Thermochromic Luminescent Nest‐Like Silver Thiolate Cluster

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.