Issue 31, 2012

The unusual thermochromic NIR luminescence of Cu(i) clusters: tuned by Cu–Cu interactions and packing modes

Abstract

Two hexanuclear Cu(I) clusters [CuI3(4-ptt)3]2·3DMF·3H2O (1) and [CuI(4-ptt)]6·8DMF·7H2O (2) (4-Hptt = 5-(pyridin-4-yl)-1H-1,2,4-triazole-3-thiol, DMF = N,N-dimethylformamide), were synthesized and characterized. Compounds 1 and 2 with similar coordination environments are isomers, but their detailed structures are different due to the reaction temperature tuning effect. Both 1 and 2 extend from monomers to 3D supramolecules with the help of hydrogen bonding between the triazole and pyridine from the 4-ptt ligands. The Cu6S6 units of 1 pack in a polydirectional array, while the Cu6S6 units in 2 extend in one direction and link the planes of adjacent ligands to enhance the delocalization of π electrons. Their varied Cu–Cu interactions and individual packing modes cause differences in luminescent and thermostable behaviors. Compound 1 exhibits an unusually long wavelength at about 900 nm and a higher thermal stability; while the emission of 2 splits into two bands (high-energy and low-energy emission bands) as the temperature decreases. Therefore, the emissions of 1 originate from a 3CC transition, and those of 2 are from a mixture of 3CC and MLCT.

Graphical abstract: The unusual thermochromic NIR luminescence of Cu(i) clusters: tuned by Cu–Cu interactions and packing modes

Supplementary files

Article information

Article type
Paper
Submitted
26 Apr 2012
Accepted
29 May 2012
First published
30 May 2012

Dalton Trans., 2012,41, 9411-9416

The unusual thermochromic NIR luminescence of Cu(I) clusters: tuned by Cu–Cu interactions and packing modes

X. Shan, F. Jiang, D. Yuan, M. Wu, S. Zhang and M. Hong, Dalton Trans., 2012, 41, 9411 DOI: 10.1039/C2DT30909B

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