Thermochromic Luminescent Nest-Like Silver Thiolate Cluster.

A novel discrete open high-nuclearity nest-like silver thiolate cluster complex, [Ag33S3(S tBu)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(S tBu)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. [ABSTRACT FROM AUTHOR]