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Spectral, Structural, and Computational Studies of a New Family of Ruthenium(II) Complexes Containing Substituted 1,10‐Phenanthroline Ligands and in situ Electropolymerization of a Phenanthrolineruthenium(II) Complex Bridging Nanogap Gold Electrodes
Author(s) -
Huang Wei,
Wang Li,
Tanaka Hirofumi,
Ogawa Takuji
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200801131
Subject(s) - chemistry , ruthenium , thiophene , phenanthroline , density functional theory , crystallography , bipyridine , electrochemistry , in situ , bridging ligand , conjugated system , electrode , photochemistry , polymer , crystal structure , computational chemistry , catalysis , organic chemistry
The synthesis and spectral and structural characterization of a new family of ruthenium(II) complexes containing 3‐bromo‐, 3,8‐dibromo‐, 3‐(thiophen‐2′,2″‐yl)‐, and 3,8‐(thiophen‐2′,2″‐yl)‐1,10‐phenanthroline (phen) ligands is described. UV/Vis spectroscopy is used to compare the differences between the conjugated π systems in these ligands and their respective [Ru(bpy) 2 ] 2+ (bpy = 2,2′‐bipyridine) analogs. Density functional theory (DFT) computations have been carried out to compare the energy differences between the single‐crystal and the energy‐minimized structures for different conformations ( trans / trans , trans / cis and cis / cis ) of the thiophene rings and their bonded phen ring. The formation of an oligothiophene semiconductor polymer bridging gold electrodes with a gap of around 25 nm gap from Ru II complex 7 by in situ electropolymerization, and its removal, is monitored by scanning electron microscopy (SEM). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)