Patent Application
20080217582
1. Field of the Invention
The present invention relates to the organometallic complexes, and more particularly to a class of luminescent iridium(III) complexes with 2-(diphenylphosphino)phenolate ligand and organic electroluminescent device thereof.
2. Description of Related Art
Organometallic complexes possessing a third-row transition-metal element are crucial for the fabrication of highly efficient organic light emitting diodes (OLEDs). The strong spin-orbit coupling induced by a heavy metal ion such as iridium (III) promotes an efficient intersystem crossing from the singlet to the triplet excited state manifold, which then facilitates strong electroluminescence by the harnessing of both singlet and triplet excitons induced by charge recombination. Because internal phosphorescence quantum efficiency (ηint) of as high as ˜100% could be achieved, these heavy metal containing emitters would be superior to their fluorescent counterparts in future OLED applications. As a result, there is a continuous trend of shifting research endeavors to these heavy transition-metal complexes. Moreover, since the manufacture of a full color display requires the usage of emitters with all three primary colors, i.e. RGB color, rationally tuning the emission wavelength of heavy transition-metal phosphorescent emitters over the entire visible range are also represent an important forthcoming research task.
In fact, the tri-substituted (or homoleptic) Ir(III) complexes with formula [Ir(ĈN)3], (ĈN)H=2-(4′,6′-difluorophenyl)pyridine, 2-phenyl pyridine and 1-phenyl isoquinoline, have shown the anticipated, blue, green and red phosphorescence in both fluid and solid states and, thus, they are highly desirable for fabrication of the phosphorescent OLEDs. Unfortunately, many of the related cyclometalating ligands (ĈN)H do not react with iridium (III) reagents to give the homoleptic iridium (III) complexes by the reported synthetic methods. As a result, researchers developed a distinctive class of iridium complexes with the formula [Ir(ĈN)2(L̂X)]. However, with respect to the chemical stabilities of these heteroleptic complexes, most of the L̂X ligand belong to the so-called weak field ligands, as they possess the O-donor or N-donor fragments. As the result, the chemical stabilities as well as the relatively energy gap for the metal centered dd transition could not be as strong as those involving the higher field-strength ligands. This case is particular true for the heteroleptic complexes [(ĈN)2Ir(L̂X)] with L̂X being acetylacetonate, for which lowered thermal stabilities and poor chemical resistance to the acidic media were reported, making the corresponding as-prepared OLED devices suffered from a situation involving the reduced device lifetime and with other inferior characteristics.
Accordingly, the present invention is directed to a new class of luminescent iridium(III) complexes with at least one 2-(diphenylphosphino)phenolate as the ancillary chelate for high efficient phosphorescence.
And, the present invention is directed to the luminescent material of the novel luminescent iridium(III) complexes, which can be used as the red, blue or green-emitting dopants.
Besides, the present invention is directed to the organic electroluminescent device of the new class luminescent iridium(III) complexes for providing the high efficiently red, blue or green light organic electroluminescent devices of commercial pursuits.
The present invention provides a new class of luminescent iridium(III) complexes, luminescent material and organic electroluminescent device thereof which comprises a formula [(ĈN)2Ir(P̂O)], for example, having the following structure:
Moreover, a synthesis of the iridium (III) complexes with the formula [(ĈN)2Ir(P̂O)] comprises the following procedures, see reaction scheme (I):
wherein the (ĈN)H is a substituted cyclometalated ligand with structure indicated below:
for which, R11, R12, R13 and R14 represent a hydrogen atom, both saturated and unsaturated alkyl, aryl group, fluorine atom, fluorinated alkyl substituent or other electron-withdrawing substituent, while Q21 represents an atomic group forming a nitrogen-containing heterocyclic ring. And, the (P̂O)H is 2-(diphenylphosphino)phenol or its alkyl, aryl, fluoro or CF3 substituted derivatives and comprises the following structure:
As all six of coordination sites on Ir(III) metal center are occupied by these ĈN and P̂O chelates, the resulting complexes become charge-neutral and sublimable, which are essentially for the subsequent fabrication of OLEDs employing direct thermal evaporation.
