TDDFT study on electronic excitations and first hyperpolarizabilities of mixed-metal carbonyl clusters MonIr4-n(μ-CO)3(β5-Cp)n(n = 1,2,3)

Li, Fujun; Liu, Caiping; Liu, Chun‐Wan; Wu, Kechen

doi:10.1080/00268970701534555

Cited by 3 publications

References 32 publications

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Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

et al. 2013

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Metal cluster core expansion at tetrahedral group 6-group 9 mixed-metal clusters MIr3(μ-CO)3(CO)8(η(5)-L) (M = W, Mo, L = C5H5; M = Mo, L = C5Me5) with the iridium capping reagents Ir(CO)2(η(5)-L') (L' = C5Me5, C5Me4H) in refluxing toluene afforded the trigonal-bipyramidal clusters MIr4(μ-CO)3(CO)7(η(5)-C5H5)(η(5)-L') (M = Mo, L' = C5Me5, 1a; M = W, L' = C5Me5, 1b; M = Mo, L' = C5Me4H, 1c; M = W, L' = C5Me4H, 1d) and MoIr4(μ3-H)(μ-CO)2(μ-η(1):η(5)-CH2C5Me4)(CO)7(η(5)-C5Me5) (2). Related reactions with M2Ir2(μ-CO)3(CO)7(η(5)-L)2 (M = W, Mo, L = C5H5; M = Mo, L = C5Me5) afforded M2Ir3(μ-CO)3(CO)6(η(5)-C5H5)2(η(5)-L') (M = Mo, L' = C5Me5, 3a; M = W, L' = C5Me5, 3b; M = Mo, L' = C5Me4H, 3c; M = W, L' = C5Me4H, 3d), W2Ir3(μ-CO)4(CO)5(η(5)-C5H5)2(η(5)-C5Me4H) (4), and Mo2Ir3(μ-CO)3(CO)6(η(5)-C5Me5)3 (5). Single-crystal X-ray diffraction studies of 1a-1d, 2, 3a-3d, and 4 confirmed their molecular structures, including the μ-η(1):η(5)-CH2C5Me4 ligand at hydrido cluster 2, derived from a C-H bond activation of one of the methyl groups. Density functional theory (DFT) studies were employed to suggest the structure of 5. The redox behavior of the new clusters was examined through cyclic voltammetry; all clusters exhibit oxidation and reduction processes (with respect to the resting state), with the oxidation processes being the more reversible, and increasingly so on decreasing Ir content of the clusters, replacing W by Mo, and increasing alkylation of the cyclopentadienyl ligands. In situ IR and UV-vis-near-IR spectroelectrochemical studies of the reversible oxidation processes in 1a and 3a were undertaken, with the spectra of the former suggesting progression to an all-terminal CO geometry concomitant with the first oxidation and a significant structural change upon the second oxidation step. DFT studies of 1a revealed that its crystallographically-confirmed Mo-equatorial core geometry is essentially isoenergetic with a possible Mo-apical isomer, and identified several bridging CO structures for the charged states.

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Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

et al. 2013

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Second-order nonlinear optical properties of transition metal clusters [MoS4Cu4X2Py2] (M = Mo, W; X = Br, I)

Wei

et al. 2009

Phys. Chem. Chem. Phys.

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We present in this paper the second-order nonlinear optical properties of a series of penta-nuclear metal clusters [MS4Cu4X2Py6] (M=Mo, W; X=Br, I) on the basis of the hyper-Rayleigh scattering experiments and the first-principle calculations (TDDFT). The measurements obtain the notably large dynamic quadratic hyperpolarizabilities at 1064 nm [beta(-2omega, omega, omega) values are around 200x10(-30) esu] and, by extrapolation, a large static values around 60x10(-30) esu. The computational results of the electronic excitation energies and quadratic hyperpolarizabilities by TDDFT method are in good agreement with the experimental values and by careful examination they are both dependent on the nature of the metals. The in-depth analysis of the mechanism for the second-order response unambiguously shows the evidence of the contribution of direct metal-metal interaction charge transfers. This provides a new tool to tune nonlinear optical properties in exploiting metal cluster materials and molecular devices.

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Mn₅: high-spin structures and energetics

2016

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TDDFT study on electronic excitations and first hyperpolarizabilities of mixed-metal carbonyl clusters Mo_nIr_4-n(μ-CO)₃(β⁵-Cp)_n(n = 1,2,3)

Cited by 3 publications

References 32 publications

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

Second-order nonlinear optical properties of transition metal clusters [MoS4Cu4X2Py2] (M = Mo, W; X = Br, I)

Mn₅: high-spin structures and energetics

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TDDFT study on electronic excitations and first hyperpolarizabilities of mixed-metal carbonyl clusters MonIr4-n(μ-CO)3(β5-Cp)n(n = 1,2,3)

Cited by 3 publications

References 32 publications

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)2(η5-C5Me4R) (R = H, Me)

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)2(η5-C5Me4R) (R = H, Me)

Second-order nonlinear optical properties of transition metal clusters [MoS4Cu4X2Py2] (M = Mo, W; X = Br, I)

Mn5: high-spin structures and energetics

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TDDFT study on electronic excitations and first hyperpolarizabilities of mixed-metal carbonyl clusters Mo_nIr_4-n(μ-CO)₃(β⁵-Cp)_n(n = 1,2,3)

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)₂(η⁵-C₅Me₄R) (R = H, Me)

Mn₅: high-spin structures and energetics