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Issue 10, 2016

Synthesis and stabilization of a hypothetical porous framework based on a classic flexible metal carboxylate cluster

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Abstract

By using pyridyl derivatives 4-cyanopyridine (4-pyCN) or nicotinate (na) as terminal ligands (LT) to decorate the flexible trigonal-prismatic trinuclear metal carboxylate M33-O/μ3-OH)(RCOO)6(LT)3 clusters, a theoretically predicted uninodal 6-connected flu-e network for [M33-O/μ3-OH)(bdc)3(LT)3] (H2bdc = 1,4-benzenedicarboxylic acid) has been realized in three new porous coordination frameworks. The flu-e topology is isomeric to the uninodal 6-connected acs (MIL-88) and tetranodal 6-connected mtn-e (MIL-101) ones observed in the classic metal carboxylate framework materials, but comprises of unique cubic cages which require exceptional conformation for the trinuclear clusters. The weak coordinating 4-pyCN terminal ligands tend to leave the clusters during thermal activation, leading to framework distortion and reduction of the long-range order of the flu-e network, which can only be restored by 4-pyCN instead of other guest molecules. On the other hand, the carboxylate ends of the adjacent na ligands coordinate with additional metal ions to crosslink the coordination networks as new binodal 4,9-connected networks with remarkably enhanced thermal/chemical stability and porosity.

Graphical abstract: Synthesis and stabilization of a hypothetical porous framework based on a classic flexible metal carboxylate cluster

Supplementary files

Article information


Submitted
07 Sep 2015
Accepted
04 Nov 2015
First published
04 Nov 2015

Dalton Trans., 2016,45, 4269-4273
Article type
Paper

Synthesis and stabilization of a hypothetical porous framework based on a classic flexible metal carboxylate cluster

Y. Wei, J. Shen, P. Liao, W. Xue, J. Zhang and X. Chen, Dalton Trans., 2016, 45, 4269 DOI: 10.1039/C5DT03478G

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