0000000000563641
AUTHOR
Klaus Hempel
Synthesis and Characterization of Extended Bis(terpyridine)ruthenium Amino Acids
(Oligopyridine)ruthenium(II) complexes have been widely used in dye sensitized solar cells and other sophisticated optical devices due to their outstanding photophysical properties and their chemical stability. Herein, we describe the longitudinal extension of our previously reported bis(terpyridine)ruthenium(II) amino acid [Ru(tpy–NH2)(tpy–COOH)]2+ (tpy = 4′-substituted 2,2′:6′,2″-terpyridine) by insertion of para-phenylene spacers –C6H4– between the terpyridine and the functional groups. The influence of the para-phenylene spacer on the absorption and emission properties is investigated using UV/Vis absorption and emission spectroscopy and is discussed within a qualitative molecular orbit…
Resonance Raman Studies of Bis(terpyridine)ruthenium(II) Amino Acid Esters and Diesters
Resonance Raman (rR) spectroscopy in combination with DFT calculations was used to elucidate the nature of the 1metal-to-ligand charge-transfer states (1MLCT) of ester derivatives of homo- and heteroleptic bis(terpyridine)ruthenium(II) complexes [RuII(tpy–COOC2H5)(tpy–R)](PF6)2 with R = NH2 (1a), R = COOC2H5 (1b) and R = NHCOCH3 (1c). The rR spectra provide evidence that the 1MLCT states of 1b and 1c are well described by the expected 1[(“t2g”)5{π*(tpy–COOC2H5)}1] electron configuration, while the 1MLCT state of the donor/acceptor-substituted complex 1a also involves the amine-substituted terpyridine ligand. The excited state of 1a can be described by a 1[{dyz/π(tpy–NH2)}1{π*(tpy–COOC2H5)}1…
Solid-Phase Synthesis of Peptide Libraries Combining α-Amino Acids with Inorganic and Organic Chromophores
The synthesis of two series of peptidic chains composed of bis(terpyridine)ruthenium(II) acceptor units and organic chromophores (coumarin, naphthalene, anthracene, fluorene) by stepwise solid-phase peptide synthesis (SPPS) techniques is described. The first series of dyads comprises directly amide linked chromophores, while the second one possesses a glycine spacer between the two chromophores. All dyads were studied by UV/Vis and NMR spectroscopy, steady-state luminescence, luminescence decay and electrochemistry, as well as by DFT calculations. The results of these studies indicate weak electronic coupling of the chromophores in the ground state. Absorption spectra of all dyads are domin…
Dinuclear bis(terpyridine)ruthenium(II) complexes by amide coupling of ruthenium amino acids: Synthesis and properties
Abstract Two redox-asymmetric amide-bridged bis(terpyridine)ruthenium(II) complexes (3a, 3b) have been prepared by amide coupling of a carboxylic acid functionalized complex with an amine substituted complex and they were fully characterized by spectroscopic analyses. They emit at 692 and 750 nm at room temperature in fluid solution with quantum yields larger than 10−3 and 3MLCT lifetimes of 22 ns. Ru···Ru distances were estimated from DFT models as 17.7 and 13.4 A for 3a and 3b, respectively. Cyclic voltammetry gives two oxidation potentials for the differently substituted ruthenium sites with splittings of 0.10 and 0.23 V for 3a and 3b, respectively. Oxidation of 3b with CeIV ions gives t…