ISSN:
0947-6539
Keywords:
chelate ligands
;
intermolecular interactions
;
reductions
;
ruthenium complexes
;
semiconductors
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
For the first time, the crystal structure of a RuII binaphthyridine complex and that of its corresponding oneelectron reduced product are reported. Reductive electrocrystallization of [Ru-(binap-2)3](PF6)2 (1, where binap-2 = 3,3′-dimethylene -2,2′ - bi [1, 8] naphthyridine) from an acetonitrile solution resulted in the formation of dark blue crystals of the one-electron reduction product, [Ru-(binap-2)3](PF6) (2) having one fewer PF-6 per formula unit. X-ray analysis reveals that the reduced complex retains the three-ligand d6 coordination around the central RuII. Based on electrostatic considerations and the positions of the PF-6 anions in the lattice, the added electron appears to be delocalized over two nearly equivalent binap-2 ligands in 2, in marked contrast to monoreduced and electrocrystallized [Na ⊂ (trisbipyridyl cryptand)]0, in which the electron is localized on only one of the bipyridyl subunits. However, based on the available data, alternative interpretations are possible. The crystal packing diagram of 2 shows several intermolecular π-π interactions, with 12 of these being shorter than 3.5 Å. In contrast, there are no intermolecular distances shorter than 3.5 Å in the crystals of 1. Two-probe electrical conductivity measurements under anaerobic conditions indicate that the crystals of 2 behave as semiconductors with a band gap of 0.53 eV, while those of the unreduced compound are insulating. This represents the first molecular semiconducting material with the potential for bidimensional behavior of its kind.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.1460020707
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