From trans-[(eta5-C5Me5)2Mo2S2(mu-S)2] to [(eta5-C5Me5)2Mo2(mu3-S)4(CuMeCN)2]2+ to [(eta5-C5Me5)2Mo2(mu3-S)4Cu2]-based polymeric and dimeric clusters: syntheses, structures and enhanced third-order non-linear optical performances.
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.
Ren
Zhi-Gang
ZG
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, 215123, P. R. China.
Yang
Jun-Yi
JY
Song
Ying-Lin
YL
Li
Ni-Ya
NY
Li
Hong-Xi
HX
Chen
Yang
Y
Zhang
Yong
Y
Lang
Jian-Ping
JP