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Influence of anions and mole ratio on the formation of 2-D coordination networks of thiacalix[4]-bis-monothiacrown-5

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Abstract

Anion and mole-ratio effects on the formation of coordination polymers (1–3) of thiacalix[4]-bis-monothiacrown-5 (L) incorporating two types of sulfur donors (crown loop and rim) are reported. In the reaction with AgPF6, an anion-uncoordinated two dimensional (2-D) coordination polymer {[Ag2L3](PF6)2}n (1) adopting a honeycomb (hcb) topology was isolated as a mole-ratio independent product. In the reactions with AgCF3CO2, an anion-coordinated honeycomb type 2-D coordination polymer {[Ag2L3(CF3CO2)2]·6CHCl3·2H2O}n (2) and a square-grid type 2-D coordination polymer {[Ag4L3(CF3CO2)4]·0.5CHCl3·0.5CH3OH·0.5toluene}n (3) with an sql topology were obtained below 1.0 equiv. and above 1.3 equiv., respectively. All products demonstrate that the only sulfur donor in the crown loop acts as a versatile bridgehead for the exo-binding probably due to its stronger basicity than that of the sulfur bridge in the rim. The powder X-ray diffraction (PXRD) studies reveal that anion-exchange between 1 (PF6, hcb) and 3 (CF3CO2, sql) in the solid state is reversible.

Graphical abstract: Influence of anions and mole ratio on the formation of 2-D coordination networks of thiacalix[4]-bis-monothiacrown-5

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Article information


Submitted
16 Aug 2020
Accepted
23 Sep 2020
First published
24 Sep 2020

CrystEngComm, 2020, Advance Article
Article type
Paper

Influence of anions and mole ratio on the formation of 2-D coordination networks of thiacalix[4]-bis-monothiacrown-5

H. Ju, J. Y. Lee and S. S. Lee, CrystEngComm, 2020, Advance Article , DOI: 10.1039/D0CE01198C

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