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- Title
Metal–ligand Lability and Ligand Mobility Enables Framework Transformation via Ligand Release in a Family of Crystalline 2D Coordination Polymers.
- Authors
Lang, Feifan; Singh, Daljit C. N. G.; Rao, Abhishek B.; Romer, Catherine; Wright, James S.; Smith, Rebecca; Adams, Harry; Brammer, Lee
- Abstract
A family of seven silver(I)‐perfluorocarboxylate‐quinoxaline coordination polymers, [Ag4(O2CRF)4(quin)4] 1–5 (RF=(CF2)n‐1CF3)4, n=1 to 5); [Ag4(O2C(CF2)2CO2)2(quin)4] 6; [Ag4(O2CC6F5)4(quin)4] 7 (quin=quinoxaline), denoted by composition as 4 : 4 : 4 phases, was synthesised from reaction of the corresponding silver(I) perfluorocarboxylate with excess quinoxaline. Compounds 1–7 adopt a common 2D layered structure in which 1D silver‐perfluorcarboxylate chains are crosslinked by ditopic quinoxaline ligands. Solid‐state reaction upon heating, involving loss of one equivalent of quinoxaline, yielding new crystalline 4 : 4 : 3 phases [Ag4(O2C(CF2)n‐1CF3)4(quin)3]n (8–10, n=1 to 3), was followed in situ by PXRD and TGA studies. Crystal structures were confirmed by direct syntheses and structure determination. The solid‐state reaction converting 4 : 4 : 4 to 4 : 4 : 3 phase materials involves cleavage and formation of Ag−N and Ag−O bonds to enable the structural rearrangement. One of the 4 : 4 : 3 phase coordination polymers (10) shows the remarkably high dielectric constant in the low electric field frequency range.
- Subjects
COORDINATION polymers; PERMITTIVITY; QUINOXALINES; ELECTRIC fields; CRYSTAL structure; LIGANDS (Chemistry)
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 51, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202201408