Syntheses, structural, theoretical, and nonlinear optical studies of non-interpenetrating three-dimensional nest-shaped-cluster [MoOS 3 Cu 3 ]-based coordination polymers

Date

2011

Authors

Zhang, Jinfang
Meng, Suci
Song, Yinglin
Zhou, Yimeng
Cao, Yuan
Li, Jianghua
Zhao, Huajian
Hu, Jingchun
Wu, Jinhua
Zhang, Chi

Journal Title

Journal ISSN

Volume Title

Publisher

American Chemical Society

Abstract

An efficient route to construct three-dimensional (3-D) M/S/Cu nest-cluster-based coordination polymers has been developed. By this method, cyanide bridges have been successfully introduced to build three new non-interpenetrating 3-D nest-shaped-cluster [MoOS3Cu 3]-based coordination polymers, 3∞{[(NO3)⊂(Me4N)3] ⊂[MoOS3Cu3(CN)3]} (1) and 3∞{[(NH4)·2DMF]⊂[Mo2O 2S6Cu6(CN)3(L)4]} (L 1 = bipy = 4,4′-bipyridine, 2; L2 = bpee = 1,2-bis(4-pyridyl)ethene, 3). The structures of 1-3 have been established by elemental analysis, IR, UV-vis, and single-crystal X-ray crystallographic studies. 1 is the first non-interpenetrating 3-D 6-connected M/S/Cu coordination polymer and possesses an unprecedented dual-inclusive structure, rare "ACS" topology and huge free volume. 2 and 3 possess unusual non-interpenetrating 3-D pillar-layer-alternating honeycomb-like frameworks with diamondoid topologies. Nonlinear optical (NLO) properties of these clusters were investigated by Z-scan employing 5 ns pulses at 532 nm, with 1-3 showing strong third-order NLO properties. Time-dependent density functional theory (TD-DFT) studies have afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

Description

Keywords

Keywords: Bipyridines; Cluster-based; Coordination Polymers; Crystallographic studies; Cyanide bridge; Diamondoid topology; Electronic transition; Elemental analysis; Functionalized; Molecular materials; NLO properties; Nonlinear optical properties; Nonlinear optic

Citation

Source

Crystal Growth & Design

Type

Journal article

Book Title

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DOI

10.1021/cg1009779

Restricted until

2037-12-31