Donor-acceptor aggregation-induced emission luminogen with multi-stimuli responsive behavior
11629289 · 2023-04-18
Assignee
Inventors
Cpc classification
C07C211/56
CHEMISTRY; METALLURGY
H10K2101/30
ELECTRICITY
H10K85/631
ELECTRICITY
H10K2101/40
ELECTRICITY
International classification
C07C211/56
CHEMISTRY; METALLURGY
Abstract
Provided herein are aggregation-induced emission luminogens, methods of preparation and use thereof, and devices and sensors comprising the same. The aggregation-induced emission luminogens can exhibit multi-stimuli responsive emissions.
Claims
1. A compound having Formula 8: ##STR00034## wherein each of R.sup.6 and R.sup.7 is independently selected from hydrogen and alkyl.
2. The compound of claim 1, wherein each of R.sup.6 and R.sup.7 is methyl.
3. A method of preparing the compound of claim 1, the method comprising: contacing a compound of Formula: ##STR00035## wherein M is lithium, sodium, MgBr, or a Zn species with a compound of Formula: ##STR00036## wherein each of R.sup.6 and R.sup.7 is independently selected from hydrogen and alkyl; and X is a halide; thereby forming the compound of claim 1.
4. A method for detecting a change in a physical-chemical parameter in a test sample comprising the compound of claim 1, the method comprising: providing the test sample; measuring a fluorescence emission of the test sample; comparing a measured fluorescence emission of the test sample with a fluorescence emission of a control sample comprising the compound of claim 1 in a ground state; and based on the difference in fluorescence emission between the test sample and the control sample determine whether there is a change in the physical-chemical parameter, wherein the ground state is a fluorescence emission of the compound of claim 1 in the absence of the physical-chemical parameter.
5. The method of claim 4, Wherein the physical-chemical parameter is at least one parameter selected from the group consisting of a temperature of the test sample, a sheer force exerted on the test sample, an oxidation state of the test sample, a solvent in the test sample; and an isotropic hydrostatic pressure of the test sample.
6. The method claim 4, wherein the compound has the formula; ##STR00037##
7. An organic light emitting diode (OLED) comprising the compound of claim 1.
8. The organic light emittig diodo (OLED) of claim 7, wherein the compound has the formula: ##STR00038##
Description
BRIEF DESCRIPTION OF THE FIGURES
(1) The above and other objects and features of the present disclosure will become apparent from the following description of the disclosure, when taken in conjunction with the accompanying drawings.
(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)
(28)
(29)
(30)
(31)
(32) The figures are not necessarily drawn to scale.
DETAILED DESCRIPTION
(33) The present disclosure generally relates to AIE-active small molecules containing TAB and amine units, which are responsive to multiple external stimuli including solvent, temperature, mechanical shearing force, hydrostatic pressure and electric field. More specifically, this new material exhibits solvatochromism and a wide range of thermoresponsive behavior with high upper limit, which can realize the visualization of both marked and subtle environmental polarity change by the dramatically amplified luminescence signal and macroscopic color change. Furthermore, it can respond to anisotropic shearing force and isotropic hydrostatic pressure with remarkable but contrasting luminescence conversion. Meanwhile, it was sensitive to external electric stimulus displaying reversibly three-color switched electrochromism and on-to-off electrochromic photoluminescence. Such properties allow the fabrication of a high-performance non-doped OLED with a high external quantum efficiency of 5.22%. The present system featuring multi-stimulus responsive properties has application in various real-life applications, including the visualization of marked or subtle polarity change, wide-range liquid thermometer, security inks and papers, electroswitchable electrochromic material for information recording, storage device and OLED.
(34) Definitions
(35) Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.
(36) In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition, an apparatus, or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein
(37) The use of the terms “include,” “includes”, “including,” “have,” “has,” or “having” should be generally understood as open-ended and non-limiting unless specifically stated otherwise.
(38) The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term “about” is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term “about” refers to a ±10%, ±7%, ±5%, ±3%, ±1%, or ±0% variation from the nominal value unless otherwise indicated or inferred.
(39) It should be understood that the order of steps or order for performing certain actions is immaterial so long as the present teachings remain operable. Moreover, two or more steps or actions may be conducted simultaneously.
(40) As used herein, “halo”, “halide”, or “halogen” refers to fluoro, chloro, bromo, and iodo.
(41) As used herein, “alkyl” refers to a straight-chain or branched saturated hydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and z′-propyl), butyl (e.g., n-butyl, z′-butyl, sec-butyl, tert-butyl), pentyl groups (e.g., n-pentyl, z′-pentyl, -pentyl), hexyl groups, and the like. In various embodiments, an alkyl group can have 1 to 40 carbon atoms (i.e., C.sub.1-C.sub.40 alkyl group), for example, 1-30 carbon atoms (i.e., C.sub.1-C.sub.30 alkyl group). In some embodiments, an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a “lower alkyl group.” Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and z′-propyl), and butyl groups (e.g., n-butyl, z′-butyl, sec-butyl, tert-butyl). In some embodiments, alkyl groups can be substituted as described herein. An alkyl group is generally not substituted with another alkyl group, an alkenyl group, or an alkynyl group.
(42) The term “aralkyl” is art-recognized and refers to an alkyl group substituted with an aryl group (e.g., an aromatic or heteroaromatic group).
