Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published April 29, 1993 | public
Journal Article

Excited-state decay processes of binuclear rhodium(I) isocyanide complexes

Abstract

Emission lifetimes, quantum yields, and polarized excitation spectra of Rh_2b_4^(2+) and Rh_2(TMB)_4^(2+) (b = 1,3-diisocyanopropane; TMB = 2,5-diisocyano-2,5-dimethylhexane) have been determined. The singlet and triplet dσ* → pσ(^(1,3)A_(2u) excited states are luminescent with radiative rates of ca. 10^8 and 10^ s^(-1), respectively, consistent with values obtained from Strickler-Berg calculations based on the corresponding absorption bands. Both singlet and triplet upper excited states (dπ → pσ and metal-to-metal charge transfer, E_u symmetry) undergo nonradiative decay primarily to ^3A_(2u), bypassing ^1A_(2u), and the branching ratios for decay through several intermediate states have been estimated. The temperature dependences of the lifetimes of the ^1A_(2u), and ^3A_(2u) states of Rh_2(TMB)_4^(2+) are interpreted in terms of a model in which potential-surface crossings with the ^3B_(2u) (dσ* - d_(x^2 - y^2)) state facilitate nonradiative decay.

Additional Information

© 1993 American Chemical Society. Received: November 18, 1992; In Final Form: January 22, 1993. We thank David Smith for helpful discussions. This work was supported by National Science Foundation Grant CHE-8922067. Work at Brookhaven National Laboratory was performed under Contract DE-AC02-76CH00016 with the US. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences.

Additional details

Created:
August 20, 2023
Modified:
October 18, 2023