Synthesis and reactivity of ruthenium(II) complexes containing hemilabile phosphine–thiophene ligands

Switchable thiophene coordination in Ru(ii) bipyridyl phosphinoterthiophene complexesElectronic supplementary information (ESI) available: synthetic details and characterization data for all complexes. See http://www.rsc.org/suppdata/cc/b2/b209035j/

“…4 Chemical modification of the electronic coupling between Ru(II) and a phosphinothiophene backbone by switching between bidentate and monodentate coordination modes has also been described. 7 The Ru(II) bis(bipyridyl) core was chosen due to its stability, redox chemistry, and photophysical properties. 8 We have used phosphinoterthiophene ligands because they have been previously demonstrated to strongly bind metal centres via the phosphine and to exhibit bidentate coordination via both S and C of the thiophene ring.…”

Syntheses, characterisations and X-ray crystal structures of 5,5′-bis(diphenylphosphino)2,2′-bithiophene derivatives, Ph2(X)P(C4H2S)2P(X)Ph2(X = O, S and CH3+ · I−)

“…These groups allow the oligothiophenes to be *Corresponding author. E-mail: gmgray@uab.edu incorporated into transition metal complexes that may either be molecular or polymeric depending on the number of phosphorus-donor substituents and the metal center used [6][7][8][9]. Some of the transition metal complexes containing oligothiophene with phosphorus-donor substituents have exhibited very interesting third-order nonlinear optical properties [10].…”

Photophysical and electrochemical properties of Ru(ii) complexes containing tridentate bisphosphino-oligothiophene ligands

“…Similar Ru(II)-oligothiophene complexes have p-based transitions on the terthiophene red-shifted from the comparable absorbance band of the oligothiophene. 43 This bathochromic shift is attributed to the Ru centre donating electron density to the terthiophene and the increased rigidity of the oligothiophene as a result of coordination to the metal, 43 and a similar effect is likely involved in the electronic spectra of the Ru(II) complexes studied here.…”

“…Different isomers can have different absorbance bands as seen in related Ru(II)-thienyl cis and trans isomers where p-p* absorption bands were separated by 560 cm -1 . 43 Lengthening the ligand conjugation in 5 results in notable changes in the low temperature absorption features where the lowest energy band separated into two bands separated by ~2300 cm -1 . The large energy difference between the bands in 5 suggests that two different electronic states, rather than vibrational coupling, may be responsible for the two bands.…”