The present invention is a new class of luminescent iridium(III) complexes having high efficient phosphorescence and provides a synthetic method thereof.
Since the luminescent iridium(III) complexes of the present invention possess 2-(diphenylphosphino)phenolate as the ancillary chelate, the energies of ππ* or MLCT manifolds, i.e. the energy gap between the ground and the emitting excited states, can be fine-tuned by addition of at least one alkyl, aryl group, or at least one electronegative fluorine atom or even the CF3 substituent at the phenolate fragment, giving emitters with higher volatility as well as both modified electrochemical and emission characteristics.
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
Reference will now be made in detail to the present embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
The present invention provides a new class of luminescent iridium(III) complexes, luminescent material and organic electroluminescent device thereof, which comprise a formula [(ĈN)2Ir(P̂O)]; for example, having the following structure:
Moreover, synthesis of the iridium (III) complexes with formula [(ĈN)2Ir(P̂O)] comprises the following procedures, see reaction scheme (I):
A luminescent material of iridium(III) complexes of the present invention comprises the new class of luminescent iridium(III) complexes with formula [(ĈN)2Ir(P̂O)], while the luminescent material further comprises a host compound and a guest compound, wherein the guest compound comprises the new class of luminescent iridium(III) complexes with the formula [(ĈN)2Ir(P̂O)].
An organic electroluminescent device of the present invention comprises at least an organic electroluminescent material layer with a emitting layer formed by a luminescent material comprising at least a new class of luminescent iridium(III) complexes comprising the formula [(ĈN)2Ir(P̂O)]. The luminescent material further comprising a host compound and a guest compound, wherein the guest compound comprises the new class of luminescent iridium(III) complexes comprising at least the formula [(ĈN)2Ir(P̂O)].
In one of the preferred embodiments, the (ĈN)H is a substituted cyclometalated ligand with structure indicated below:
for which, R11, R12, R13 and R14 represent a hydrogen atom, saturated and unsaturated alkyl substituent, aryl substituent, fluorine atom, fluorinated alkyl substituent or other electron-withdrawing substituent, while Q21 represents an atomic group forming a nitrogen-containing heterocyclic ring. In the reaction (I), the chloride bridged dimers [(ĈN)2Ir(μ-Cl)]2, where (ĈN)H stands for 2-(4′,6′-difluorophenyl)pyridine, 2-phenylpyridine, 1-phenylisoquinoline or 4-phenylquinazoline, were synthesized from the direct reaction employing 4.0 equiv. of the cyclometalated (ĈN)H ligand mixed with IrCl3 hydrate in refluxing methoxyethanol solvent. Subsequent treatment of [(ĈN)2Ir(μ-Cl)]2 with stoichiometric amount of (P̂O)H ligand and Na2CO3 as proton scavenger gave isolation of the heteroleptic Ir(III) complexes [(ĈN)2Ir(P̂O)].
In one of the preferred embodiments, the (P̂O)H can be the 2-(diphenylphosphino)phenol or its alkyl, aryl, fluoro or CF3 substituted derivatives and comprise the following structure:
In one of the preferred embodiments, a synthesis of the (P̂O)H comprises at least the following reaction (II):
wherein R1 is —H, alkyl, aryl, —F or —CF3 and R2 is —H alkyl, aryl, —F or —CF3 and PPh2 is diphenylphosphino group or its functionalized derivatives with alkyl, fluorine atom, or fluorinated alkyl substituent at the phenyl sites.
As depicted in the above synthesis, the required 2-(diphenylphosphino)phenol and its fluoro or CF3 substituted derivatives, denoted as (P̂O)H, were obtained in multi-steps synthetic sequences involving the first preparation of 1-(methoxymethoxy)benzene (or its fluoro or CF3 substituted derivatives) using the phenol reagents and chloromethyl methyl ether, followed by direct lithiation of 1-(methoxymethoxy)benzene with n-BuLi, addition of chlorodiphenylphosphine and the deprotection of phenol functional group using anhydrous HCl in methanol.
