title: Thermochromic luminescent nest-like silver thiolate cluster.
abstract: A novel discrete open high-nuclearity nest-like silver thiolate cluster complex, [Ag33 S3 (StBu)16 (CF3 COO)9 (NO3 )(CH3 CN)2 ](NO3 ) (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 [Ag31 S3 (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.
authors.affiliation: College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (P.R. China).
authors.forename: Bo
authors.initials: B
authors.lastname: Li
authors.forename: Ren-Wu
authors.initials: RW
authors.lastname: Huang
authors.forename: Jian-Hua
authors.initials: JH
authors.lastname: Qin
authors.forename: Shuang-Quan
authors.initials: SQ
authors.lastname: Zang
authors.forename: Guang-Gang
authors.initials: GG
authors.lastname: Gao
authors.forename: Hong-Wei
authors.initials: HW
authors.lastname: Hou
authors.forename: Thomas C W
authors.initials: TC
authors.lastname: Mak
mesh_terms: D049449:Luminescence; D049408:Luminescent Agents / Q000737:chemistry*; D008958:Models, Molecular; D009566:Nitrates / Q000737:chemistry; D012834:Silver / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013696:Temperature
chemical_list: D049408:Luminescent Agents; D009566:Nitrates; D013438:Sulfhydryl Compounds; D012834:Silver
keywords: cluster compounds; nest-like structures; silver; template synthesis; thermochromism