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Yun Chi

Publications and source records attributed to Yun Chi.

At least 19 recordsLinked to original sources
PubMed2007

Chiral fluorous dialkoxy-diamino zirconium complexes: synthesis and use in stereospecific polymerization of 1-hexene.

New catalysts for the isospecific polymerization of 1-hexene based on cationic zirconium complexes incorporating the tetradentate fluorous dialkoxy-diamino ligands [OC(CF(3))(2)CH(2)N(Me)(CH(2))(2)N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(2)NO)(2-)] and [OC(CF(3))(2)CH(2)N(Me)(1R,2R-C(6)H(10))N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(Cy)NO)(2-)] have been developed. The chiral fluorous diamino-diol [(ON(Cy)NO)H(2), 2] was prepared by ring-opening of the fluorinated oxirane (CF(3))(2)COCH(2) with (R,R)-N,N'-dimethyl-1,2-cyclohexanediamine. Proligand 2 reacts cleanly with [Zr(CH(2)Ph)(4)] and [Ti(OiPr)(4)] precursors to give the corresponding dialkoxy complexes [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3) and [Ti(OiPr)(2)(ON(Cy)NO)] (4), respectively. An X-ray diffraction study revealed that 3 crystallizes as a 1:1 mixture of two diastereomers (Lambda-3 and Delta-3), both of which adopt a distorted octahedral structure with trans-O, cis-N, and cis-CH(2)Ph ligands. The two diastereomers Lambda-3 and Delta-3 adopt a C(2)-symmetric structure in toluene solution, as established by NMR spectroscopy. Cationic complexes [Zr(CH(2)Ph)(ON(2)NO)(THF)(n)](+) (n=0, anion=[B(C(6)F(5))(4)](-), 5; n=1, anion=[PhCH(2)B(C(6)F(5))(3)](-), 6) and [Zr(CH(2)Ph)(ON(Cy)NO)(THF)](+)[PhCH(2)B(C(6)F(5))(3)](-) (7) were generated from the neutral parent precursors [Zr(CH(2)Ph)(2)(ON(2)NO)] (H) and [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3), and their possible structures were determined on the basis of (1)H, (19)F, and (13)C NMR spectroscopy and DFT methods. The neutral zirconium complexes H and 3 (Lambda-3/Delta-3 mixture), when activated with B(C(6)F(5))(3) or [Ph(3)C](+)[B(C(6)F(5))(4)](-), catalyze the polymerization of 1-hexene with overall activities of up to 4500 kg PH mol Zr(-1) h(-1), to yield isotactic-enriched (up to 74 % mmmm) polymers with low-to-moderate molecular weights (M(w)=4800-47 200) and monodisperse molecular-weight distributions (M(w)/M(n)=1.17-1.79).

Journal Article↗
PubMed2007

Iridium(I) pyridyl azolate complexes with saturated red metal-to-ligand charge transfer phosphorescence; fundamental and potential applications in organic light-emitting diodes.

Preparation of a new series of neutral metal complexes [(cod)Ir(fppz)] (1), [(cod)Ir(bppz)] (2), [(cod)Ir(fptz)] (3) and [(cod)Ir(bptz)] (4), bearing one cod ligand and a pyridyl azolate chelate are reported. A single-crystal X-ray diffraction study of 3 reveals the expected distorted square-planar geometry. The lowest absorption band consists of IrI atom increased triplet dpi-->pi* transitions (3MLCT), the assignment of which is firmly supported by the theoretical approaches. Complexes 1-4 exhibit weak phosphorescence in degassed solution at room temperature, whereas much more intense, solid-state phosphorescence appears in the range 622-649 nm. The pure MLCT emission was used as a prototypical model to address its remarkable spectral differences from the IrIII isoquinoline pyrrolide complex (5), which has mainly 3pipi phosphorescence. Complex 3 was used as a dopant to fabricate red-emitting phosphorescent organic light-emitting diodes (OLEDs). For the 7 % doped device, a maximum brightness of 3010 cd m-2 was achieved at an applied voltage of 15 V and with CIE coordinates of (0.56, 0.33), demonstrating for the first time the potential of neutral IrI complexes in OLED applications.