(43) As used herein, “cycloalkyl” by itself or as part of another substituent means, unless otherwise stated, a monocyclic hydrocarbon having between 3-12 carbon atoms in the ring system and includes hydrogen, straight chain, branched chain, and/or cyclic substituents. Exemplary cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
(44) As used herein, “alkenyl” refers to a straight-chain or branched alkyl group having one or more carbon-carbon double bonds. Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl groups, and the like. The one or more carbon-carbon double bonds can be internal (such as in 2-butene) or terminal (such as in 1-butene). In various embodiments, an alkenyl group can have 2 to 40 carbon atoms (i.e., C.sub.2-C.sub.40 alkenyl group), for example, 2 to 20 carbon atoms (i.e., C.sub.2-C.sub.20 alkenyl group). In some embodiments, alkenyl groups can be substituted as described herein. An alkenyl group is generally not substituted with another alkenyl group, an alkyl group, or an alkynyl group.
(45) As used herein, a “fused ring” or a “fused ring moiety” refers to a polycyclic ring system having at least two rings where at least one of the rings is aromatic and such aromatic ring (carbocyclic or heterocyclic) has a bond in common with at least one other ring that can be aromatic or non-aromatic, and carbocyclic or heterocyclic. These polycyclic ring systems can be highly p-conjugated and optionally substituted as described herein.
(46) As used herein, “heteroatom” refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
(47) As used herein, “aryl” refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings. An aryl group can have 6 to 24 carbon atoms in its ring system (e.g., C.sub.6-C.sub.24 aryl group), which can include multiple fused rings. In some embodiments, a polycyclic aryl group can have 8 to 24 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical structure. Examples of aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic), pentacenyl (pentacyclic), and like groups. Examples of polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a benzimidazolinyl group, which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system), and pyran (i.e., a chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system). Other examples of aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like. In some embodiments, aryl groups can be optionally substituted as described herein. The aryl ring may be substituted at one or more positions with such substituents as described herein, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, a heterocyclyl, an aromatic or heteroaromatic moiety, —CF.sub.3, —CN, or the like. In some embodiments, an aryl group can have one or more halogen substituents, and can be referred to as a “haloaryl” group. Perhaloaryl groups, i.e., aryl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., —C.sub.6F.sub.5), are included within the definition of “haloaryl.” In certain embodiments, an aryl group is substituted with another aryl group and can be referred to as a biaryl group. Each of the aryl groups in the biaryl group can be optionally substituted as disclosed herein.
(48) As used herein, “heteroaryl” refers to an aromatic monocyclic ring system containing at least one ring heteroatom selected from oxygen (O), nitrogen (N), sulfur (S), silicon (Si), and selenium (Se) or a polycyclic ring system where at least one of the rings present in the ring system is aromatic and contains at least one ring heteroatom. Polycyclic heteroaryl groups include those having two or more heteroaryl rings fused together, as well as those having at least one monocyclic heteroaryl ring fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromatic cycloheteroalkyl rings. A heteroaryl group, as a whole, can have, for example, 5 to 24 ring atoms and contain 1-5 ring heteroatoms (i.e., 5-20 membered heteroaryl group). The heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure. Generally, heteroaryl rings do not contain O—O, S—S, or S—O bonds. However, one or more N or S atoms in a heteroaryl group can be oxidized (e.g., pyridine N-oxide thiophene S-oxide, thiophene S,S-dioxide). Examples of heteroaryl groups include, for example, the 5- or 6-membered monocyclic and 5-6 bicyclic ring systems shown below: where T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (e.g., N-benzyl), SiH.sub.2, SiH(alkyl), Si(alkyl).sub.2, SiH(arylalkyl), Si(arylalkyl).sub.2, or Si(alkyl)(arylalkyl). Examples of such heteroaryl rings include pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, 1H-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuyl, naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl, furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl groups, and the like. Further examples of heteroaryl groups include 4,5,6,7-tetrahydroindolyl, tetrahydroquinolinyl, benzothienopyridinyl, benzofuropyridinyl groups, and the like. In some embodiments, heteroaryl groups can be optionally substituted as described herein. The heterocyclic ring may be substituted at one or more positions with such substituents as described herein, as for example, halogen, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, a heterocyclyl, an aromatic or heteroaromatic moiety, —CF.sub.3, —CN, or the like.
(49) The term “optionally substituted” refers to a chemical group, such as alkyl, cycloalkyl, aryl, heteroaryl, and the like, wherein one or more hydrogen may be replaced with a with a substituent as described herein, for example, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, —CF.sub.3, —CN, or the like
(50) The representation “I” as used herein in connection to chemical a group or moiety is intended to represent the covalent bond that the aforementioned chemical group or moiety is covalently bonded to another chemical group or moiety.
(51) The phrase “aggregation-induced emission” or “AIE” as used herein refers to the enhancement of light-emission by a fluorescent compound upon aggregation in the amorphous or crystalline (solid) states of the fluorescent compound, whereas the fluorescent compound exhibits weak or substantially no emission in dilute solutions.
(52) The term “λ.sub.ex” as used herein refers to the excitation wavelength.
(53) The term “λ.sub.em” as used herein refers to the emission wavelength.
(54) Inspired by the distinctive stimuli-responsive behaviors of natural creatures, a simple but versatile class of aggregation-induced emission luminogen (AIEgen) compounds with donor-acceptor structure and pronounced intramolecular charge transfer property, exemplified by AIEgen 1, was developed. The compounds described herein can exhibit solvatochromism and a wide range of thermoresponsive behavior with high upper limit, which can realize the visualization of both marked and subtle environmental polarity change by the dramatically amplified luminescence signal and macroscopic color change. Furthermore, the compounds described herein can respond to numerous environmental or physical-chemical changes, such as anisotropic shearing force and isotropic hydrostatic pressure with remarkable but contrasting luminescence conversion due to the distinct disturbance of the weak intermolecular interactions and charge transfer processes.
