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- Title
Linker Flexibility‐Dependent Cluster Transformations and Cluster‐Controlled Luminescence in Isostructural Silver Cluster‐Assembled Materials (SCAMs).
- Authors
Wang, Jia‐Yin; Huang, Ren‐Wu; Wei, Zhong; Xi, Xiao‐Juan; Dong, Xi‐Yan; Zang, Shuang‐Quan
- Abstract
Silver chalcogenolate clusters (SCCs) and silver cluster‐assembled materials (SCAMs) are an important category of novel luminescent materials, the emission of which can be modulated by variation of the cluster nodes and linker species. Here, the successfully synthesis of two isostructural 2D SCAMs is reported: Ag12bpa and Ag12bpe are formed by using two linkers with different conformational freedom (bpa=1,2‐bis(4‐pyridyl)ethane, bpe=1,2‐bis(4‐pyridyl)ethylene), with dodenuclear silver chalcogenolate clusters as secondary building units (SBUs). Interestingly, nonluminescent Ag12bpa at room temperature could quickly transform into 1D Ag10bpa, with concomitant dissociation of two silver atoms and the remaining ten silver atoms rearranging in the cluster, thus exhibiting an intense yellow phosphorescence after being triggered by acetonitrile (CH3CN). Similarly, stimulating Ag12bpe with CH3CN, by contrast, gave another 2D structure Ag12bpe‐1b with the distorted SBUs and different topology structure, and both of them are merely red‐emissive at low temperature. To note, after exchanging ligands, room‐temperature nonluminescent 2D Ag12bpe‐1b can be transformed into intensely luminescent 1D Ag10bpa. This linker‐flexibility‐dependent structural transformation and cluster‐based SBU controlled luminescence remains scarce. Our work provides new insights into structure–luminescence relationship in clustered metal–organic frameworks and intelligent stimulus‐responsive luminescent materials. What a SCAM! Isostructural silver cluster‐assembled materials (SCAMs) Ag12bpa and Ag12bpe (bpa=1,2‐bis(4‐pyridyl)ethane, bpe=1,2‐bis(4‐pyridyl)ethylene) were synthesized by using bidentate pyridine to give identical length yet different flexibility. Ag12bpa and Ag12bpe differently respond to acetonitrile: 2D Ag12bpa, which is only red‐emissive at low temperature transforms into yellow‐emissive 1D Ag10bpa at room temperature (see figure).
- Subjects
SILVER clusters; PHOSPHORS; ACETONITRILE; PHOSPHORESCENCE; SILVER
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 13, p3376
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201805808