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基于双齿到四齿桥连配体的零维到三维的调谐三唑银(I)发光配合物。

Tuned triazolatesilver(I) luminescent complexes from zero- to three-dimensionality based on bi- to tetratopic bridged ligands.

作者信息

Wang Ying, Ding Bin, Cheng Peng, Liao Dai-Zheng, Yan Shi-Ping

机构信息

Department of Chemistry, Nankai University, Tianjin 300071, People's Republic of China.

出版信息

Inorg Chem. 2007 Mar 19;46(6):2002-10. doi: 10.1021/ic060855y. Epub 2007 Feb 10.

Abstract

The self-assembly of silver(I) salts with bitopic triazole ligands 4-(salicylideneamino)-1,2,4-triazole (L1) and 4-(2-pyridinyl)-1,2,4-triazole (L2) produced dinuclear complexes and a 1D molecular-ladder coordination polymer, while the reaction of tritopic ligand 4-(3-pyridinyl)-1,2,4-triazole (L3) with AgClO4 afforded a right-handed helical 2D network with (4,4) topology, a meso layer constructed via left- and right-handed helical chains with AgBF4, and a 2D 4.8(2) net containing no helical chain with AgNO3. Using a tetratopic triazole ligand 2,6-bis(4-triazolyl)pyridine (L4), a 3D coordination polymer was isolated. This complex contains a cationic 4.63 network with rhombic channels, accepting two columns of uncoordinated ClO4(-) anions filling into every central cavity. Our results show that (i) the increase of coordination sites of the ligands is an effective route to obtaining higher-dimensional structures and (ii) anions could influence the configuration of the ligand to tune the coordination network topology from those with helical chains to those without. In the solid state, all of the complexes exhibit strong fluorescent emission bands, which may be assigned to intraligand fluorescent emission. The luminescent properties of these complexes in a water solution varied from blue light to green light at ambient temperature.

摘要

银(I)盐与双位点三唑配体4-(水杨基亚氨基)-1,2,4-三唑(L1)和4-(2-吡啶基)-1,2,4-三唑(L2)的自组装产生了双核配合物和一维分子梯状配位聚合物,而三位点配体4-(3-吡啶基)-1,2,4-三唑(L3)与高氯酸银反应得到了具有(4,4)拓扑结构的右手螺旋二维网络,与四氟硼酸银形成了由左手和右手螺旋链构成的中观层,与硝酸银反应得到了不含螺旋链的二维4.8(2)网络。使用四位点三唑配体2,6-双(4-三唑基)吡啶(L4),分离得到了一种三维配位聚合物。该配合物包含一个具有菱形通道的阳离子4.63网络,每个中心腔中容纳两列未配位的高氯酸根阴离子。我们的结果表明:(i)配体配位位点的增加是获得更高维结构的有效途径;(ii)阴离子可以影响配体的构型,从而将配位网络拓扑结构从具有螺旋链的结构调整为无螺旋链的结构。在固态下,所有配合物均表现出强荧光发射带,这可能归因于配体内荧光发射。这些配合物在水溶液中的发光性质在室温下从蓝光变为绿光。

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