(55) The compounds described herein can also be sensitive to external electric stimulus displaying reversibly three-color switched electrochromism and on-to-off electrochromic photoluminescence. Such property allowed the fabrication of high-performance non-doped OLED with a high external quantum efficiency of 5.22%. The present results may offer an efficient guideline for multifunctional molecular design and provide an important step forward in expanding the real-life applications of AIE-active materials.
(56) Provided herein is a compound of Formula 1:
(57) ##STR00015##
(58) wherein each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 is independently selected from the group consisting of aryl and heteroaryl.
(59) In certain embodiments, the Ar.sup.4—N nitrogen is covalently bonded to Ar.sup.5 in a position in which the lone pair on the said nitrogen is conjugated through the pi system of Ar.sup.5 with the boron.
(60) In certain embodiments, each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 is independently optionally substituted aryl or heteroaryl. Each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 can independently be optionally substituted with a substituent selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl, wherein R is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl. Each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 can independently be optionally substituted with 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 substituents.
(61) In certain embodiments, each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 is independently optionally substituted phenyl.
(62) In certain embodiments, the compound has the Formula 2:
(63) ##STR00016##
(64) wherein each of m and n is independently 1, 2, 3, or 4;
(65) R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instance of R.sup.1 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or two instance of R.sup.2 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or one instance of R.sup.1 and one instance of R.sup.2 taken together form a covalent bond; and
(66) R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl.
(67) In certain embodiments of the compound of Formula 2, each of m and n is 1 or 2; and R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(68) In certain embodiments of the compound of Formula 2, each of Ar.sup.1, Ar.sup.2, Ar.sup.4, Ar.sup.6, and Ar.sup.7 is independently aryl. In certain embodiments, each of Ar.sup.1, Ar.sup.2, Ar.sup.4, Ar.sup.6, and Ar.sup.7 is independently optionally substituted phenyl.
(69) In certain embodiments, the compound has the Formula 3:
(70) ##STR00017##
(71) wherein each of m and n is independently 1, 2, 3, or 4;
(72) each of o, p, q, t, and u is independently 1, 2, 3, 4, or 5;
(73) R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instance of R.sup.1 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or two instance of R.sup.2 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or one instance of R.sup.1 and one instance of R.sup.2 taken together form a covalent bond;
(74) R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or one instance of R.sup.4 and on instance of R.sup.5 form a covalent bond; or one instance of R.sup.3 and one instance of R.sup.1 taken together form a covalent bond; or one instance of R.sup.3 and one instance of R.sup.4 taken together form a covalent bond; or one instance of R.sup.1 and one instance of R.sup.5 taken together form a covalent bond; or one instance of R.sup.2 and one instance of R.sup.5 taken together form a covalent bond; or one instance of R.sup.2 and one instance of R.sup.7 taken together form a covalent bond; or one instance of R.sup.6 and one instance of R.sup.7 taken together form a covalent bond; and
(75) R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl.
(76) In certain embodiments of the compound of Formula 3, each of m and n is 1; and each of o, p, q, t, and u is 1.
(77) In certain embodiments, the compound has Formula 3a:
(78) ##STR00018##
(79) wherein each of u and t is independently 1, 2, or 3;
(80) R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; and R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl.
(81) In certain embodiments of the compound of Formula 3a, R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(82) In certain embodiments of the compound of Formula 3a, each of R.sup.1 and R.sup.2 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl. In certain embodiments of the compound of Formula 3a, R.sup.1 and R.sup.2 are hydrogen.
(83) In certain embodiments of the compound of Formula 3a, each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(84) In certain embodiments of the compound of Formula 3a, R.sup.1 and R.sup.2 are hydrogen; R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 for each instance is independently selected from hydrogen, —OR, —SR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; and R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(85) In certain embodiments, the compound has Formula 4:
(86) ##STR00019##
(87) each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl, wherein R is alkyl, aryl, or heteroaryl.
(88) In certain embodiments of the compound of Formula 4, each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently selected from the group consisting of hydrogen, —OR, alkyl, alkenyl, alkynyl, aryl, and heteroaryl, wherein R is alkyl, aryl, or heteroaryl.
(89) In certain embodiments, the compound has Formula 5:
(90) ##STR00020##
(91) wherein each of m and n is independently 1 or 2;
(92) each of R.sup.1 and R.sup.2 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl;
(93) each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; and
(94) R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl.
(95) In certain embodiments of the compound has Formula 5, each of R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(96) In certain embodiments of the compound of Formula 5, each of R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(97) In certain embodiments of the compound has Formula 5, each of R.sup.6 and R.sup.7 is hydrogen, alkyl, cycloalkyl, aryl, or heteroaryl.
(98) In certain embodiments of the compound has Formula 5, each of R.sup.1 and R.sup.2 is hydrogen; each of R.sup.3, R.sup.4, and R.sup.5 is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; and each of R.sup.6 and R.sup.7 is hydrogen, alkyl, cycloalkyl, aryl, or heteroaryl.