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(dfppy)2Ir(dppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(dfppy)2Ir(4Tdppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(dfppy)2Ir(6Tdppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(dfppy)2Ir(4Fdppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(ppy)2Ir(dppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(ppy)2Ir(6Tdppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(ppy)2Ir(4Fdppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(nazo)2Ir(dppp)] of the following structure:
In one of the preferred embodiments, the formula [(ĈN)2Ir(P̂O)] comprises the complex of [(piq)2Ir(dppp)] of the following structure:
In the above complexes of the formula [(ĈN)2Ir(P̂O)], their photophysical properties are somewhat analogous to other iridium metal complexes that possess the similar cyclometalated ligands, albeit with notable distinction at their third, ancillary ligand site. In addition, all the (P̂O) substituted complexes are highly soluble in chlorinated organic solvents and showing negligible decomposition in solution within a period of 24 hours.
The present invention provides a systematic design, synthesis and characterization of heteroleptic iridium (III) complexes possessing the 2-(diphenylphosphino)phenolate as the third, ancillary ligand. The high rigidity of the ligand framework as well as the strong σ-donating and concomitant π-accepting strength of the unique diphenylphosphino fragment would significantly reduce the vibration induced nonradiative decay transition and the unwanted thermal quenching by population to the upper-lying metal centered dd excited state, respectively. On the other hand, the energies of ππ* or MLCT manifolds, i.e. the energy gap between the ground and the emitting excited states, can be fine-tuned by adding at least one electronegative fluorine atom or even the CF3 substituent at the phenolate fragment, giving emitters with higher volatility as well as both modified electrochemical and emission characteristics.
Moreover, with respect to the chemical stabilities of these heteroleptic complexes, most of the L̂X ligand mentioned in previous technologies belong to the so-called weak field ligands, as they possess the O-donor or N-donor fragments. As the result, the chemical stabilities as well as the relatively energy gap for the metal centered dd transition could not be as strong as those involving the higher field-strength ligands, such as the cyclometalated ĈN ligand as observed in the homoleptic complexes [Ir(ĈN)3] or even chelating ligand with at least one phosphine substituent.
The present invention provides the synthetic method of new class of luminescent iridium(III) complexes for simple synthesizing the iridium(III) complexes with 2-(diphenylphosphino)phenolate as the ancillary chelate.
The present invention provides a new class of luminescent iridium(III) complexes, which have various derivatives with different substituents, for fabricating diversified luminescent materials and organic electroluminescent devices.
The present invention provides a new class of luminescent iridium(III) complexes, which can be used as the red, blue or green-emitting dopants. These luminescent materials can be applied in fabrication of the light-emitting layer of organic electroluminescent devices for high efficient phosphorescence.
While the invention has been described by way of example and in terms of a preferred embodiment, it is to be understood that the invention is not limited thereto. To the contrary, it is intended to cover various modifications and similar arrangements and procedures, and the scope of the appended claims therefore should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements and procedures.
Without intending to limit it in any manner, the present invention will be further illustrated by the following examples.
Reactions were performed under nitrogen. Solvents were distilled from appropriate drying agent prior to use. Commercially available reagents were used without further purification unless otherwise stated. Reactions were monitored by TLC with Merck pre-coated glass plates (0.20 mm with fluorescent indicator UV254). Compounds were visualized with UV light irradiation at 254 nm and 365 nm. Flash column chromatography was carried out using silica gel from Merck (230-400 mesh). Mass spectra were obtained on a JEOL SX-102A instrument operating in electron impact (EI) mode or fast atom bombardment (FAB) mode. 1H and 13C NMR spectra were recorded on Varian Mercury-400 or INOVA-500 instruments; chemical shifts are quoted with respect to the internal standard tetramethylsilane for 1H and 13C NMR data.
