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Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster
Author(s) -
Li Bo,
Huang RenWu,
Qin JianHua,
Zang ShuangQuan,
Gao GuangGang,
Hou HongWei,
Mak Thomas C. W.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404049
Subject(s) - thermochromism , luminescence , nest (protein structural motif) , crystallography , cluster (spacecraft) , ligand (biochemistry) , ion , single crystal , crystal structure , fluorescence , chemistry , materials science , receptor , optoelectronics , optics , physics , biochemistry , organic chemistry , computer science , programming language
A novel discrete open high‐nuclearity nest‐like silver thiolate cluster complex, [Ag 33 S 3 (S t Bu) 16 (CF 3 COO) 9 (NO 3 )(CH 3 CN) 2 ](NO 3 ) ( 1 ), has been isolated with nitrate and S 2− anions acting as structure‐directing templates. Its similar nest‐like structure has been assembled into an extended layer [Ag 31 S 3 (S t Bu) 16 (NO 3 ) 9 ] n ( 2 ) by adjustment of auxiliary ligand. More interestingly, both complexes exhibit temperature‐dependent luminescence of high sensitivity with a large fluorescence enhancement (12‐fold for 1 , 21‐fold for 2 ), which can be easily recognized by the naked‐eye (dramatic red‐shift Δ =104 nm for 1 , larger Δ =113 nm for 2 at 77 K compared to those at 298 K). The correlation between luminescent thermochromism and temperature‐dependent variation of the coordination modes of template NO 3 − anion, Ag⋅⋅⋅S and Ag⋅⋅⋅Ag distances are also elucidated through variable‐temperature single‐crystal X‐ray crystal structure (VT‐SCXRD) analyses.