Thermochromic Luminescent Nest-Like Silver Thiolate Cluster

• Published in: Chemistry : a European journal 2014-09, Vol.20 (39), p.12416-12420
• Main Authors: Li, Bo, Huang, Ren-Wu, Qin, Jian-Hua, Zang, Shuang-Quan, Gao, Guang-Gang, Hou, Hong-Wei, Mak, Thomas C. W.
• Format: Article
• Language: English
• Subjects: Adjustment; Anions; Chemistry; cluster compounds; Clusters; Crystal structure; Fluorescence; Ligands; Luminescence; Luminescent Agents - chemistry; Models, Molecular; nest-like structures; Nitrates; Nitrates - chemistry; Silver; Silver - chemistry; Sulfhydryl Compounds - chemistry; Temperature; template synthesis; thermochromism
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201404049

A novel discrete open high‐nuclearity nest‐like silver thiolate cluster complex, [Ag33S3(StBu)16(CF3COO)9(NO3)(CH3CN)2](NO3) (1), has been isolated with nitrate and S2− anions acting as structure‐directing templates. Its similar nest‐like structure has been assembled into an extended layer [Ag31S3(StBu)16(NO3)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 NO3− anion, Ag⋅⋅⋅S and Ag⋅⋅⋅Ag distances are also elucidated through variable‐temperature single‐crystal X‐ray crystal structure (VT‐SCXRD) analyses. Stirring up a nest: A novel discrete open high‐nuclearity nest‐like silver thiolate cluster complex, [Ag33S3(StBu)16(CF3COO)9(NO3)(CH3CN)2](NO3) (1), has been isolated with nitrate and S2− anions acting as structure‐directing templates. Its similar nest‐like structure has been assembled into an extended layer [Ag31S3(StBu)16(NO3)9]n (2) by adjustment of auxiliary ligand. Both complexes exhibit temperature‐dependent luminescence of high sensitivity with a large fluorescence enhancement (see figure).