A 25 mL flask was charged with [(dfppy)2Ir(μ-Cl)]2 (122 mg, 0.1 mmol), 2-(diphenylphosphino)phenol (dpppH, 61 mg, 0.22 mmol), Na2CO3 (106 mg, 1.0 mmol) and 2-methoxyethanol (10 mL). After the mixture was heated at 120° C. for 1.5 h, the reaction was quenched by addition of excess water (15 mL). The precipitate was filtered and washed with anhydrous ethanol and diethyl ether in sequence. The product was purified by silica gel column chromatography using EA/hexane=1:1 as eluent, followed by recrystallization from a mixture of CH2Cl2 and hexane at RT, giving a pale yellow crystalline solid [(dfppy)2Ir(dppp)] (53 mg, 0.06 mmol) in 56% yield. The related Ir(III) complexes [(dfppy)2Ir(4Tdppp)], [(dfppy)2Ir(6Tdppp)], and [(dfppy)2Ir(4Fdppp)] were prepared using similar procedures; yield 46% ˜56%.
Spectra data for [(dfppy)2Ir(dppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 850 [M+], 660 [M+-dfppy], 573 [M+-dpp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.38 (dd, J=5.8, 0.6 Hz, 1H), 8.23 (dd, J=8.4, 2.4 Hz, 1H), 8.06 (d, J=6.0 Hz, 1H), 7.74 (t, J=8.2 Hz, 2H), 7.60 (t, J=7.4 Hz, 2H), 7.46-7.36 (m, 4H), 7.34 (t, J=7.8 Hz, 1H), 7.24 (t, J=8.4 Hz, 1H), 7.07 (dd, J=8.4, 6.0 Hz, 1H), 7.02 (t, J=7.6 Hz, 1H), 6.86˜6.82 (m, 3H), 6.65 (t, J=7.2 Hz, 1H), 6.56 (d, J=7.2 Hz, 1H), 6.54 (d, J=8.4 Hz, 1H), 6.45˜6.33 (m, 3H), 6.04 (dd, J=8.4, 2.2 Hz, 1H), 5.48 (ddd, J=8.2, 5.6, 2.6 Hz, 1H). 19F{1H} NMR (470 MHz, CDCl3, 294K): δ −108.22 (s, 1F), −108.77 (s, 1F), −109.89 (s, 1F), −111.33 (s, 1F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 12.56 (s, 1P). Anal. Calcd for C40H26F4IrN2OP: N, 3.30; C, 56.53; H, 3.08. Found: N, 3.63; C, 56.15; H, 3.55.
Spectra data for [(dfppy)2Ir(4Tdppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 918 [M+], 573 [M+−4Tdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.28 (dd, J=5.6, 0.6 Hz, 1H), 8.25 (dd, J=8.4, 2.4 Hz, 1H), 8.08 (d, J=6.0 Hz, 1H) 7.71˜7.62 (m, 5H), 7.49˜7.35 (m, 5H), 7.05 (t, J=7.4 Hz, 2H), 6.87˜6.83 (m, 3H), 6.53˜6.48 (m, 3H), 6.44˜6.35 (m, 2H), 6.04 (dd, J=8.6, 2.5 Hz, 1H), 5.47 (ddd, J=8.0, 5.6, 2.4 Hz, 1H). 19F{1H} NMR (470 MHz, CDCl3, 294K): δ −60.28 (s, 3F), −107.78 (s, 1F), −109.31 (s, 1F), −109.56 (s, 1F), −111.02 (s, 1F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 11.79 (s, 1P). Anal. Calcd for C41H25F7IrN2OP: N, 3.05; C, 53.65; H, 2.75. Found: N, 3.35; C, 53.73; H, 3.20.
