Connick, William B. and Miskowski, Vincent M. and Houlding, Virginia H. and Gray, Harry B. (2000) Lowest Electronic Excited States of Platinum(II) Diimine Complexes. Inorganic Chemistry, 39 (12). pp. 2585-2592. ISSN 0020-1669. doi:10.1021/ic991369w. https://resolver.caltech.edu/CaltechAUTHORS:20170808-095512740
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Abstract
Absorption and emission spectra of Pt(diimine)L_2 complexes (diimine = 2,2‘-bipyridine (bpy) or 4,4‘-dimethyl-2,2‘-bipyridine (dmbpy); L = pyrazolate (pz-), 3,5-dimethylpyrazolate (dmpz-), or 3,4,5-trimethylpyrazolate (tmpz-)) have been measured. Solvent-sensitive absorption bands (370−440 nm) are attributed to spin-allowed metal-to-ligand charge-transfer (^1MLCT) transitions. As solids and in 77 K glassy solution, Pt(bpy)(pz)_2 and Pt(dmbpy)(pz)_2 exhibit highly structured emission systems (λ_(max)≈ 494 nm) similar to those of the diprotonated forms of these complexes. The highly structured bands (spacings 1000−1400 cm^(-1)) indicate that the transition originates in a diimine-centered ^3(π→π*) (^3LL) excited state. The intense solid-state and 77 K glassy solution emissions from ^3MLCT[d(Pt)→π*(bpy)] excited states of complexes with dmpz- and tmpz- ligands occur at longer wavelengths (λ_(max) = 500−610 nm), with much broader vibronic structure. These findings are consistent with increasing electron donation of the pyrazolate ligands, leading to a distinct crossover from a lowest ^3LL to a ^3MLCT excited state.
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| Additional Information: | © 2000 American Chemical Society. Received November 29, 1999. Publication Date (Web): May 19, 2000. We thank J. A. Bailey, A. J. DiBilio, and J. R. Winkler for many helpful discussions and expert technical assistance. This work was supported by NSF. | |||||||||
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| Issue or Number: | 12 | |||||||||
| DOI: | 10.1021/ic991369w | |||||||||
| Record Number: | CaltechAUTHORS:20170808-095512740 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170808-095512740 | |||||||||
| Official Citation: | Lowest Electronic Excited States of Platinum(II) Diimine Complexes William B. Connick, Vincent M. Miskowski, Virginia H. Houlding, and Harry B. Gray Inorganic Chemistry 2000 39 (12), 2585-2592 DOI: 10.1021/ic991369w | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 79923 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 09 Aug 2017 19:29 | |||||||||
| Last Modified: | 15 Nov 2021 17:51 |
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