Luminescent copper(I) halide butterfly dimers coordinated to [Au(CH3imCH2py)2]BF4 and [Au(CH3imCH2quin)2]BF4.
Luminescent copper(I) halide butterfly dimers coordinated to [Au(CH3imCH2py)2]BF4 and [Au(CH3imCH2quin)2]BF4.
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发光卤化铜 (I) 蝴蝶二聚体与 [Au(CH3imCH2py)2]BF4 和 [Au(CH3imCH2quin)2]BF4 配位。
DOI：
10.1021/ic901914n
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发表时间：
2009
影响因子：
4.6
通讯作者：
Jineun Kim
中科院分区：
文献类型：
--
作者：
V. Catalano;Adam L. Moore;J. Shearer;Jineun Kim
研究了卤化铜(I)与均配的N-杂环卡宾Au(I)配合物[Au(CH(3)imCH(2)quin)(2)]BF(4)和Au(CH(3)imCH(2)py)(2)]BF(4)的配位化学。 CuX (X = Cl, Br, I) 与 [Au(CH(3)imCH(2)quin)(2)]BF(4) 或 [Au(CH(3)imCH(2)py)(2)]BF(4) 反应生成含有与两个亚胺部分配位的 Cu(2)X(2)-蝶形铜簇的三金属配合物。金属的三角形排列使金 (I) 中心非常接近（大约 2.5-2.6 A）Cu-Cu 矢量的质心。 Cu-Cu 分离随着桥接卤化物的变化而变化，在碘配合物中发现的最短 Cu-Cu 分离约为 2.5 A，在桥接氯化物配合物中发现的最长分离为 2.9 A。在所有六种配合物中，Au-Cu 分离范围约为 2.8 至 3.0 A。在没有卤化物的情况下，形成双金属配合物 [AuCu(CH(3)imCH(2)py)(2)(NCCH(3))(2)](BF(4))(2)，其中包含约 4.72 A 的长 Au-Cu 距离。此外，作为 CuBr 与 [Au(CH(3)imCH(2)quin)(2)]BF(4) 反应的副产物，深红色双金属化合物 AuCuBr(2)(CH(3)imCH(2)quin)(2) 的分离收率非常低。所有这些配合物均通过核磁共振波谱法、质谱法进行了研究，并且还通过 X 射线晶体学对含铜物质进行了表征。在溶液中，铜中心从金络合物中解离，但如 XANES 和 EXAFS 光谱所示，在低温下，Cu-Cu 连接被破坏，并且各个卤化铜 (I) 重新定位到金络合物的相对侧，同时保持与一个亚胺部分的配位。在固态下，所有配合物都是光致发光的，但激发态的性质尚未确定。
The coordination chemistry of copper(I) halides to the homoleptic, N-heterocyclic carbene Au(I) complexes [Au(CH(3)imCH(2)quin)(2)]BF(4) and Au(CH(3)imCH(2)py)(2)]BF(4) was explored. The reaction of CuX (X = Cl, Br, I) with either [Au(CH(3)imCH(2)quin)(2)]BF(4) or [Au(CH(3)imCH(2)py)(2)]BF(4) produces trimetallic complexes containing Cu(2)X(2)-butterfly copper clusters coordinated to the two imine moieties. The triangular arrangement of the metals places the gold(I) center in close proximity (approximately 2.5-2.6 A) to the centroid of the Cu-Cu vector. The Cu-Cu separations vary as a function of bridging halide with the shortest Cu-Cu separations of approximately 2.5 A found in the iodo-complexes and the longest separations of 2.9 A found in the bridging chloride complexes. In all six complexes the Au-Cu separations range from approximately 2.8 to 3.0 A. In the absence of halides, the dimetallic complex [AuCu(CH(3)imCH(2)py)(2)(NCCH(3))(2)](BF(4))(2), containing a long Au-Cu distance of approximately 4.72 A is formed. Additionally, as the byproduct of the reaction of CuBr with [Au(CH(3)imCH(2)quin)(2)]BF(4) the deep-red, dimetallic compound, AuCuBr(2)(CH(3)imCH(2)quin)(2), was isolated in very low yield. All of these complexes were studied by NMR spectroscopy, mass spectrometry, and the copper containing species were additionally characterized by X-ray crystallography. In solution the copper centers dissociate from the gold complexes, but as shown by XANES and EXAFS spectroscopy, at low temperature the Cu-Cu linkage is broken, and the individual copper(I) halides reposition themselves to opposite sides of the gold complex while remaining coordinated to one imine moiety. In the solid state all of the complexes are photoluminescent, though the nature of the excited state was not determined.