Spectra data for [(dfppy)2Ir(6Tdppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 918 [M+], 573 [M+−6Tdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.26˜8.22 (m, 2H), 8.10 (d, J=6.0 Hz, 1H), 7.69˜7.65 (m, 3H), 7.62 (t, J=8.0 Hz, 1H), 7.53 (t, J=8.0 Hz, 1H), 7.48˜7.38 (m, 5H), 7.04 (t, J=7.4 Hz, 1H), 6.85 (t, J=7.4 Hz, 1H), 6.84 (t, J=7.8 Hz, 1H), 6.78 (t, J=6.6 Hz, 1H), 6.58 (t, J=7.6 Hz, 1H), 6.54 (d, J=8.0 Hz, 1H), 6.51 (d, J=8.0 Hz, 1H), 6.46 (t, J=7.4 Hz, 1H), 6.43˜6.36 (m, 2H), 6.16 (dd, J=8.8, 2.5 Hz, 1H), 5.42 (dd, J=8.4, 5.6 Hz, 1H). 19F NMR (470 MHz, CDCl3, 294K): δ −63.64 (s, 3F), −108.38 (s, 1F), −108.77 (s, 1F), −110.16 (s, 1F), −111.22 (s, 1F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 11.46 (s, 1P). Anal. Calcd for C41H25F7IrN2OP: N, 3.05; C, 53.65; H, 2.75. Found: N, 3.34; C, 53.31; H, 3.05.
Spectra data for [(dfppy)2Ir(4Fdppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 868 [M+], 573 [M+−4Fdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.37 (d, J=5.8 Hz, 1H), 8.23 (d, J=6.8 Hz, 1H), 8.11 (d, J=5.6 Hz, 1H), 7.72 (d, J=6.4 Hz, 1H), 7.70 (d, J=8.4 Hz, 1H), 7.63 (t, J=8.4 Hz, 2H), 7.45˜7.24 (m, 4H), 7.08˜6.96 (m, 4H), 6.86˜6.82 (m, 3H), 6.55˜6.47 (m, 3H), 6.42˜6.34 (m, 2H), 6.05 (d, J=8.8 Hz, 1H), 5.46 (m, 1H). 19F{1H}NMR (470 MHz, CDCl3, 294K): δ −107.99 (s, 1F), −108.56 (s, 1F), −109.76 (s, 1F), −110.17 (s, 1F), −131.27 (s, 1F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 12.63 (s, 1P). Anal. Calcd for C40H25F5IrN2OP: N, 3.23; C, 55.36; H, 2.90. Found: N, 3.28; C, 54.74; H, 3.13.
A 25 mL flask was charged with [(ppy)2Ir(μ-Cl)]2 (107 mg, 0.1 mmol), 2-(diphenylphosphino)phenol (dpppH, 61 mg, 0.22 mmol), Na2CO3 (106 mg, 1.0 mmol) and 2-methoxyethanol (10 mL). The mixture was allowed to heat at 120° C. for 1.5 h. After the solution was cooled to RT, the reaction was quenched by addition of deionized water (15 mL). The precipitate was filtered and washed with anhydrous ethanol and diethyl ether in sequence. Purification was carried out by silica gel column chromatography using pure EA as eluent, followed by recrystallization from a mixture of CH2Cl2 and hexane at RT, giving a pale yellow crystalline solid [(ppy)2Ir(dppp)] (80 mg, 0.05 mmol) in 51% yield. Synthesis of related derivative complexes [(ppy)2Ir(6Tdppp)], and [(ppy)2Ir(4Fdppp)] followed similar experimental procedures; yield 55˜58%.
Spectra data for [(ppy)2Ir(dppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 778 [M+], 624 [M+−ppy], 501 [M+−4Fdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.37 (d, J=5.2 Hz, 1H), 8.06 (d, J=5.6 Hz, 1H), 7.81˜7.74 (m, 3H), 7.59 7.53 (m, 2H), 7.43 (td, J=7.8, 1.6 Hz, 1H), 7.39˜7.30 (m, 4H), 7.27 (d, J=7.2 Hz, 1H), 7.24−7.19 (m, 3H), 7.03 (dd, J=7.6, 6.0 Hz, 1H), 6.97 (t, J=6.0 Hz, 1H), 6.88˜6.82 (m, 3H), 6.82˜6.76 (m, 4H), 6.62 (t, J=6.4 Hz, 2H), 6.53 (t, J=8.4 Hz, 2H), 6.42 (t, J=6.0 Hz, 1H), 6.07 (dd, J=6.8, 4.4 Hz, 1H). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 12.30 (s, 1P). Anal. Calcd for C40H30IrN2OP: N, 3.60; C, 61.76; H, 3.89. Found: N, 3.68; C, 61.45; H, 4.24.
