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Issue 20, 2012
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Orbital directing effects in copper and zinc based paddle-wheel metal organic frameworks: the origin of flexibility

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Abstract

We have used density functional theory calculations to study non-periodic model systems for the ubiquitous layer-pillar metal organic frameworks built from paddle-wheel building blocks. Experimentally, these porous materials show nearly identical structures for both copper and zinc forming the paddle-wheel, but differ depending on the type of the metal center in their properties. Our theoretical results clearly reveal orbital directing effects for the d9 Cu(II) center, enforcing a square planar conformation, to be the main reason for the difference in contrast to the flexible d10 Zn(II) system. Surprisingly, this difference is directly visible in the structure of the bare vertex model without axial ligands, whereas in the case of pyridine coordination both copper and zinc complexes are structurally nearly indistinguishable. However, in the vibrational normal modes the higher degree of flexibility for the zinc-based systems is still noticeable, explaining the higher flexibility of the corresponding periodic MOFs.

Graphical abstract: Orbital directing effects in copper and zinc based paddle-wheel metal organic frameworks: the origin of flexibility

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Publication details

The article was received on 10 Nov 2011, accepted on 19 Jan 2012 and first published on 17 Feb 2012


Article type: Paper
DOI: 10.1039/C2JM15778K
Citation: J. Mater. Chem., 2012,22, 10249-10254
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    Orbital directing effects in copper and zinc based paddle-wheel metal organic frameworks: the origin of flexibility

    S. Bureekaew, S. Amirjalayer and R. Schmid, J. Mater. Chem., 2012, 22, 10249
    DOI: 10.1039/C2JM15778K

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