(99) In certain embodiments, the compound has Formula 6:
(100) ##STR00021##
(101) wherein each of m and n is independently 1 or 2;
(102) each of t and u is independently 1, 2, or 3;
(103) R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instance of R.sup.1 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or two instance of R.sup.2 taken together form a 5-6 membered cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; or one instance of R.sup.1 and one instance of R.sup.2 taken together form a covalent bond; or one instance of R.sup.2 and one instance of R.sup.6 taken together form a covalent bond;
(104) R.sup.6 and R.sup.7 for each instance is independently selected from the group consisting of hydrogen, halide, nitrile, nitro, —OR, —SR, —NR.sub.2, —(C═O)R, —(C═O)OR, —(C═O)NR.sub.2, —N(R)(C═O)R, —O(C═O)R, —N(R)(C═O)OR, —O(C═O)NR.sub.2, —SO.sub.2R, —SO.sub.2NR.sub.2, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or one instance of R.sup.4 and on instance of R.sup.5 form a covalent bond; or one instance of R.sup.3 and one instance of R.sup.1 taken together form a covalent bond; or one instance of R.sup.3 and one instance of R.sup.4 taken together form a covalent bond; or one instance of R.sup.1 and one instance of R.sup.5 taken together form a covalent bond; or one instance of R.sup.2 and one instance of R.sup.5 taken together form a covalent bond; or one instance of R.sup.2 and one instance of R.sup.7 taken together form a covalent bond; or one instance of R.sup.6 and one instance of R.sup.7 taken together form a covalent bond; and
(105) R for each instance is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; or two instances of R taken together form a 3-6 membered heterocycloalkyl.
(106) In certain embodiments, the compound has Formula 7:
(107) ##STR00022##
(108) wherein each of m and n is independently 1 or 2; each of Ar.sup.1, Ar.sup.2, and Ar.sup.4 is independently selected from the group consisting of aryl and heteroaryl; R.sup.1 and R.sup.2 for each instance is independently selected from the group consisting of hydrogen alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl; each of R.sup.6 and R.sup.7 for each instance is independently selected from the group consisting of hydrogen, halide, —OR, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocycloalkyl, and heteroaryl.
(109) In certain embodiments of the compound of Formula 7, Ar.sup.1, Ar.sup.2, and Ar.sup.4 is independently optionally substituted phenyl. In certain embodiments of the compound of Formula 7, each R.sup.1 and R.sup.2 is hydrogen; each of Ar.sup.1, Ar.sup.2, and Ar.sup.4 is independently optionally substituted phenyl; and each of R.sup.6 and R.sup.7 for each instance is independently selected from the group consisting of hydrogen, alkyl, aryl, and heteroaryl.
(110) In certain embodiments, the compound has the Formula 8:
(111) ##STR00023##
(112) wherein each of R.sup.6 and R.sup.7 is independently selected from hydrogen and alkyl. In certain embodiments, each of R.sup.6 and R.sup.7 is C.sub.1-C.sub.6 alkyl. In certain embodiments, each of R.sup.6 and R.sup.7 is methyl.
(113) In certain embodiments, the compound is selected from the group consisting of:
(114) ##STR00024## ##STR00025##
wherein z is 0-12.
(115) The compounds described herein can be covalently conjugated to a targeting agent. The targeting agent can be an antibody, an antibody fragment (such as Fab, Fab′, F(ab′).sub.2, and Fv), single chain (ScFv)) a peptide, an aptamer, or a small molecule that is capable of selectively binding to a target of interest, such as a carbohydrate, polynucleotide, lipid, polypeptide, protein, small molecule, cellular receptor, etc.
(116) The compound described herein can be directly attached to the targeting agent or attached to the targeting agent via a chemical linker. In instances where the compound described herein is attached to the targeting agent via a linker, any linker in the art can be used to attach the compound described herein and the targeting agent. The selection of the linker is well within the skill of a person skilled in the art. Exemplary linkers include, but are not limited to polyethylene glycol linkers, alkyl amides, alkyl esters, alkyl sulfonamides, alkyl sulfones, alkanes, aryl amides, aryl esters, aryl sulfonamides, aryl sulfones, aryl, and combinations thereof. The linker can be covalently attached to the targeting agent by an amide bond, ester bond, sulfone bond, sulfur bond, a bond to a trizole, urea bond, ether bond or the like.
(117) In certain embodiments, the compounds described herein comprise a linker. The linker can be covalently attached to the compounds described herein at any at position of the compound subject to the rules of valency. In certain embodiments of any of the compounds described herein, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, or R.sup.7 is the linker, wherein the linker is represented by the formula: -Q.sup.1(CH.sub.2).sub.vY.sup.2, wherein v is a whole number selected between 0-10; Q.sup.1 is a bond, —O—, —(C═O)O—, —O(C═O)—, —(C═O)NH—, or —NH(C═O)—; and Y.sup.2 is —NH.sub.2, —OH, —SH, —CO.sub.2H, alkyne, azide, or N-maleimide; or the linker is represented by the formula: —(OCH.sub.2CH.sub.2).sub.vY.sup.2 or —(CH.sub.2CH.sub.2).sub.v(CH.sub.2).sub.wY.sup.2, wherein each of v and w is independently 1-10; and Y.sup.2 is —NH.sub.2, —OH, —SH, —CO.sub.2H, alkyne, azide, or N-maleimide.
(118) The compounds described herein can be readily prepared using well known organic synthetic methodologies. Synthetic chemists can devise numerous synthetic routes for preparing the compound of Formula 1 using retrosynthetic analysis.
(119) ##STR00026##
(120) In one exemplary approach the carbon boron covalent bond can be formed in the final step of the synthetic methodology as shown below:
(121) ##STR00027##
wherein Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, Ar.sup.5, Ar.sup.6, and Ar.sup.7 are as defined herein.