Spectra data for [(ppy)2Ir(6Tdppp)]: MS (FAB, 192,r): observed m/z [assignment]: 846 [M+], 692 [M+−ppy], 501 [M+−6Tdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.28 (d, J=6.0 Hz, 1H), 8.10 (d, J=5.6 Hz, 1H), 7.77 (d, J=8.0 Hz, 1H), 7.73 (t, 8.4 Hz, 2H), 7.57 (d, J=7.6 Hz, 1H), 7.53 (t, J=7.8 Hz, 2H), 7.45 (d, J=7.2 Hz, 1H), 7.41˜7.34 (m, 4H), 7.29 (d, J=4.8 Hz, 2H), 6.98 (t, J=7.4 Hz, 1H), 6.90˜6.69 (m, 8H), 6.56˜6.48 (m, 3H), 6.42 (t, J=6.0 Hz, 1H), 6.01 (dd, J=7.6, 4.4 Hz, 1H), 19F{1H} NMR (470 MHz, CDCl3, 294K): δ−63.41 (s, 3F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 11.17 (s, 1P). Anal. Calcd for C41H29F3IrN2OP: N, 3.31; C, 58.22; H, 3.46. Found: N, 3.33; C, 53.97.45; H, 3.60.
Spectra data for [(ppy)2Ir(4Fdppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 796 [M+], 642 [M+−ppy], 501 [M+−4Fdppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 8.36 (d, J=6.6 Hz, 1H), 8.12 (d, J=6.6 Hz, 1H), 7.81 (d, J=8.0 Hz, 1H), 7.71 (t, J=8.6 Hz, 2H), 7.57 (t, J=7.8 Hz, 2H), 7.41˜7.31 (m, 4H), 7.29˜7.25 (t, J=7.6 Hz, 2H), 7.06 (t, J=8.0 Hz, 1H), 7.02˜6.73 (m, 10H), 6.62 (d, J=7.2 Hz, 1H), 6.53˜6.45 (m, 3H), 6.05 (dd, J=7.4, 4.0 Hz, 1H). 19F{1H} NMR (470 MHz, CDCl3, 294K): δ−132.03 (s, 3F). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 12.37 (s, 1P). Anal. Calcd for C40H29FIrN2OP: N, 3.52; C, 60.37; H, 3.67. Found: N, 3.39; C, 56.36; H, 4.30
A 25 mL flask was charged with [(nazo)2Ir(μ-Cl]2 (64 mg, 0.05 mmol), 2-(diphenylphosphino)phenol (dpppH, 31 mg, 0.11 mmol), Na2CO3 (53 mg, 0.5 mmol) and 2-methoxyethanol (10 mL). The mixture was heated at 120° C. for 2 h. After the solution was cooled to RT, the reaction was quenched with deionized water (15 mL). The precipitate was filtered and rinsed with anhydrous ethanol and diethyl ether in sequence. The solid was further purified by silica gel column chromatography using EA/hexane=1:1 as eluent, followed by recrystallization from a mixture of CH2Cl2 and methanol at RT, giving a dark red crystalline solid [(nazo)2Ir(dppp)] (57 mg, 0.06 mmol) in 65% yield.
Spectra data for [(nazo)2Ir(dppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 880 [M+], 675 [M+−nazo], 603 [M+−dppp]. 1H NMR (400 MHz, CDCl3, 294K): δ 9.21 (s, 1H), 8.80 (d, J=7.2 Hz, 1H), 8.65 (s, 1H), 8.44 (d, J=8.4 Hz, 1H), 8.28 (d, J=8.4 Hz, 1H), 8.17 (d, J=8.0 Hz, 1H), 7.93 (t, J=7.4 Hz, 2H), 7.84 (t, J=7.6 Hz, 1H), 7.78˜7.68 (m, 4H), 7.59 (t, J=7.8 Hz, 1H), 7.44˜7.38 (m, 4H), 7.16 (t, J=8.8 Hz, 1H), 7.03˜6.91 (m, 3H), 6.90˜6.85 (m, 2H), 6.81 (t, J=7.6 Hz, 1H), 6.60 (t, J=7.4 Hz, 1H), 6.49˜6.42 (m, 5H), 6.36 (dd, J=8.4, 4.0 Hz, 1H). 31P{1H} NMR (202 MHz, CDCl3, 294K): δ 12.30 (s, 1P). Anal. Calcd for C46H32IrN4OP: N, 6.37; C, 62.79; H, 3.67. Found: N, 6.57; C, 61.52; H, 3.93.
