Nonlinear Optical Properties of Inorganic Clusters

Shi, Shaoyun

doi:10.1007/978-1-4757-6101-6_3

Cited by 24 publications

(26 citation statements)

References 36 publications

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“…Remarkably all the osmium carbonyl clusters here investigated are quite stable and do not decompose upon laser excitation to give M−M bond cleavage (as previously observed for Ru 3 (CO) 12 , Rh 4 (CO) 12 , and Ir 4 (CO) 12 ); in addition, some complexes here described have μβ 0 values comparable to those of Disperse Red 1 ( trans- 4,4‘-O 2 NC 6 H 4 NNC 6 H 4 NEt(CH 2 CH 2 OH), μβ 0 = 500 × 10 -48 esu), which is currently used in electrooptic polymers …”

Section: Discussionsupporting

confidence: 80%

“…To our knowledge there is no experimental report about second-order NLO properties of molecular metal clusters. Some attempts to study third-order NLO properties of metal carbonyl clusters such as Ru 3 (CO) 12 , Rh 4 (CO) 12 , and Ir 4 (CO) 12 failed due to their photoinstability upon laser excitation, which induces facile M−M bond cleavage of the clusters and subsequent fragmentation …”

Section: Introductionmentioning

confidence: 99%

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Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

et al. 2004

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Coordination to the "Os 3 (CO) 11 " cluster core of substituted styrylpyridines such as trans-4-(4′-NMe 2 -styryl)pyridine (L 1 ), trans-4-(4′-t-Bu-styryl)pyridine (L 2 ), trans-4-(4′-CF 3 -styryl)pyridine (L 3 ), or trans,trans-4-(4′-NMe 2 -phenyl-1,3-butadienyl)pyridine (L 4 ) produces an enhancement of their quadratic hyperpolarizability, β EFISH , measured by the solution-phase dc electric-field-induced second harmonic (EFISH) generation method. This effect is due either to a red-shift of the intraligand charge-transfer (ILCT) transition upon coordination (when the substituent in para position is a strong electron donor) or to a metal-to-ligand chargetransfer (MLCT) transition (when the substituent is a strong electron acceptor). In the latter case the quadratic hyperpolarizability has a negative sign, due to the negative value of ∆µ eg . Therefore the "Os 3 (CO) 11 " cluster core displays an ambivalent acceptor or donor role. Some of the complexes investigated in this study show significant values (between 500 × 10 -48 and 900 × 10 -48 esu) of the product µβ 0 .

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Section: Discussionsupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

et al. 2004

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“…Recently, transition-metal sulfur clusters have grown into a new promising class of NLO material [4], and have gradually been paid attention to by virtue of their possessing the combined advantages of both organic polymers and inorganic semiconductors [5,6]. The multinuclear molybdenum and tungsten complexes are one of the systems that having been investigated [7]. The binuclear molybdenum carbonyl complexes containing thiolate bridges, with a planar [Mo 2 S 2 ] core were synthesized in 1984 by reaction of Mo(CO) 6 with thiolate ligands [8].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures and calculated nonlinear optical properties of seven di-nuclear metal (0,I) carbonyl cyclohexanthiolates, [M2(μ-SC6H11)x(CO)y]n− (M=Mo,W; x=2,3; y=6,8; n=0,1,2)

Zhou

Zhuang

et al. 2007

Journal of Organometallic Chemistry

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“…They differ from poly-nuclear metal cluster complexes due to their weak metal-metal interactions but notable cooperative effect between adjacent metal centres [5][6][7][8]. Since 1988, mixed-metal cluster chemistry has been extensively studied and many interesting complexes have been synthesized and characterized [9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

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)

Liu

et al. 2007

Molecular Physics

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A series of mixed-metal carbonyl clusters, Mo n Ir 4-n (-CO) 3 (CO) 9-n ( 5 -Cp) n (n ¼ 1, 2; Cp ¼ C 5 H 4 Me, C 5 HMe 4 , C 5 Me 5 , C 5 H 5 ), have been investigated using the TDDFT method. The results estimated the medium magnitude of the first static hyperpolarizabilities ( tot $ 2 Â 10 À30 esu) of these tetrahedral mixed-metal clusters, most of which originate from the intra-cluster charge transfer of the metal skeleton consisting of polar metal-metal interactions. No direct contributions of the Cp ligands to the relevant charge transfer were found, but the cooperative effect between the metal centres and Cp ligands impacts the . Based on these studies a mixed-metal cluster Mo 3 Ir(-CO) 3 (CO) 7 ( 5 -Cp) 2 was designed that exhibits enhanced first hyperpolarizability.

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Nonlinear Optical Properties of Inorganic Clusters

Cited by 24 publications

References 36 publications

Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

Synthesis, crystal structures and calculated nonlinear optical properties of seven di-nuclear metal (0,I) carbonyl cyclohexanthiolates, [M2(μ-SC6H11)x(CO)y]n− (M=Mo,W; x=2,3; y=6,8; n=0,1,2)

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)

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Nonlinear Optical Properties of Inorganic Clusters

Cited by 24 publications

References 36 publications

Effect of the Coordination to the “Os3(CO)11” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe2,t-Bu, CF3) andtrans,trans-4-(4‘-NMe2-phenyl-1,3-butadienyl)pyridine

Effect of the Coordination to the “Os3(CO)11” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe2,t-Bu, CF3) andtrans,trans-4-(4‘-NMe2-phenyl-1,3-butadienyl)pyridine

Synthesis, crystal structures and calculated nonlinear optical properties of seven di-nuclear metal (0,I) carbonyl cyclohexanthiolates, [M2(μ-SC6H11)x(CO)y]n− (M=Mo,W; x=2,3; y=6,8; n=0,1,2)

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)

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Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

Effect of the Coordination to the “Os₃(CO)₁₁” Cluster Core on the Quadratic Hyperpolarizability oftrans-4-(4‘-X-styryl)pyridines (X = NMe₂,t-Bu, CF₃) andtrans,trans-4-(4‘-NMe₂-phenyl-1,3-butadienyl)pyridine

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)