(122) This synthetic transformation can be accomplished any number of ways. For example, metal catalyzed (e.g., palladium) cross coupling of a tetraryl diborane (e.g., wherein Y.sup.1=—B(Ar.sup.6)(Ar.sup.7)) and a suitably functionalized aryl or heteroaryl halide, tosylate, mesylate, trifluormesylate, or other suitable leaving group (e.g., wherein X.sup.1=halide, tosylate, mesylate, trifluormesylate, and the like). This approach suffers from the waste of half the tetraryldiborane, as only one diaryl borane is coupled in the reaction.
(123) Alternatively, a substitution reaction can be used to couple an aryl or heteroaryl active metal (e.g., wherein X.sup.1 is Li, Na, MgBr, or a zinc species, such as Znalkyl, Znhalide, or
(124) ##STR00028##
and Y.sup.1 is a leaving group (e.g., wherein Y.sup.1 is halide or alkoxide).
(125) In another aspect, provided herein is a method for preparing the compound of Formula 1, the method comprising: the method comprising: contacting a compound of Formula 1a:
(126) ##STR00029##
(127) wherein each of Ar.sup.1, Ar.sup.2, Ar.sup.3, Ar.sup.4, and Ar.sup.5 is independently selected from the group consisting of aryl and heteroaryl; and M is lithium, sodium, MgBr, or a Zn species; with a compound of Formula 1b:
(128) ##STR00030##
(129) wherein each of Ar.sup.6, and Ar.sup.7 is independently selected from the group consisting of aryl and heteroaryl; and X is a halide; thereby forming the compound Formula 1.
(130) Any of the compounds described herein can be prepared in a similar fashion. For example, AIEgen 1 can be prepared when the compound of Formula 1a is:
(131) ##STR00031##
and the compound of Formula 1b is:
(132) ##STR00032##
(133) An exemplary synthesis of AIEgen 1 is depicted in
(134) A person of ordinary skill in the art can readily conceive of the chemical structures of starting materials for preparing any of the compounds described herein based on the teachings provided herein and general knowledge in the art.
(135) The step of contacting the compound of Formula 1a and the compound of Formula 1b can be conducted in relatively unreactive aprotic solvents. Exemplary solvents include, but are not limited to ethers, aromatics, and combinations thereof. Suitable ethers include, but are not limited to diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, dioxane, 1,2,-dimethoxyether (DME), tert-butyl methyl ether, and the like. Suitable aromatics include, but are not limited to, benzene, toluene, xylenes, and the like.
(136) The step of contacting the compound of Formula 1a and the compound of Formula 1b can be first be conducted at a temperature in the range of −100° C. to 20° C. and then optionally be allowed to warm to room temperature. In certain embodiments, the step of contacting the compound of Formula 1a and the compound of Formula 1b can first be conducted at a temperature in the range of −100° C. to 20° C.; −100° C. to 10° C.; −100° C. to 0° C.; −90° C. to 0° C.; −80° C. to 0° C.; −80° C. to −10° C.; −80° C. to −20° C.; −80° C. to −30° C.; or −80° C. to −40° C.; −100° C. to 40° C.; −60° C. to 40° C.; −100° C. to 50° C.; −90° C. to 80° C.; and then allowed to optionally warm to room temperature.
(137) As described in greater detail in this disclosure, the compounds described herein can exhibit multi-stimuli responsive fluorescent emissions. Such properties enable the use of the compound described herein as sensors that are responsive to changes in a physical-chemical parameter.
(138) Thus in another aspect, provided herein is a method for detecting a change in a physical-chemical parameter in a test sample comprising the compound described herein, the method comprising: providing the test sample; measuring the fluorescence emission of the test sample; comparing the measured fluorescence emission of the test sample with the fluorescence emission of a control sample comprising the compound described herein in a ground state; and based on the difference in fluorescence emission between the test sample and the control sample determine whether there is a change in the physical-chemical parameter, wherein the ground state is the fluorescence emission of the compound described herein in the absence of the physical-chemical parameter.
(139) In certain embodiments, the physical-chemical parameter is at least one parameter selected from the group consisting of the temperature of the test sample, the sheer force exerted on the test sample, the oxidation state of the test sample, the solvent in the test sample; the solvent composition of the test sample; and the isotropic hydrostatic pressure of the test sample.
(140) The multi-stimuli responsive emissive behavior of the compounds described herein have numerous applications, such as in liquid thermometers, security inks and papers, electroswitchable electrochromic material for information recording, storage devices and OLED.
(141) The difference in fluorescence emission can be a change in the emission wavelength, change in emission intensity, or a combination thereof.
(142) The EL properties of the compounds described herein can be particularly useful in the fabrication of luminescent devices, such as variously configured OLEDs. OLEDs that can be fabricated using the compound of Formula I include from very simple structures having a single anode and cathode (e.g., monolayer OLEDs) to more complex devices, such as 2-layer or multilayer heterostructure configurations.
(143) In certain embodiments, the OLED comprises an anode, a cathode, and a light emissive layer disposed between the anode and the cathode. In certain embodiments the OLED further comprises a hole-transport layer.
(144) In certain embodiments, the OLED has the structure shown in
(145) In certain embodiments, the electron-injection layer 160 can be subdivided into two or more sublayers (not shown). In one illustrative example of the OLED, the electron-injection layer 170 is further divided into two sublayers, a first electron-injection layer adjacent to the electron-transport layer 150 and a second electron-injection layer located between the first electron-injection layer and the cathode.
