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Issue 2, 2012
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Selective carbon dioxide uptake and crystal-to-crystal transformation: porous 3D framework to 1D chain triggered by conformational change of the spacer

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Abstract

α-Po type 3D porous frameworks, {[M(bpe)2(N(CN)2)]N(CN)2·xH2O}n, (M = Zn(II) (x = 5) (1)/Co(II) (x = 4) (2)) (bpe = 1,2-bis(4-pyridyl)ethane, N(CN)2 = dicyanamide anion) composed of mixed ligand systems have been synthesized and structurally characterized. Upon two-fold interpenetration both 3D frameworks 1 and 2 show a bimodal channel structure; the small channels contain non-coordinated N(CN)2 anions and the bigger channels are occupied by guest water molecules. High framework stability for both compounds was realized by similarity in the PXRD pattern in dehydrated state and even a reversible single-crystal-to-single-crystal transformation for framework 1. Both the frameworks display unprecedented structural transformation from 3D framework to 1D {[M(bpe)(N(CN)2)2]}n (M = Zn(II) (1b)/Co(II) (2b)) coordination chain upon removal of one molecule of bpe and concomitant bridging of non-coordinated N(CN)2 and conformational change (anti to gauche) by another bridging bpe linker. Moreover, the dehydrated solid {[Co(bpe)2(N(CN)2)]N(CN)2}n (2a) exhibits highly selective CO2 uptake relative to a number of adsorbates (H2, N2, O2 and Ar) at 195 K.

Graphical abstract: Selective carbon dioxide uptake and crystal-to-crystal transformation: porous 3D framework to 1D chain triggered by conformational change of the spacer

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Supplementary files

Article information


Submitted
07 Jul 2011
Accepted
27 Sep 2011
First published
10 Nov 2011

CrystEngComm, 2012,14, 684-690
Article type
Paper

Selective carbon dioxide uptake and crystal-to-crystal transformation: porous 3D framework to 1D chain triggered by conformational change of the spacer

R. Haldar and T. K. Maji, CrystEngComm, 2012, 14, 684
DOI: 10.1039/C1CE05847A

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