on the concentration of the solution. For a sample concentration of about 1.0 mg in 0.5 mL solvent, the precursor compound DT1 can be converted to the corresponding azaborine compound DT1-aza under irradiation for 24 hours.
(183) .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=8.29 (d, J=6.7 Hz, 1H), 8.18 (d, J=8.7 Hz, 1H), 8.04 (d, J=8.6 Hz, 1H), 7.87 (d, J=8.5 Hz, 1H), 7.65 (s, 1H), 7.42 (t, J=8.2 Hz, 1H), 7.16 (m, 1H), 6.86-6.77 (m, 2H), 6.37-6.28 (m, 2H). .sup.11B NMR ?=(128 MHz, C.sub.6D.sub.6) ? 32.31 (J=138.8 Hz).
Example 3. Fabrication on EL Device
(184) An OLED device was fabricated in a glove box under an inert atmosphere. 100 ?L of 1,2-dicholorobenzene solution of 3 wt % of PVK with 5 wt % BN-3 as the dopant was placed onto freshly-treated ITO glass (UV and Ozone for 10 min) and spin-cast at 2,000 rpm for 2 min, 4,000 rpm for 1 min, and 9,000 rpm for 2 min. Films were dried at 50? C. for at least 2 h before UV-irradiation was applied. The thickness of the films was less than 100 nm. The films were then irradiated by UV light at 265 or 350 nm to convert the BN-3 dopant to BN-3a. A layer of Calcium metal (200 nm) was thermally evaporated as electrode under vacuum (<2.0?10?6 torr). A Keithley 237 source measurement unit, a Keithley 2010 multimeter, and a Hamamatsu amplified photodiode were used to drive the devices and to measure the current-voltage-light intensity characteristics of the devices. The EL spectra of the devices are recorded by using an Ocean optics HR2000 high-resolution spectrometer. See
Example 4. Synthesis of Elimination Products Via Thermoelimination
(185) General Procedure for the Generation of Elimination Products (e.g., Azaborine Compounds) by Thermoelimination
(186) Pyrolysis was carried out in a sealed flask or a sealed Wilmad-lab Glass pressure/vacuum NMR tube. Solid samples of precursor compounds were placed inside the flask or the NMR tube and sealed under vacuum. An oil bath or a sand bath was placed on top of a hot plate and heated to the desired temperature as monitored by a thermometer. The flask or tube containing the precursor compound was then placed in either the oil bath or the sand bath. Conversion of the precursor compound to azaborine via heating to induce a thermoelimination reaction was monitored by appearance of bright fluorescence, which is characteristic of the azaborine compound. The reaction time required was dependent on the amount of sample used. After the reaction was completed, the product was isolated by crystallization from either toluene or THF and characterized by .sup.1H/.sup.11B NMR spectra. Details of this general procedure are illustrated with BN-1a as a representative example.
(187) In a NMR tube was placed ?10 mg of non-fluorescent precursor compound BN-1. The NMR tube was then evacuated under vacuum and the valve of the NMR tube was closed. An oil bath was heated to 230? C. on top of a Corning hot plate. After the temperature of the oil bath was stabilized, the NMR tube was placed in the oil bath and maintained for ?10 minutes. Bright green fluorescence was observed from the reaction mixture. After the tube and contents were cooled to ambient temperature, a fluorescent solid was observed. A sample of this product of pyrolysis was dissolved in C.sub.6D.sub.6 and .sup.1H and .sup.11B NMR spectra were recorded. The spectra confirmed the presence of azaborine product BN-1a. In addition, the NMR spectra showed evidence of a second azaborine product that was larger (higher molecular weight) than BN-1a. Although not wishing to be bound by theory, the inventors suggest that the second azaborine may be a dimer or trimer of BN-1a.
(188) High resolution mass spectra (electron-spray ionization, ESI mode) for a sample of the pyrolysis mixture were recorded on an AB Sciex Qsar XL ESI Quadrupole Time of Flight Mass Spectrometer. Calculated {[BN-1a]+1} ion, 297.1765; observed: 298.1758. Other high MS peaks were observed: 418.2813, 440.2717 and 536.6386.
(189) It will be understood by those skilled in the art that this description is made with reference to certain preferred embodiments and that it is possible to make other embodiments employing the principles of the invention which fall within its spirit and scope as defined by the claims.
Schemes
(190) ##STR00022##
(191) ##STR00023##
(192) ##STR00024##
(193) ##STR00025## ##STR00026##
(194) ##STR00027##
(195) ##STR00028## ##STR00029##
(196) ##STR00030## ##STR00031##
(197) ##STR00032##
(198) ##STR00033##
(199) ##STR00034##
(200) ##STR00035##
(201) ##STR00036##
(202) ##STR00037##
(203) ##STR00038##
(204) ##STR00039##
(205) TABLE-US-00001 TABLE 1 Structural formulae of starting materials and photoelimination products. Ligand Precursor Elimination Product Terms
(206) TABLE-US-00002 TABLE 2 Selective examples of fully conjugated molecules based on trimer compounds
(207) TABLE-US-00003 TABLE 3 Electronic and photophysical properties of selected azaborines Fluores- UV/Vis in Fluorescence UV/Vis cence PMMA.sup.c in PMMA.sup.c E.sub.l/2.sup.red (nm).sup.a (nm).sup.a ?.sub.FL.sup.b (nm) (nm) (V).sup.d BN-1a 422, 447, 493 513 0.27 447, 470 505 ?2.49 470 BN-2a 428, 455, 500 ~1.00 452, 476 510 ?2.48 478 BN-3a 430,455, 524 0.16 455, 483 514 ?2.44 481 BN-4a 425, 449, 509 ~1.00 454, 479 507 n/a.sup.g 474 .sup.a1.0 ? 10.sup.?5 in toluene. .sup.bDetermined using Ir(ppy).sub.3 as the standard (? = 0.92) in toluene. .sup.c10 wt % PMMA films. .sup.dRelative to the potential of FeCp.sub.2.sup.0/+, recorded in a CH.sub.3CN-THF solvent mixture.