(146) In certain embodiments, the hole-injection layer 120 can be subdivided into two or more sublayers (not shown). In one illustrative example of the OLED device, the hole-injection layer 120 is further divided into two sublayers, a first hole-injection layer adjacent to the hole-transport layer 130 and a second hole-injection layer located between the first hole-injection layer and the anode.
(147) In certain embodiments, there is a hole-blocking layer between the light-emitting layer 140 and the electron-transport layer 150 (not shown).
(148) The OLED can be configured such that the EL emission of the anode or alternatively through the cathode. When the EL emission occurs through the anode, the anode 110 should be transparent or substantially transparent to the emitted wavelengths. Commonly used transparent anode materials include, but are not limited to, indium-tin oxide (ITO), indium-zinc oxide (IZO) tin oxide, aluminum- or indium-doped zinc oxide, magnesium-indium oxide, nickel-tungsten oxide, gallium nitride, zinc selenide, zinc sulfide. When the EL emission occurs through the cathode 170, the optical properties of the anode 110 are immaterial and any conductive material, transparent, opaque or reflective can be used. Example conductors for this application include, but are not limited to, gold, iridium, molybdenum, palladium, and platinum.
(149) The anode 110 can be deposited any suitable way such as evaporation, sputtering, chemical vapor deposition, or electrochemical processes. Anodes can be patterned using, e.g., conventional photolithographic processes.
(150) The hole-injection material can serve to facilitate injection of holes into the hole-transport layer 130. The hole-injection layer 120 can be formed of any hole-injection material including those that are commonly used. Non-limiting examples of hole-injection materials are N,N′-diphenyl-N,N′-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4′-diamine (DNTPD), a phthalocyanine compound such as copper phthalocyanine, 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), N,N′-di(1-naphthyl-N,N′-diphenylbenzidine) (NPB), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris-(N-(naphthylen-2-yl)-N-phenylamino)triphenylamine (2-TNATA), polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (Pani/CSA), (polyaniline)/poly(4-styrenesulfonate) (PANI/PSS), tetracyanoquinonedimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ) and additional hole-injection materials, such as dipyrazino[2,3-f:2′,3′-h]quinoxalinehexacarbonitrile (HATCN) are described in U.S. Publication 2004/0113547 A1 and U.S. Pat. No. 6,720,573.
(151) The hole-injection material can be deposited using any suitable conventional method known in the art including, but not limited to, vacuum deposition, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
(152) The hole-transport layer 130 can be formed of any hole-transport material including those that are commonly used. Non-limiting examples of suitable known hole-transport materials are carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole, N,N′-bis(3-methylphenyl-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), (4,4′-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline)) (TAPC), and N,N′-di(1-naphthyl-N,N′-diphenylbenzidine) (NPB).
(153) The hole-transport material can be deposited using any suitable conventional method known in the art including, but not limited to, vacuum deposition, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
(154) The light-emitting layer 140 can comprise a substantially pure thin film comprising a compound of Formula 1 or a host matrix doped with a compound of Formula I. In instance in which the light-emitting layer comprises a host matrix, the host matrix can be any host matrix material known in the art. Non-limiting examples of host matrix materials include bis(4-(3,6-diphenyl-9H-carbazol-9-yl)phenyl)methanone, 9-(4-(4,6-diphenylpyrimidin-2-yl)phenyl)-9H-carbazole, 4-(4-diphenylaminophenyl)diphenylsulfone, 9-(9-phenyl-9H-carbazol-3-yl)-9-p-tolyl-9H-fluorene-3-carbonitrile, 3,5-di(9H-carbazol-9-yl)benzonitrile, 2-(diphenylphosphinyl)-spiro[9H-fluorene-9,9′-quino[3,2,1-kl]phenoxazine], 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene, 4,4′-bis(carbazol-9-yl)biphenyl, 4,4′,4″-tris(carbazol-9-yl)triphenylamine, 2,6-bis(9,9-diphenylacridin-10(9H)-yl)pyrazine, 1,3-bis(carbazol-9-yl)benzene, 4,4′,4″-Tris(carbazol-9-yl)triphenylamine, 4,4′-bis(carbazol-9-yl)biphenyl, 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene, bis[2-(diphenylphosphino)phenyl]ether oxide, 2,6-di(9H-carbazol-9-yl)pyridine, 3′,5′-di(carbazol-9-yl)-[1,1′-biphenyl]-3,5-dicarbonitrile, 4,4′-(9H,9′H-3,3′-bicarbazole-9,9′-diyl)bis(N,N-diphenylaniline), 4′-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile, 3′-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile, 2,8-bis(diphenylphosphoryl)dibenzo[b,d]furan, and 3,5-di(carbazol-9-yl)-1-phenylsulfonylbenzene. The compound of Formula 1 can be present in the host material at a concentration of 1-20% w/w.
(155) The light-emitting material can be deposited using any suitable conventional method known in the art including, but not limited to, vacuum deposition, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
(156) Any suitable electron-transport material may be used to form the electron-transport layer 150. As the electron-transport material, any electron-transporting material that can stably transport electrons injected from an electron injecting electrode (cathode) may be used as a material for the electron-transport layer. Non-limiting examples of useful electron-transport materials may include quinoline derivatives such as tris(8-quinolinorate)aluminum (Alq3), 3-(biphenyl-4-yl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), bis(2-methyl-8-quinolinato-N1,08)-(1,1′-biphenyl-4-olato)aluminum (BAlq), beryllium bis(benzoquinolin-10-olate) (Bebg2), 9,10-di(naphthalene-2-yl)anthracene (ADN), 1,3,5-Tris(3-pyridyl-3-phenyl)benzene (TmPyPB), and (3,3″,5,5″-tetra(pyridin-3-yl)-1,1′: 3′,1″-terphenyl (BmPyPhB).
