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Excited state properties of Rh(phi)_2(phen)^(3+) and related complexes: a strong photooxidant

Turro, Claudia and Evenzahav, Ariella and Bossmann, Stefan H. and Barton, Jacqueline K. and Turro, Nicholas J. (1996) Excited state properties of Rh(phi)_2(phen)^(3+) and related complexes: a strong photooxidant. Inorganica Chimica Acta, 243 (1). pp. 101-108. ISSN 0020-1693. http://resolver.caltech.edu/CaltechAUTHORS:20170408-162652102

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Abstract

The excited state properties and reactivity of Rh(phi)_2(phen)^(3+) (phi = 9,10-phenanthrenequinone diimine, phen = 1,10-phenanthroline) were investigated and compared to those of related rhodium(III) and zinc(II) complexes. At 77 K Rh(phi)_2(phen)^(3+) exhibits LC^3ππ∗ dual emission from both phi and phen ligands, whose energies are 2.8 eV and 3.0 eV, respectively, with a biexponential decay that can be fit to 5 ns (98%) and 60 ns (2%) lifetime components. A longer-lived transient is observed by transient absorption both at 77 K and 298 K, which decays monoexponentially with a time constant of 900 ns and 235 ns at each temperature, respectively, in ethanol. The transient can be attained with visible excitation (420 nm to 532 nm) and it is assigned to be intra-ligand charge transfer (ILCT) in nature. It was determined from transient absorption experiments that the ILCT excited state of Rh(phi)_2(phen)^(3+) lies approximately 2.0 eV above the ground state and that it is a powerful oxidizing agent with E_(12)([Rh]^(3+∗/2+))≈2.0V versus NHE. The transient absorption experiments with electron donors reveal that the one-electron reduced Rh(phi)_2(phen)^(2+) absorbs at 540 nm with ε ≈ 3300 M^(−1)cm^(−1).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/0020-1693(95)04896-0DOIArticle
https://www.sciencedirect.com/science/article/pii/0020169395048960PublisherArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 1996 Published by Elsevier. This paper is dedicated m Professor Harry B. Gray. We thank Michelle Arkin and Dr. Eric Stemp for helpful discussions. C.T. thanks the Jane Coffin Childs Memorial Fund for Medical Research for a post-doctoral fellowship. This investigation has been aided by a grant from The Jane Coffin Childs Memorial Fund for Medical Research. Further support has been provided by Upjohn Pharmaceuticals (A.E.) and the Deutsche Forschungsgemeinshaft (S.H.B.). N.J.T. thanks the National Science Foundation and J.K.B. the National Institutes of Health for their generous support of this research.
Funders:
Funding AgencyGrant Number
Jane Coffin Childs Memorial Fund for Medical ResearchUNSPECIFIED
Upjohn PharmaceuticalsUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)UNSPECIFIED
NSFUNSPECIFIED
NIHUNSPECIFIED
Subject Keywords:Electron transfer; Excited state properties; Rhodium; Phenanthrene diimine complexes; Phenanthroline
Record Number:CaltechAUTHORS:20170408-162652102
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170408-162652102
Official Citation:Claudia Turro, Ariella Evenzahav, Stefan H. Bossmann, Jacqueline K. Barton, Nicholas J. Turro, Excited state properties of Rh(phi)2(phen)3+ and related complexes: a strong photooxidant, Inorganica Chimica Acta, Volume 243, Issues 1–2, 1996, Pages 101-108, ISSN 0020-1693, https://doi.org/10.1016/0020-1693(95)04896-0. (http://www.sciencedirect.com/science/article/pii/0020169395048960)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76185
Collection:CaltechAUTHORS
Deposited By: 1Science Import
Deposited On:07 Mar 2018 00:14
Last Modified:07 Mar 2018 00:14

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