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PubMed2007

Phosphorescent dyes for organic light-emitting diodes.

This article presents general concepts that have guided important developments in our recent research progress regarding room-temperature phosphorescent dyes and their potential applications. We first elaborate the theoretical background for emissive metal complexes and the strategic design of the chelating C-linked 2-pyridylazolate ligands, followed by their feasibility in functionalization and modification in an aim to fine-tune the chemical and photophysical properties. Subsequently, incorporation of 2-pyridylazolate chromophores is illustrated in the synthesis of the highly emissive, charge-neutral Os, Ru, Ir, and Pt complexes. Insights into their photophysical properties are gained from spectroscopy, relaxation dynamics, and theoretical approaches, from which the lowest-lying excited states, competitive radiative decay, and radiationless processes are then analyzed in detail. In view of applications, their potentials for OLEDs have been evaluated. The results, in combination with the fundamental basis, give a conceptual design contributed to the future advances in the field of OLEDs.

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PubMed2006

En route to the formation of high-efficiency, osmium(II)-based phosphorescent materials.

Triosmium cluster complexes [Os3(CO)8(fppz)2] (2a) and [Os3(CO)8(fptz)2] (2b) bearing two 2-pyridyl azolate ligands were synthesized in an attempt to establish the reaction mechanism that gives rise to the blue-emitting phosphorescent complexes [Os(CO)2(fppz)2] (1a) and [Os(CO)2(fptz)2] (1b) [(fppz)H = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole; (fptz)H = 3-(trifluoromethyl)-5-(2-pyridyl)triazole]. X-ray structural analysis of 2b showed an open triangular metal framework incorporating multisite-coordinated 2-pyridyltriazolate ligands. Treatment of 2 with the respective 2-pyridylazolate ligand led to the formation of blue-emitting complex 1b, confirming their intermediacy, while the reaction of 2b with phosphine ligand PPh2Me afforded two hitherto novel hydride complexes 3 and 4, for which the reversible interconversion was clearly established at higher temperatures (> 180 degrees C). The single-crystal X-ray diffraction analyses of 3 and 4 confirmed their monometallic and isomeric nature, together with the coordination of two phosphine ligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolate chelate. Subtle differences in photophysical properties were examined for isomers 3 and 4 on the basis of steady state absorption and emission, the relaxation dynamics, and temperature-dependent luminescent studies. The results, in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights into the future design and preparation of highly efficient phosphorescent emitters.

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PubMed2006

Neutral Ru(II)-based emitting materials: a prototypical study on factors governing radiationless transition in phosphorescent metal complexes.

In addition to the metal-centered dd transition that is widely accepted as a dominant radiationless decay channel, other factors may also play important roles in governing the loss of phosphorescence efficiency for heavy-transition-metal complexes. To conduct our investigation, we synthesized two dicarbonylruthenium complexes with formulas [Ru(CO)2(BQ)2] (1) and [Ru(CO)2(DBQ)2] (2), for which the cyclometalated ligands BQ and DBQ denote benzo[h]quinoline and dibenzo[f,h]quinoxaline, respectively. Replacing one CO ligand with a P donor ligand such as PPh2Me and PPhMe2 caused one cyclometalated ligand to undergo a 180 degrees rotation around the central metal atom, giving highly luminous metal complexes [Ru(CO)L(BQ)2] and [Ru(CO)L(DBQ)2], where L = PPh2Me and PPhMe2 (3-6), with emission peaks lambda(max) in the range of 571-656 nm measured in the fluid state at room temperature. It is notable that the S0-T1 energy gap for both 1 and 2 is much higher than that of 3-6, but the corresponding phosphorescent spectral intensity is much weaker. Using these cyclometalated Ru metal complexes as a prototype, our experimental results and theoretical analysis draw attention to the fact that, for complexes 1 and 2, the weaker spin-orbit coupling present within these molecules reduces the T1-S0 interaction, from which the thermally activated radiationless deactivation may take place. This, in combination with the much smaller 3MLCT contribution than that observed in 3-6, rationalizes the lack of room-temperature emission for complexes 1 and 2.

