Construction of cluster-based supramolecular wire and rectangle

Yi Tan  , Zhi-Kang Wang , Fei-Fan Lang , Hui-Min Yu , Chen Cao, Chun-Yan Ni , Meng-Yi Wang  , Ying-Lin Song  , Jian-Ping Lang 

Reactions of [Et4N][Tp*WS3(CuCl)3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv. of AgOTf (OTf− = trifluoromethanesulfonate) and 1 equiv. of several bidentate pyridine ligands including 2,5-bis(pyridine-4-yl)thiazolo[5,4-d]thiazole (L1), 2,7-di(pyridin-4-yl)-9H-fluorene (L2), 2,7-di(pyridin-4-yl)-9H-carbazole (L3), and 2,7-di(pyridin-4-yl)-9H-fluoren-9-one (L4) afforded four W/Cu/S cluster-based supramolecular compounds [(Tp*WS3Cu2Cl)2(L1)] (2), {[(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2(L2)2}(OTf)2 (3), {[(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2(L3)2}(OTf)2 (4) and {[(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2(L4)2}(OTf)2 (5). Compounds 2–5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray diffraction analysis. The neutral cluster 2 behaves as a supramolecular wire constructed by L1 bridging two butterfly-shaped [Tp*WS3Cu2Cl] cores. The cluster cations of 3–5 contain two [(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]+ cores linked by two L2, L3, or L4 ligands, which finally formed a cationic supramolecular rectangle. The third-order nonlinear-optical (NLO) properties of 3–5 in DMF were also investigated by Z-scan techniques and their NLO responses were enhanced compared to those of their precursor 1.

基于簇的超分子线和矩形的构建

[Et 4 N][Tp*WS 3 (CuCl) 3 ] ( 1 ) (Tp* = Hydrodotris(3,5-dimethylpyrazol-1-yl)borate) 与 2 equiv 的反应。AgOTf (OTf - = 三氟甲磺酸盐) 和 1 equiv。几种双齿吡啶配体，包括 2,5-双(吡啶-4-基)噻唑并[5,4-d]噻唑 ( L1 )、2,7-二(吡啶-4-基)-9 H-芴 ( L2 ) )、2,7-di(pyridin-4-yl)-9 H-咔唑 ( L3 ) 和 2,7-di(pyridin-4-yl)-9 H -fluoren-9-one ( L4 ) 得到四种基于W/Cu/S簇的超分子化合物[(Tp*WS 3 Cu 2 Cl) 2( L1 )] ( 2 ), {[(Tp*WS 3 Cu 3 ) 2 (μ-Cl) 2 (μ 4 -Cl)] 2 ( L2 ) 2 }(OTf) 2 ( 3 ), {[(Tp *WS 3 Cu 3 ) 2 (μ-Cl) 2 (μ 4 -Cl)] 2 ( L3 ) 2 }(OTf) 2 ( 4 ) 和 {[(Tp*WS 3 Cu 3 ) 2 (μ-Cl) 2 (μ4-Cl)] 2 (L4 ) 2 }(OTf) 2 ( 5 )。通过元素分析、IR、UV-vis、1 H NMR 和单晶 X 射线衍射分析对化合物2-5进行了表征。中性簇2表现为由L1桥接两个蝴蝶形 [Tp*WS 3 Cu 2 Cl] 核构成的超分子线。3-5的簇阳离子包含两个 [(Tp*WS 3 Cu 3 ) 2 (μ-Cl) 2 (μ 4 -Cl)] +核，由两个L2、L3或L4配体，最终形成阳离子超分子矩形。还通过Z扫描技术研究了 DMF 中3-5的三阶非线性光学 (NLO) 特性，与它们的前体1相比，它们的 NLO 响应得到了增强。

DOI: 10.1039/d2dt00344a