(157) The electron-transport material can be deposited using any suitable conventional method known in the art including, but not limited to, vacuum deposition, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
(158) Any suitable electron-injection material may be used to form the electron-injection layer 160. Non-limiting examples of electron injecting materials useful for forming the electron-injection layer 160 are LiF, NaCl, CsF, Li.sub.2O, 8-hydroxyquinolinolato-lithium (Liq) and BaO.
(159) The electron-injection material can be deposited using any suitable conventional method known in the art including, but not limited to, vacuum deposition, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
(160) The cathode 170 can comprise any anodic material known to those of skill in the art. In certain embodiments, the anode comprises lithium, magnesium, calcium, aluminum, gold, indium, copper, silver, or a combination thereof. In certain embodiments, the anode comprises aluminum.
(161) The cathode 170 can be deposited using any suitable way such as evaporation, sputtering, chemical vapor deposition, or electrochemical processes. Anodes can be patterned using, e.g., conventional photolithographic processes.
(162) In certain embodiments, the OLED comprises thin layers of ITO/HATCN/TAPC/AIEgen 1/TmPyPB/LiF/Al, wherein HATCN and LiF serve as the hole-injection and electron-injection layers, respectively; TAPC and TmPyPB serve as the hole-transport and electron-transport layers, respectively; AIEgen 1 serves as the light-emitting layer; and ITO and Al are used as the anode and electrode, respectively.
(163) The luminescent devices described herein can be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, sensors, heads up displays, fully transparent displays, flexible displays, cell phones, personal laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign.
(164) The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures described herein.
(165) AIEgen 1 featuring a propeller shaped structure exhibits AIE properties (
(166) A large molecular dipole of D-A structures can yield intriguing photoluminescence behavior depending on the solvent polarity due to the conversion between less polarized locally excited (LE) state and polarized twisted intramolecular charge transfer (TICT) state. AIEgen 1 demonstrated a strong solvatochromic effect. When the solvent polarity was increased gradually from low-polarity hexane to high-polarity acetonitrile, the emission of its solution exhibited a dramatic bathochromic shift and the intensity gradually weakened due to the susceptibility of the TICT state to various nonradiative quenching processes. Meanwhile, its solution colors changed from bright blue in nonpolar hexane over green, yellow and orange in lower polar solvents (such as ether, ethyl acetate, THF and DCM) and then to dark red in high polar solvents (acetone, DMF and acetonitrile), thus covering the whole visible region as shown in the CIE diagram obtained from the PL spectra (
(167)
where h is Plank's constant, c is the velocity of light, f is the orientational polarizability of the solvent, v.sub.a.sup.0−v.sub.f.sup.0 corresponds to the Stokes shifts when f is zero, μ.sub.e is the excited-state dipole moment, μ.sub.g is the ground-state dipole moment, α is the solvent Onsager cavity radius, and ε and n are the solvent dielectric and the solvent refractive index, respectively (Table 2,
(168) In general, the luminescence of organic compounds in solution state is quenched with the increase of temperature. However, it is intriguing that the compounds described herein can achieve a continuously enhanced emission by increasing temperature. From another perspective, this temperature effect is also powerful evidence to reinforce that the TICT process is really involved. Typically, in THF solvent with a moderate polarity, two discernable bands centered at 556 and 596 nm related to the LE state and the TICT state, respectively, could be observed. As demonstrated in
(169) Herein, it is noteworthy to mention that polarity is an important parameter in chemistry, nanotechnology, and even life science. In biological systems, especially at the cellular level, polarity determines the interaction activity of large numbers of proteins and enzymes or reflects the permeability of membrane compartments. Furthermore, abnormal changes in polarity are closely linked with disorders and diseases (e.g., diabetes, liver cirrhosis). However, the environmental polarity change in many cases is relatively subtle, especially for the above biological systems and the aforementioned temperature-dependent systems, thus it is very difficult to realize its accurate measurement in a straightforward manner, let alone its macroscopic visualization. Therefore, the compounds described herein, involving simple ratiometric measurement of fluorescence signals, readily realized a dramatic amplification of the subtle polarity change as a function of temperature. Additionally, this microcosmic change has been well presented by macroscopic color changes of the system. Therefore, the present signal amplification and visualization method provides a valuable tool for the measurement of subtle polarity change. In another aspect, thermochromic solutions of the compounds described herein, such as AIEgen 1, also allow a simple quantitative determination of the temperature dependence, thus possessing great potential to be used as luminescent thermometer. In order to test its response range and facilitate its application, we have selected tetraethylene glycol dimethyl ether (TRIEDM) with a very high boiling point of 275° C. and ideal stability as the solvent. As shown in
(170) Thus, provided herein is a method for measuring the temperature, the method comprising measuring the fluorescence emission of a sample comprising a compound described herein; and determining the temperature based on the measured fluorescence emission. The step of determining the temperature based on the measured fluorescence can comprise comparing the measured fluorescence to fluorescence of a standardized curve or comparing to the measured fluorescence to a color chart. The measured temperature can be any temperature. In certain embodiments, the measured temperature is in the range of −100 to 350° C. In certain embodiments, the measured temperature in the range of −50 to 300° C., 0 to 300° C., 0 to 250° C., 0 to 200° C., 10 to 200° C., 20 to 200° C., 20 to 180° C., 25 to 175° C. or higher.
