Issue 5, 2012

Anion-controlled conformational variation: Structural modulation and anion exchange of Ag(i) coordination networks

Abstract

From our recently reported [Ag2L2]2+ metallacyclic species (L = 2,5-bis(4-pyridinylmethylthio)-1,3,4-thiadiazole), four coordination networks [Ag2L2]n·2n(ClO4)·7nH2O (1), [Ag2L2]n·2n(BF4)·5nH2O (1a), [Ag2L2]n·n[Ag2L2]·4n(NO3) (2) and [AgL(NO2)]n (3) were synthesized under the different anion conditions, which can be classified into three distinct supramolecular structures. Complexes 1/1a are constructed by disilver(I) macrocyclic motifs with the chair conformation, whereas 2 consists of two types of boat-form metallacycles. In 3, the bridging L adopts an extended conformation in sharp contrast to that in 1/1a/2. In this system, conformations of the metallacyclic subunit and flexible ligand L are modulated by various counter anions. For weakly coordinating anions, anion-exchange results indicate that complexes 1/1a maintain the primary structures and have an affinity order in agreement with the Hofmeister series. It is noteworthy that when complexes 1/1a/2 are treated with an aqueous solution containing NO2, they all undergo a fast and quantitative anion-exchange process to afford complex 3. This process accompanies remarkable conformational conversion of L from cis, cis, syn to trans, trans, syn form. Atomic force microscopy studies indicate a solvent-mediated rather than a solid-state mechanism for the anion exchange.

Graphical abstract: Anion-controlled conformational variation: Structural modulation and anion exchange of Ag(i) coordination networks

Supplementary files

Article information

Article type
Paper
Submitted
04 Sep 2011
Accepted
10 Nov 2011
First published
21 Dec 2011

CrystEngComm, 2012,14, 1693-1700

Anion-controlled conformational variation: Structural modulation and anion exchange of Ag(I) coordination networks

W. Wei, H. Yu, F. Jiang, B. Liu, J. Ma and M. Hong, CrystEngComm, 2012, 14, 1693 DOI: 10.1039/C1CE06141K

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