Ren Zhi-Gang, Yang Jun-Yi, Song Ying-Lin, Li Ni-Ya, Li Hong-Xi, Chen Yang, Zhang Yong, Lang Jian-Ping
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, 215123, P. R. China.
Dalton Trans. 2009 Apr 14(14):2578-87. doi: 10.1039/b819240e. Epub 2009 Feb 17.
Reactions of trans-[(eta5-C5Me5)2Mo2S2(mu-S)2] (1) with 2 equiv. of [Cu(MeCN)4]X (X = PF6-, ClO4-) produced two acetonitrile-coordinated cubane-like cationic clusters [(eta5-C5Me5)2Mo2(mu3-S)4Cu2(MeCN)2]X2 (X = PF6- (2), ClO4- (3)). Treatment of 2 or 3 with 4,4'-bipyridine (4,4'-bipy) or trans-1,2-bis(4-pyridyl)ethylene) (bpee) afforded two polymeric clusters {[(eta5-C5Me5)2Mo2(mu3-S)4Cu2(L)]X2}n (4: L = 4,4'-bipy, X = PF6-; 5: L = bpee, X = ClO4-), while analogous reactions of 2 or 3 with 1,2-bis(4-pyridyl)ethane (bpea), 1,2-bis(diphenylphosphine)ethane (dppe), or 1,4-bis-(diphenylphosphine)butane) (dppb) formed three dimeric clusters [(eta5-C5Me5)2Mo2(mu3-S)4Cu2(L)]2X4 (6: L = bpea; X = PF6-; 7: L = dppe, X = ClO4-; 8: L = dppb, X = ClO4-). Clusters 2-8 consist of a cubane-like [(eta5-C5Me5)2Mo2(mu3-S)4Cu2] core with each Cu being coordinated by one labile MeCN molecule (2, 3) or by bridging dipyridyl or diphosphino ligands (4-8). 4 or 5 has a 1D zigzag chain structure while 6-8 contain cyclic dimeric structures. The third-order non-linear optical (NLO) properties of 2-8 in MeCN were investigated by Z-scan technique at 532 nm. These compounds showed strong third-order NLO absorption effects and self-defocusing properties, and their NLO performances were remarkably enhanced relative to those of 1.
反式 - [(η⁵ - C₅Me₅)₂Mo₂S₂(μ - S)₂]（1）与2当量的[Cu(MeCN)₄]X（X = PF₆⁻，ClO₄⁻）反应生成了两个乙腈配位的类立方烷阳离子簇[(η⁵ - C₅Me₅)₂Mo₂(μ₃ - S)₄Cu₂(MeCN)₂]X₂（X = PF₆⁻（2），ClO₄⁻（3））。用4,4'-联吡啶（4,4'-bipy）或反式 - 1,2 - 双（4 - 吡啶基）乙烯（bpee）处理2或3得到两个聚合物簇{[(η⁵ - C₅Me₅)₂Mo₂(μ₃ - S)₄Cu₂(L)]X₂}ₙ（4：L = 4,4'-bipy，X = PF₆⁻；5：L = bpee，X = ClO₄⁻），而2或3与1,2 - 双（4 - 吡啶基）乙烷（bpea）、1,2 - 双（二苯基膦）乙烷（dppe）或1,4 - 双（二苯基膦）丁烷（dppb）的类似反应形成了三个二聚体簇[(η⁵ - C₅Me₅)₂Mo₂(μ₃ - S)₄Cu₂(L)]₂X₄（6：L = bpea；X = PF₆⁻；7：L = dppe，X = ClO₄⁻；8：L = dppb，X = ClO₄⁻）。簇2 - 8由一个类立方烷[(η⁵ - C₅Me₅)₂Mo₂(μ₃ - S)₄Cu₂]核心组成，每个Cu由一个不稳定的MeCN分子（2, 3）配位或由桥连的二吡啶或二膦配体（4 - 8）配位。4或5具有一维锯齿链结构，而6 - 8包含环状二聚体结构。通过Z - 扫描技术在532 nm波长下研究了2 - 8在乙腈中的三阶非线性光学（NLO）性质。这些化合物表现出强烈的三阶NLO吸收效应和自散焦性质，并且它们的NLO性能相对于1有显著增强。
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