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

作者：Laurila Elina; Oresmaa Larisa; Hassinen Jorma; Hirva Pipsa; Haukka Matti^*

来源：Dalton Transactions, 2013, 42(2): 395-398.

DOI：10.1039/c2dt31671d

The metallophilic interactions were investigated within chains of oppositely charged rhodium carbonyl complexes. The cationic [Rh(CO)(2)(L)](+) (L = 2,2%26apos;-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%26apos;-bpy)][RhCl2(CO)(2)]}(n) was found to be nearly linear with a Rh center dot center dot center dot Rh center dot center dot center dot Rh angle of 170.927(11)degrees and Rh center dot center dot center dot Rh distances of 3.3174(5) angstrom and 3.4116(5) angstrom. 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 center dot center dot center dot Rh center dot center dot center dot Rh angles (170.275(9)degrees and 159.573(9)degrees). The higher linearity allowed closer packing of the rhodium complexes. The Rh center dot center dot center dot Rh distances were 3.2734(3) angstrom and 3.3155(3) angstrom for the more linear and 3.3498(3) angstrom and 3.3211(3) angstrom 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.

• 出版日期2013