Self-assembly of square planar rhodium carbonyl complexes with 4,4-disubstituted-2,2’-bipyridine ligands
Kolari, K., Laurila, E., Chernysheva, M., Hirva, P., & Haukka, M. (2020). Self-assembly of square planar rhodium carbonyl complexes with 4,4-disubstituted-2,2’-bipyridine ligands. Solid State Sciences, 100, Article 106103. https://doi.org/10.1016/j.solidstatesciences.2019.106103
Published inSolid State Sciences
© 2020 Elsevier B.V.
The impact of non-covalent interactions and reaction conditions on formation and self-assembly of ionic pairs of Rh complexes with 4,4’-disubstituted bipyridine ligands ([Rh(L1)(CO)2][Rh(CO)2Cl2])n (1), [Rh(L1)2Cl2][Rh(CO)2Cl2] (2), ([Rh(L1)(CO)2][Rh(CO)2Cl2][Rh(L1)(CO)2]n([Rh(CO)2(Cl)2])n) (3), ([Rh(L2)CO2] [Rh(CO)2Cl2])n∙EtOH (4), ([Rh(L2)(CO)2])n ([Rh(CO)2Cl2])n (5) (L1 = 4,4’-dimethyl-2,2’-bipyridine, L2 = 4,4’-diamine-2,2’-bipyridine) have been studied. Packing of square planar Rh complexes favor formation of one-dimensional chains. In structure 1, the polymeric chain is formed by the alternating cationic [Rh(L1)(CO)2]+ and the anionic [Rh(CO)2Cl2]- units leading to a neutral pseudo linear 1D chain with metallophilic contacts. In compound 2, the square planar [Rh(CO)2Cl2]- anions form only dinuclear anion pairs instead of polymeric chains. Structure 3 consists of an alternative arrangement of cations and anions compared to 1, the repeating sequence of ions being [Rh(L1)(CO)2]+[Rh(CO)2Cl2]- [Rh(L1)(CO)2]+. The overall positive charge is balanced by outlying [Rh(CO)2Cl2]- counterion. In structures 4 and 5, only the cationic [Rh(L2)(CO)2]+ units are involved in formation of the polymeric chains and the positive charge of the chain is balanced by the [Rh(CO)2Cl2]- (4 and 5). In structures 1 and 3 the metallophilic interactions have an important role in chain formation. In 4 and 5, the arrangement of the square planar building blocks is dominated by the hydrogen bonding between the NH2-substituents of the bipyridine ligand and the chlorides of the anion or solvent of crystallization. ...
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Related funder(s)Academy of Finland
Funding program(s)Academy Project, AoF
Additional information about fundingFinancial support of Magnus Ehrnrooth foundation (K.K), Academy of Finland, project no. 295581 (M.H) as well as the European Network on Smart Inorganic Polymers (SIPs) COST CM1302 project.
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