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Issue 29, 2012
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Theoretical exploration of uranyl complexes of a designed polypyrrolic macrocycle: structure/property effects of hinge size on Pacman-shaped complexes

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Abstract

A polypyrrolic macrocycle with naphthalenyl linkers between the N4-donor compartments (L2) was designed theoretically according to its experimentally-known analogues with phenylenyl (L1) and anthracenyl (L3) linkers. The uranyl and bis(uranyl) complexes formed by this L2 ligand have been examined using scalar-relativistic density functional theory. The calculated structural properties of the mononuclear uranyl-L2 complexes are similar to those of their L1 counterparts. The binuclear L2 complexes exhibit a butterfly-like bis(uranyl) core in which a linear uranyl is coordinated in a side-by-side fashion to a cis-uranyl unit. The calculated U[double bond, length as m-dash]O bond orders in the uranyl-L2 complexes indicate partial triple bonding character with the only exceptions being the U–Oendo bonds in the U2O4 core of the butterfly-shaped binuclear complexes. Overall, the bond orders agree with the trends in the calculated U[double bond, length as m-dash]O stretching vibrational frequencies. Regarding the bis(uranyl) L1, L2 and L3 complexes, the phenylenyl-hinge L1 complexes adopt a butterfly-like and a T-shaped isomer in the oxidation state of U(VI), but only a butterfly-like one in the U(V), which differs from that of the naphthalenyl-hinge L2 complexes as well as the lateral twisted structure of the anthracenyl-hinge L3 complexes. The intramolecular cationcation interactions are found in the L1 and L2 complexes, but are absent in the L3 complexes. Finally, using model uranyl transfer reactions from the L1 complexes, the formation of the mononuclear L2 complexes is calculated to be a slightly endothermic process. This suggests that it should be possible to synthesize the L2 complexes using similar protocols as employed for the L1 complexes.

Graphical abstract: Theoretical exploration of uranyl complexes of a designed polypyrrolic macrocycle: structure/property effects of hinge size on Pacman-shaped complexes

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Publication details

The article was received on 15 May 2012, accepted on 22 May 2012 and first published on 11 Jun 2012


Article type: Paper
DOI: 10.1039/C2DT31055D
Citation: Dalton Trans., 2012,41, 8878-8885
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    Theoretical exploration of uranyl complexes of a designed polypyrrolic macrocycle: structure/property effects of hinge size on Pacman-shaped complexes

    Q. Pan, S. O. Odoh, G. Schreckenbach, P. L. Arnold and J. B. Love, Dalton Trans., 2012, 41, 8878
    DOI: 10.1039/C2DT31055D

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