Issue 10, 2016

Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks

Abstract

Herein we report a synthetic study focused on the preparation of solid-solution metal–organic frameworks, MOFs, with the use of two kinds of linkers. In particular, we have explored the system composed by zinc, cobalt, 1,2,4-triazole and 4,4′-hexafluoroisopropylidenebisbenzoic acid (H2hfipbb). During this study, four new MOFs have been isolated, denoted TMPF-88 [M3(hfipbb)2(triazole)2(H2O)], TMPF-90 [M2(triazole)3(OCH2CH3)], TMPF-91 [M2(hfipbb)(triazole)2(H2O)] and TMPF-95 [M5(hfipbb)4(triazole)2(H2O)] (TMPF = transition metal polymeric framework, M = Zn, Co, or mixture of them). The study demonstrates that the addition of a second metal element during the MOF synthesis has a major effect in the formation of new phases, even at very high Zn/Co metal ratios. Furthermore, we show that during the MOF formation reaction, there is a competition among different crystal phases, where kinetically favoured phases of various compositions crystallize in short reaction times, precluding the formation of the pure solid-solution phases of other energetically more stable MOFs.

Graphical abstract: Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks

Supplementary files

Article information

Article type
Paper
Submitted
02 Dit 2015
Accepted
02 Kax 2015
First published
03 Kax 2015

Dalton Trans., 2016,45, 4327-4337

Author version available

Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks

C. Castillo-Blas, N. Snejko, V. A. de la Peña-O'Shea, J. Gallardo, E. Gutiérrez-Puebla, M. A. Monge and F. Gándara, Dalton Trans., 2016, 45, 4327 DOI: 10.1039/C5DT03856A

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