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Structure and Conductivity of an Electrocrystallized Ruthenium [1,8]Binaphthyridine Complex
Author(s) -
PérezCordero Eduardo,
Brady Nancy,
Echegoyen Luis,
Thummel Randolph,
Hung ChiYing,
Bott Simon G.
Publication year - 1996
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19960020709
Subject(s) - binap , ruthenium , chemistry , delocalized electron , intermolecular force , crystal structure , acetonitrile , crystallography , conductivity , ligand (biochemistry) , molecule , catalysis , organic chemistry , biochemistry , receptor , enantioselective synthesis
For the first time, the crystal structure of a Ru II binaphthyridine complex and that of its corresponding oneelectron reduced product are reported. Reductive electrocrystallization of [Ru‐(binap‐2) 3 ](PF 6 ) 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 ](PF 6 ) ( 2 ) having one fewer PF − 6 per formula unit. X‐ray analysis reveals that the reduced complex retains the three‐ligand d 6 coordination around the central Ru II . 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.