Pressure effects on the photochemical and photophysical properties of the rhodium(III) complexes RhA5X2+ (A = NH3, ND3; X = Cl, Br) in aqueous solution

Abstract

Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this work. The authors also wish to thank Johnson-Matthey, Inc., for loan of the ruthenium used in this study. In addition, the help of Dr. K. Klabunde and Mr. R. Zoellner in preparing the starting materials and Dr. D. Mueller in obtaining 31P NMR spectra is gratefully acknowledged.Registry No. tra«s-Ru(dmpe)2Cl2, 19206-05-4; m-Ru(dmpe)2Cl2, 84172-85-0; t7wu-Ru(dmpe)2(H20)Cl+, 84130-50-7; trans-Ru-(dmpe)2(Me2SO)Cl+, 84130-51-8; [Ru2(Cl)3(PEt2Ph)6]Cl, 84130-52-9.

Metal centered ligand field excited states: Their roles in the design and performance of transition metal based photochemical molecular devices

“…For instance, solvent effects on the rate constant for Cl − labilization from the LEES of Rh(NH 3 ) 5 Cl 2+ [135] have been rationalized in terms of significant charge separation along the Rh 3+ -Cl − bond at the transition state, the energy of which is influenced strongly by the ability of the solvent to stabilize the charge separation [127]. Consistently, the pattern shown by activation volumes for the ES substitution rate constants for the LF excited states support this interpretation [136][137][138][139]. Finally, theoretical models similar to those applied to predict substitution patterns for the quartet states of d 3 complexes via a dissociative mechanism are also successful in predicting photosubstitution patterns for d 6 complexes [100,101].…”

Ligand macrocycle effects on the photophysical properties of rhodium(III) complexes: a detailed investigation of cis- and trans-dicyano(1,4,8,11-tetraazacyclotetradecane)rhodium(III) and related species

“…Lifetime measurements were recorded utilizing a Quanta Ray DCR-1A Q-switched Nd:YAG pulsed laser operating at 10 Hz as the excitation source. The system was equipped with an HG-1 harmonic generator and a PHS-1 harmonic separator to isolate the desired frequency.…”

From curiosity to applications. A personal perspective on inorganic photochemistry

“… 19 – 22 In this manner we were also able to probe the 3 MC* state ligand substitution and nonradiative decay mechanisms with hydrostatic pressure effects in collaboration with R. van Eldik. 23 …”

“…In this context, a collaborative investigation with Rudi van Eldik 23 measured the photoreaction quantum yields and lifetimes for aq. Rh(NH 3 ) 5 Cl 2+ as a function of hydrostatic pressure up to 200 MPa, and activation volumes Δ V ‡ i were determined.…”