Assembly of [Tp*WS3Cu2]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances
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- 作者：Quan Liu ; Xin Zhao ; Feng Zhou ; Ying-Lin Song ; Wen-Hua Zhang ; Jian-Ping Lang
- 刊名：Crystal Growth & Design
- 出版年：2016
- 出版时间：June 1, 2016
- 年：2016
- 卷：16
- 期：6
- 页码：3206-3214
- 全文大小：648K
- 年卷期：0
- ISSN：1528-7505
文摘
We have prepared a family of [WS3Cu2]-based coordination polymers with a rare μ-N type coordination by a simple one-pot assembly of [Et4N][Tp*WS3] (1) with CuCN in the presence of pyridine (py), 4,4′-bipyridine (bipy), 1,2-bis(4-pyridyl)ethane (bpea), and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) at room temperature. The resulting coordination polymers [Tp*WS3Cu2(CN)(μ-py)]2·py (2·py), [Tp*WS3Cu2(CN)2Cu(μ-py)2]2·3py (3·3py), [Et4N][{Tp*WS3(CuCN)2Cu}2(CN)(μ4-bipy)] (4), [Tp*WS3Cu2(CN)(μ4-bpea)0.5]2·CH2Cl2 (5·CH2Cl2), and [Tp*WS3Cu2(CN)(μ6-tpt)1/3]2 (6) share a butterfly-shaped [Tp*WS3Cu2] motif with sizable concave to accommodate pyridyl ligands. The approximate mirror symmetry of the motif also induces the orthogonal coalignment of the pyridyl ligands, reinforcing a unique μ-type association with the Cu centers of the cluster skeleton. Such a coordination mode, though scarce in general coordination chemistry, is universal in our series with good ligand tolerance including ligand size and symmetry. In addition, each butterfly-shaped [Tp*WS3Cu2] motif is linked by CN (2), Cu(CN)2 (3), Cu2(CN)5/μ4-bipy (4), CN/μ4-bpea (5), and CN/μ6-tpt (6) to yield diverse polydimensional structures showing one-dimensional zigzag chains (2 and 3), two-dimensional networks (4 and 5), and a three-dimensional net (6). The third-order nonlinear optical (NLO) property of 2–6 in DMF measured using a Z-scan technique at 532 nm demonstrated that 2–6 have a reverse saturable absorption and self-focusing effects with the hyperpolarizability γ values in the range of 6.32 × 10–30 esu to 9.82 × 10–30 esu. Such values are remarkably larger than that of their precursor complex 1 (1.07 × 10–32 esu). The results provide an interesting insight into how the μ-type coordination mode of N-donor ligands affects the self-assembly of the [Tp*WS3Cu2]-supported coordination polymers and their structural topologies, as well as their third-order NLO performances.