A 25 flask was charged with [(piq)2Ir(μ-Cl)]2 (64 mg, 0.05 mmol), 2-(diphenylphosphino)phenol (dpppH, 31 mg, 0.11 mmol), Na2CO3 (53 mg, 0.5 mmol), and 2-methoxyethanol (10 mL). The reaction mixture was heated at 120° C. for 10 min then allowed to cool to RT. After then, excess water was added to qunch the reaction, the precipitate was filtered and washed by anhydrous ethanol and diethyl ether in sequence. The resulting solid was further purified by silica gel column chromatography using pure EA as eluent, followed by recrystallization from a mixture of CH2Cl2 and methanol at RT, giving red crystalline solid [(piq)2Ir(dppp)] (27 mg, 0.03 mmol) in 31% yield.
Spectra data for [(piq)2Ir(dppp)]. MS (FAB, 192Ir): observed m/z [assignment]: 878 [M+], 601 [M+-dpp]. 1H NMR (500 MHz, CD2Cl2, 294K): δ 8.88 (d, J=8.0 Hz, 1H), 8.55 (d, J=8.0 Hz, 1H), 8.37 (d, J=6.5 Hz, 1H), 8.17 (d, J=8.5 Hz, 1H), 8.10 (d, J=8.5 Hz, 1H), 7.99 (d, J=6.5 Hz, 1H), 7.76 (t, J=8.3 Hz, 3H), 7.71˜7.66 (m, 3H), 7.59˜7.55 (m, 2H), 7.45 (t, J=7.3, 1H), 7.42 (t, J=6.8 Hz, 1H), 7.35 (t, J=8.0 Hz, 2H), 7.20 (t, J=7.0 Hz, 1H), 7.17 (d, J=6.5 Hz, 1H), 7.01 (t, J=8.0 Hz, 1H), 6.97 (t, J=8.0 Hz, 1H), 6.91 (t, J=7.0 Hz, 1H), 6.81 (d, J=7.0 Hz, 1H), 6.80 (d, J=7.0 Hz, 1H), 6.76 (t, J=7.8 Hz, 1H), 6.65 (d, J=8.0 Hz, 1H), 6.60 (t, J=7.3 Hz, 1H), 6.48˜6.45 (m, 4H), 6.39˜6.37 (m, 2H). 31P{1H} NMR (202 MHz, CD2Cl2, 294K): δ 13.31 (s, 1P). Anal. Calcd for C48H34IrN2OP: N, 3.19; C, 65.66; H, 3.90. Found: N, 3.06; C, 64.33; H, 4.12.
Steady-state absorption and emission spectra were recorded by a Hitachi (U-3310) spectrophotometer and an Edinburgh (FS920) fluorimeter, respectively. Both wavelength-dependent excitation and emission response of the fluorimeter have been calibrated. A configuration of front-face excitation was used to measure the emission of the solid sample, in which the cell was made by assembling two edge-polished quartz plates with various Teflon spacers. A combination of appropriate filters was used to avoid the interference from the scattering light.
Lifetime studies were performed by an Edinburgh FL 900 photon-counting system with a hydrogen-filled/or a nitrogen lamp as the excitation source. Data were analyzed using the nonlinear least squares procedure in combination with an iterative convolution method. The emission decays were analyzed by the sum of exponential functions, which allows partial removal of the instrument time broadening and consequently renders a temporal resolution of ˜200 ps. The combined spectroscopic data are listed in Table 1, while their emission spectra are depicted in