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PubMed2006

Platinum(II) complexes with pyridyl azolate-based chelates: synthesis, structural characterization, and tuning of photo- and electrophosphorescence.

A new series of luminescent platinum(II) azolate complexes with a formula of [Pt(NwedgeN)(2)], in which NwedgeN = mppz (1), bppz (2a), bzpz (2b), bmpz (2c), bqpz (2d), fppz (3a), hppz (3b), bptz (4), hptz (5), were synthesized, and their photophyscial properties were examined. Single-crystal X-ray diffraction studies of 2c and 3b revealed a planar molecular geometry, in which the NwedgeN chelates adopt a trans configuration and show notable interligand C-H...N hydrogen bonding within the complex. Interesting intermolecular interactions were observed in the solid state. Complex 2c formed a slipped-stack structure with a Pt...Pt separation distance of 6.432 Angstroms, while complex 3b showed a columnar stacking with the molecules oriented in an alternating order in relation to the chain axis, giving a much reduced Pt...Pt distance of 3.442 Angstroms. The lowest absorption band for all complexes revealed strong state mixings between the singlet and triplet (MLCT and intraligand pipi) manifolds. Complexes 1 and 2 showed mixed (3)MLCT and (3)pipi phosphorescence in fluid solution. While radiationless deactivation was apparently dominant for complexes 3-5 in solution, resulting in rather weak emission, strong phosphorescence was observed in the room-temperature solid state with the peak wavelength being significantly red shifted compared to that in solution. The emission nature has been tentatively assigned to be (3)MMLCT in character. OLED devices with a multilayer configuration of ITO/NPB/CBP:2a/BCP/Alq(3)/LiF/Al were successfully fabricated using a CBP layer doped with various amount of 2a, ranging from 6 to 100%, as the emitting layer. A substantial red shift with increasing doping concentrations was observed in electroluminescence. With a neat film of 2a, the device showed a green emission with lambda(max) at 556 nm and an external QE of approximately 1.6% at a driving current of 20 mA. Similarly, for the device using a neat film of 3a, an electroluminescence centered at 616 nm with a slightly reduced external QE of approximately 2.1% was recorded. Aggregation of platinum(II) complexes in the solid state was proposed to account for the large red-shift in electroluminescence.

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PubMed2006

[Effect of compound glycyrrhizin on peripheral T-lymphocyte subset in AIDS patients].

OBJECTIVE: To probe the effect and mechanism of Compound Glycyrrhizin in treating AIDS. METHODS: Forty AIDS patients were randomly divided into a treatment group and a control group, both treated with HAART. In addition, the former was given Compound Glycyrrhizin for 6 months, and the CD4+ T count and the expressions of CD8+ and HLA-DR on the surface of peripheral blood lymphocytes (PBL) were studied before and after the treatment. RESULTS: After 6 months of treatment, the expressions of CD8+ and CD38+ of PBL in the treatment group [(6.6 +/- 2.1)%] were found lower than in the control [(11.4 +/- 3.8)%] (t = 5.043, P < 0.01) and CD4+ T count [(243.6 +/- 91.2) x 10(6)/L vs (170.8 +/- 55.7) x 10(6)/L] rose more significantly (t = 3.045, P < 0.01). CONCLUSION: Compound Glycyrrhizin can lower the expression of active T-lymphocyte subset, inhibit HIV and help immune reconstitution.

ADP-ribosyl Cyclase 1↗
PubMed2005

Design and synthesis of iridium(III) azacrown complex: application as a highly sensitive metal cation phosphorescence sensor.

A new metal cation probe bearing a central Ir(III) element and 1-aza-15-crown-5-ether substituted pyridyl pyrazolate as the chelate was synthesized. The octahedral molecular structure of was confirmed using single crystal X-ray diffraction analyses. Subsequent photophysical study showed yellow-green emission at approximately 560 nm in both fluid solution and solid state at room temperature. Remarkable differentiation in spectral properties upon metal cation (e.g. Ca2+) complexation makes complex a highly sensitive phosphorescence probe.

