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Issue 2, 2013
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Neutral one-dimensional metal chains consisting of alternating anionic and cationic rhodium complexes

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Abstract

The metallophilic interactions were investigated within chains of oppositely charged rhodium carbonyl complexes. The cationic [Rh(CO)2(L)]+ (L = 2,2′-bipyridine and 1,10-phenanthroline) and anionic [RhCl2(CO)2] units were self-assembled into one dimensional rhodium chains supported by electrostatic interactions. The array of Rh centers in {[Rh(CO)2(2,2′-bpy)][RhCl2(CO)2]}n was found to be nearly linear with a Rh⋯Rh⋯Rh angle of 170.927(11)° and Rh⋯Rh distances of 3.3174(5) Å and 3.4116(5) Å. The crystal structure of {[Rh(CO)2(1,10-phen)][RhCl2(CO)2]} consisted of two sets of crystallographically independent chains with slightly different Rh⋯Rh⋯Rh angles (170.275(9)° and 159.573(9)°). The higher linearity allowed closer packing of the rhodium complexes. The Rh⋯Rh distances were 3.2734(3) Å and 3.3155(3) Å for the more linear and 3.3498(3) Å and 3.3211(3) Å for the less linear system. The existence of metallophilic interactions was confirmed computationally by TD-DFT and QTAIM analysis. The computational results also indicated that the intermolecular charge transfer from the cation to the anion had a significant contribution to the absorption properties of the chain compounds.

Graphical abstract: Neutral one-dimensional metal chains consisting of alternating anionic and cationic rhodium complexes

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Publication details

The article was received on 25 Jul 2012, accepted on 28 Sep 2012 and first published on 04 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT31671D
Citation: Dalton Trans., 2013,42, 395-398
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    Neutral one-dimensional metal chains consisting of alternating anionic and cationic rhodium complexes

    E. Laurila, L. Oresmaa, J. Hassinen, P. Hirva and M. Haukka, Dalton Trans., 2013, 42, 395
    DOI: 10.1039/C2DT31671D

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