Cu4I4 Clusters Supported by P∧N-type Ligands: New Structures with Tunable Emission Colors

被引：148
作者：
Liu, Zhiwei [1 ]
Djurovich, Peter I. [1 ]
Whited, Matthew T. [1 ]
Thompson, Mark E. [1 ]
机构：
[1] Univ So Calif, Dept Chem, Los Angeles, CA 90089 USA
来源：
INORGANIC CHEMISTRY | 2012年 / 51卷 / 01期
基金：
美国国家科学基金会;
关键词：
LEWIS-BASE ADDUCTS; GROUP-11 METAL(I) COMPOUNDS; DER-WAALS RADII; X = CL; COPPER(I) COMPLEXES; CRYSTAL-STRUCTURE; PHOTOPHYSICAL PROPERTIES; LUMINESCENT COPPER(I); PHOTOLUMINESCENCE PROPERTIES; THERMOCHROMIC-LUMINESCENCE;
D O I：
10.1021/ic2015226
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A series of Cu4I4 clusters (1-5) supported by two (PN)-N-boolean AND-type ligands 2-[(diRphosphino)methyl]pyridine (1, R = phenyl; 2, R = cyclohexyl; 3, R = tert-butyl; 4, R = iso-propyl; 5, R = ethyl) have been synthesized. Single crystal X-ray analyses show that all five clusters adopt a rare "octahedral" geometry. The central core of the cluster consists of the copper atoms arranged in a parallelogram with mu(4)-iodides above and below the copper plane. The copper atoms on the two short edges of the parallelogram (Cu-Cu = 2.525(2)-2.630(1) angstrom) are bridged with mu(2)-iodides, whereas the long edges (Cu-Cu = 2.839(3)-3.035(2) angstrom) are bridged in an antiparallel fashion by the (PN)-N-boolean AND ligands. This Cu4I4 geometry differs significantly from the "cubane" and "stairstep" geometries reported for other Cu4I4L4 clusters. Luminescence spectra of clusters 3 and 4 display a single emission around 460 nm at room temperature that is assigned to emission from a triplet halide-to-ligand charge-transfer ((XLCT)-X-3) excited state, whereas clusters 1, 2, and 5 also have a second band around 570 nm that is assigned to a Cu4I4 cluster-centered ((CC)-C-3) excited state. The structural and photophysical properties of a dinuclear Cu2I2((PN)-N-boolean AND)(2) complex obtained during the sublimation of cluster 3 is also provided.
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页码：230 / 236
页数：7
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