Cations↗
PubMed2005

Heteroleptic cyclometalated iridium(III) complexes displaying blue phosphorescence in solution and solid state at room temperature.

A series of heteroleptic Ir(III) metal complexes 1-3 bearing two N-phenyl-substituted pyrazoles and one 2-pyridyl pyrazole (or triazole) ligands were synthesized and characterized to attain highly efficient, room-temperature blue phosphorescence. The N-phenylpyrazole ligands, dfpzH = 1-(2,4-difluorophenyl)pyrazole, fpzH = 1-(4-fluorophenyl)pyrazole, dfmpzH = 1-(2,4-difluorophenyl)-3,5-dimethylpyrazole, and fmpzH = 1-(4-fluorophenyl)-3,5-dimethylpyrazole, show a similar reaction pattern with respect to the typical cyclometalated (C(wedge)N) chelate, which utilizes its ortho-substituted phenyl segment to link with the central Ir(III) atom, while the second 2-pyridylpyrazole (or triazole) ligand, namely, fppzH = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole, fptzH = 3-(trifluoromethyl)-5-(2-pyridyl)triazole, and hptzH = 3-(heptafluoropropyl)-5-(2-pyridyl)triazole, undergoes typical anionic (N--N) chelation to complete the octahedral framework. X-ray structural analyses on complexes [(dfpz)(2)Ir(fppz)] (1a) and [(fmpz)(2)Ir(hptz)] (3d) were established to confirm their molecular structures. Increases of the pipi energy gaps of the Ir(III) metal complexes were systematically achieved with two tuning strategies. One involves the substitution for one or two fluorine atoms at the N-phenyl segment or the introduction of two electron-releasing methyl substituents at the pyrazole segment of the H(C--N) ligands. Alternatively, we have applied the more electron-accepting triazolate in place of the pyrazolate segment for the third (N--N)H ligand. Our results, on the basis of steady-state, relaxation dynamics, and theoretical approaches, lead to a conclusion that, for complexes 1-3, the weakening of iridium metal-ligand bonding strength in the T(1) state plays a crucial role for the fast radiationless deactivation. For the case of [(fmpz)(2)Ir(hptz)] (3d), a thermal deactivation barrier of 4.8 kcal/mol was further deduced via temperature-dependent studies. The results provide a theoretical basis for future design and synthesis of the corresponding analogues suited to blue phosphorescent emitters.

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PubMed2005

Interplay between intra- and interligand charge transfer with variation of the axial N-heterocyclic ligand in osmium(II) pyridylpyrazolate complexes: extensive color tuning by phosphorescent solvatochromism.

The rational design and syntheses of a new series of Os(II) complexes with formula [Os(fppz)(2)(CO)(L)] (1: L=4-dimethylaminopyridine; 2: L = pyridine; 3: L = 4,4'-bipyridine; 4: L = pyridazine; 5: L = 4-cyanopyridine), bearing two (2-pyridyl)pyrazolate ligands (fppz) together with one carbonyl and one N-heterocyclic ligand at the axial positions are reported. Single-crystal X-ray diffraction studies of, for example, 2 reveal a distorted octahedral geometry in which both fppz ligands reside in the equatorial plane with a trans configuration and adopt a bent arrangement at the metal center with a dihedral angle of approximately 23 degrees , while the carbonyl and pyridine ligands are located at the axial positions. Variation of the axial N-heterocyclic ligand leads to remarkable changes in the photophysical properties as the energy gap and hence the phosphorescence peak wavelength can be tuned. For complexes 1 and 2 the solvent-polarity-independent phosphorescence originates from a combination of intraligand (3)pi-pi* ((3)ILCT) and metal-to-ligand charge transfer transitions ((3)MLCT). In sharp contrast, as supported by cyclic voltammetry measurements and theoretical calculations, complexes 3--5 exhibit mainly ligand-to-ligand charge transfer (LLCT) transitions, resulting in a large dipolar change. The phosphorescence of complexes 3--5 thus exhibits a strong dependence on the polarity of the solvent, being shifted for example, from 560 (in C(6)H(12)) to 665 nm (in CH(3)CN) and from 603 (in C(6)H(12)) to 710 nm (in CH(3)CN) for complexes 3 and 5, respectively. The results clearly demonstrate that a simple, straightforward derivatization of the axial N-heterocyclic ligand drastically alters the excitation properties per se from intraligand charge transfer (ILCT) to LLCT transitions. The latter exhibit remarkable LLCT phosphorescence solvatochromism so that a broad range of color tunability can be achieved.

