Abstract
In this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.
Highlights
Dinuclear complexes with a paddlewheel structure show a rich chemistry and different electronic configurations as a consequence of the distribution of the energy levels and the number of electrons in the dimetallic unit [1,2]
Many dirhodium molecular complexes have been reported owing to the facility of the rhodium ions to coordinate monodentate donor ligands at the axial positions of the paddlewheel structure [1,2,14,15,16,17]
The use of other metal complexes as connectors between the paddlewheel units can lead to the formation of heterometallic one-dimensional coordination polymers, whose versatile chemical and physical properties, such as temperature dependent luminescence or modulation of their electronic structures, make those polymers promising materials [22,23,24,25]
Summary
Dinuclear complexes with a paddlewheel structure show a rich chemistry and different electronic configurations as a consequence of the distribution of the energy levels and the number of electrons in the dimetallic unit [1,2]. The use of charged cyanidometallates to bridge the neutral Rh(II)-Rh(II) units requires the presence of counter-cations to compensate the negative charge, which can be alkali cations [32] or bulkier groups like tetraphenylphosphonium [33]. The interest of the latter lays in its higher arrangement diversity owing to the supramolecular structures that can be formed by phenyl–phenyl interactions through double, quadruple, or sextuple phenyl embraces [33,41,42,43,44].
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