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Yu-Shan Yeh

Publications and source records attributed to Yu-Shan Yeh.

8 recordsLinked to original sources
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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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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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

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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