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PubMed2005

New CVD precursors capable of depositing copper metal under mixed O2/Ar atmosphere.

Volatile low-melting CuII metal complexes Cu[OC(CF3)2CH2C(Me)=NMe]2 (4) and Cu[OC(CF3)2CH2CHMeNHMe]2 (5) were synthesized and characterized by spectroscopic methods. A single-crystal X-ray diffraction study on complex 4 shows the anticipated N2O2 square-planar geometry with the imino alcoholate ligand arranged in the all-trans orientation. In contrast, a highly distorted N2O2 geometry with a dihedral angle of 33 degrees was observed for complex 5, suggesting that the fully saturated amino alcoholate ligand produces a much greater steric congestion around the metal ion. Metal CVD experiments were conducted, showing that both complexes, 4 and 5, are capable of depositing copper metal at temperatures of 275-300 degrees C using an inert argon carrier gas mixed with low concentrations (2-8%) of O2. The best copper thin film showed a purity of approximately 96 at. % and a resistivity of 2.11 microOmega cm versus that of the bulk standard (1.7 microOmega cm), as revealed by XPS and four-point probe analyses, respectively. We speculate that the low concentration of O2 promotes partial ligand oxidation, thus releasing the reduced copper on the substrate and affording the high-purity copper deposit.

Journal Article↗
PubMed2005

Highly efficient red-electrophosphorescent devices based on polyfluorene copolymers containing charge-transporting pendant units.

We have systematically examined the photoluminescence (PL) and electroluminescence (EL) behavior of blends comprising two efficient red phosphors doped, respectively, into the blue-emitting polyfluorene derivatives PF-TPA-OXD and PF-OXD. The host polymers, which contain both hole- and electron-transporting or merely electron-transporting side chains, are capable of facilitating charge injection and transport. After determining the HOMO and LUMO energy levels of these materials, we were able to match the dopant with its most suitable host to achieve the direct formation and confinement of an exciton at the dopant. This configuration also leads to a reduction in the electrical excitation of the host polymer, which in turn decreases the degree of exciton loss arising from nonradiative decay of the host triplet. Using this approach, we were able to realize the production of high-performance red-electrophosphorescent devices. For Os(fppz)-doped devices, we obtain a balanced charge recombination in conjunction with higher current and luminance when using PF-TPA-OXD as the host matrix; this device reached a maximum external quantum efficiency of 8.37% with a peak brightness of 16 720 cd/m2. The absence of charge-transporting pendant units, i.e., the device fabricated from poly[9,9-dioctylfluorene-2,7-diyl] (POF), led, however, to relatively poor electroluminescence characteristics (5.81% and 2144 cd/m2).

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PubMed2005

Dual room-temperature fluorescent and phosphorescent emission in 8-quinolinolate osmium(II) carbonyl complexes: rationalization and generalization of intersystem crossing dynamics.