(171) Also provided is a device for measuring the temperature comprising the compound described herein and a solvent. In certain embodiments, the solvent is an organic solvent. The selection of the organic solvent and its respective boiling point can be selected based on the desired temperature monitoring range. In certain embodiments, the boiling point of the solvent is 50 to 500° C., 100 to 400° C., 100 to 300° C., 100 to 300° C., 150 to 300° C., or 200 to 300° C. In certain embodiments, the solvent is TRIEDM.
(172) The underlying mechanism of the thermochromic PL of the compounds described herein was then investigated, with the goal of providing an initial guideline for the design of new thermochromic materials. Taking all the experimental data together, we proposed that raising temperature will lead to the increase of solvent hydrophobicity, thus benefiting the LE state prone to planar geometry and resulting in intensified emission intensities and blue-shifted luminescence. Given that temperature switching is considered to induce dynamic changes in molecular structures. Considering there are multiple flexible aryl rotors in the compounds described herein, various conformations of the excited state S1 were attempted. Ultimately, it was observed that the central plane formed by atoms C16, N2 and C25 is the pivot to determine the flexible conformation, and is also the critical position linking the charge separated donor and acceptor units. Upon excitation to S1, the molecule rotates around the N2-C25 bond, and the associated C16-N2-C25-C30 dihedral angle varies from ˜30° to ˜90°, thus possessing a more twisted conformation as demonstrated in
(173) Excitingly, this compound is very sensitive to the external shear force stimulus and exhibits attractive tribochromic PL behavior (
(174) Powder X-ray diffraction (pXRD) measurement was performed on an AIEgen 1 sample in different states to examine the tribochromic PL mechanism. As demonstrated in
(175) Given that the compounds described herein can respond to anisotropic shearing force, the compound's responsive behavior to isotropic hydrostatic pressure was examined. As shown in
(176) Combined with the DFT calculation results (Table 3,
(177) The above observations raise a question: why the mechanical grinding and hydrostatic pressure trigger distinct luminescence alterations? The analyses of crystal structure were expected to provide some clues to address this issue. As shown in
(178) The electrochemical behavior of AIEgen 1 was investigated by cyclic voltammetry and square-wave voltammetry in deaerated CH.sub.2Cl.sub.2 containing 10.sup.−1 mol/L n-Bu.sub.4NPF.sub.6 as the supporting electrolyte (
(179) Interestingly, AIEgen 1 can also respond to the external electric stimulus and exhibited remarkable change in its electronic spectra in the near-infrared (NIR) region and different colors associated with its different oxidation states during the in situ spectroelectrochemical measurements (
(180) In light of its excellent luminescent behavior of AIEgen 1 in the solid state, its potential application as solid-state emitter was evaluated. Thermogravimetric analysis (TGA) was also performed to analyze the thermal properties of AIEgen 1 under nitrogen atmosphere, as shown in
EXAMPLES
(181) The following examples are illustrative of the presently described subject matter and are not intended to be limitations thereon.
(182) Preparation of AIEgen 1
(183) ##STR00033##
(184) The general synthetic route to AIEgen 1 is outlined above. All manipulations were carried out under a dry argon atmosphere using standard Schlenk techniques, unless stated otherwise. Solvents were pre-dried and distilled under argon prior to use, except those used directly for spectroscopic measurements, which were of spectroscopic grade. The precursor 1 was prepared according to procedure described in the literature (J. Phys. Chem. A, 2015,119, 1933-1942.). Other reagents were purchased and used as received.
(185) Synthesis of AIEgen 1: N.sup.1-(4-bromophenyl)-N,N.sup.4,N.sup.4-triphenylbenzene-1,4-diamine (Precursor 1) (490 mg, 1.00 mmol) was dissolved in anhydrous THF (30 mL) under nitrogen, and the resulting mixture was cooled to −78° C. To this solution, n-BuLi (0.5 mL, 2.5 M in hexane) was added slowly and the resulting solution was stirred for 1 h at −78° C. Dimesitylboron fluoride (402 mg, 1.5 mmol) was dissolved in THF (10 mL) and then slowly added to the reaction solution at −78° C. The mixture was allowed to warm to room temperature with stirring overnight. The solvent was then removed in vacuo, and the residue was purified by chromatography on silica gel (petroleum ether/dichloromethane 8:1, v/v). The product was precipitated from a solution in CH.sub.2Cl.sub.2 by adding MeOH to give 547 mg (79%) of AIEgen 1 as a yellow-green powder. .sup.1H NMR (CDC.sub.3, 400 MHz, ppm): δ 7.35 (d, J=8 Hz, 2H), 7.18-7.31 (m, 8H), 6.98-7.10 (m, 11H), 6.90 (d, J=8 Hz, 2H), 6.79 (s, 4H), 2.28 (s, 6H), 2.06 (s, 12H); .sup.13C NMR (CDC.sub.3, 100 MHz, ppm): 151.4, 147.7, 146.6, 144.2, 141.9, 141.2, 140.7, 138.7, 137.9, 129.4, 129.2, 129.1, 128.0, 127.1, 125.6, 124.9, 124.1, 124.0, 122.7, 118.9 (Ar); HRMS (MALDI-TOF): m/z: [M]+ calcd for C.sub.48H.sub.45BN.sub.2.sup.+: 660.3676; found: 660.3665.