A new series of quinolinolate osmium carbonyl complexes were synthesized and characterized by spectroscopic methods. Single-crystal X-ray diffraction studies indicate that these complexes consist of an octahedral ligand arrangement with one chelating quinolinolate, one tfa or halide ligand, and three mutually orthogonal terminal CO ligands. Variation of the substituents on quinolinolate ligands imposes obvious electronic or structural effects, while changing the tfa ligand to an electron-donating iodide slightly increases the charge density on the central osmium atom. These Os(II) complexes show salient dual emissions consisting of fluorescence and phosphorescence, the spectral properties and relaxation dynamics of which have been studied comprehensively. The results, in combination with the theoretical approaches, lead us to propose that the emission mainly originates from the quinolinolate pi pi* state. Both experimental and theoretical approaches generalize various types of intersystem crossing versus those of the tris(quinolinolate) iridium Ir(Q)3, and their relative efficiencies were accessed on the basis of the associated frontier orbital configurations. Our results suggest that [1d(pi)pi* absolute value(H(so))3 pi pi*] (or [3d(pi)pi* absolute value(H(so))1 pi pi*]) in combination with a smaller deltaE(S1-T1) gap (i.e., increasing the MLCT (d(pi)pi*) character) is the main driving force to induce the ultrafast S1 --> T1 intersystem crossing in the third-row transition metal complexes, giving the strong phosphorescent emission.

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PubMed2005

Synthesis, characterization, and photophysical properties of Os(II) diimine complexes [Os(N(wedge)N)(CO)(2)I(2)] (N(wedge)N = bipyridine, phenanthroline, and pyridyl benzoxazole).

A new series of Os(II) diimine complexes with the general formula [Os(N(wedge)N)(CO)(2)I(2)], N(wedge)N = 2,2'-bipyridine (bpy) (1), 4,4'-di-tert-butyl-2,2'-bipyridine (dbubpy) (2), 4,7-diphenyl-1,10-phenanthroline (dpphen) (3), 2-(2'-pyridyl)benzoxazole (pboz) (4), and 5-tert-butyl-2-(2'-pyridyl)benzoxazole (bupboz) (5), were synthesized and characterized by spectroscopic methods and by a single-crystal X-ray diffraction study on the dpphen complex 3. The corresponding photophysical properties were studied using UV-vis and emission spectrometry. The resulting phosphorescence features both in solution and as a solid film, in combination with the MO calculation, lead us to conclude that the emissions originate from mixed halide-to-ligand (XLCT approximately 70%) and metal-to-ligand (MLCT approximately 30%) transitions instead of the typical MLCT transition. Using complexes 4 and 5 as the dopant emitters, we evaluated their potential to serve as a phosphor for organic light emitting diodes by examining their electroluminescent performances. Reddish orange electroluminescence centered around 600 nm was observed for organic light emitting diodes (OLEDs) fabricated using complex 5 as the emitter; the device efficiency was shown to be as high as 2.8% (and 5.0 cd/A or 2.7 lm/W), and the peak luminance was shown to be 5600 cd/m(2) at a driving voltage of approximately 15 V.

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PubMed2005

Iridium(III) complexes with orthometalated quinoxaline ligands: subtle tuning of emission to the saturated red color.

Rational design and syntheses of four iridium complexes (1-4) bearing two substituted quinoxalines and an additional 5-(2-pyridyl) pyrazolate or triazolate as the third coordinating ligand are reported. Single-crystal X-ray diffraction studies of 1 reveal a distorted octahedral geometry, in which two dpqx ligands adopt an eclipse configuration, for which the quinoxaline N atoms and the C atoms of orthometalated phenyl groups are located at the mutual trans- and cis-positions, respectively. The lowest absorption band for all complexes consists of a mixture of heavy-atom Ir(III)-enhanced 3MLCT and 3pipi* transitions, and the phosphorescent peak wavelength can be fine-tuned to cover the spectral range of 622-649 nm with high quantum efficiencies. The cyclic voltammetry was measured, showing a reversible, metal-centered oxidation with potentials at 0.76-1.03 V, as well as two reversible reduction waves with potentials ranging from -1.61 to -2.06 V, attributed to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C/N ligands. Complex 1 was used as the representative example to fabricate the red-emitting PLEDs by blending it into a PVK-PBD polymer mixture. The devices exhibited the characteristic emission profile of 1 with peak maxima located at 640 nm. The maximum external quantum efficiency was 3.15% ph/el with a brightness of 1751 cd/m2 at a current density of 67.4 mA/cm2, and the maximum brightness of 7750 cd/m2 was achieved at the applied voltage of 21 V and with CIE coordinates of (0.64, 0.31).

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