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Structural Control of ^1A_(2u)-to-^3A_(2u) Intersystem Crossing in Diplatinum(II,II) Complexes

Durrell, Alec C. and Keller, Gretchen E. and Lam, Yan-Choi and Sýkora, Jan and Vlček, Antonín, Jr. and Gray, Harry B. (2012) Structural Control of ^1A_(2u)-to-^3A_(2u) Intersystem Crossing in Diplatinum(II,II) Complexes. Journal of the American Chemical Society, 134 (34). pp. 14201-14207. ISSN 0002-7863.

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Analysis of variable-temperature fluorescence quantum yield and lifetime data for per(difluoroboro)tetrakis(pyrophosphito)diplatinate(II) ([Pt_2(μ-P_2O_5(BF_2)_(2)4)]^(4–), abbreviated Pt(pop-BF_2)), yields a radiative decay rate (k_r = 1.7 × 10^8 s^(–1)) an order of magnitude greater than that of the parent complex, Pt(pop). Its temperature-independent and activated intersystem crossing (ISC) pathways are at least 18 and 142 times slower than those of Pt(pop) [ISC activation energies: 2230 cm^(–1) for Pt(pop-BF_2); 1190 cm^(–1) for Pt(pop)]. The slowdown in the temperature-independent ISC channel is attributed to two factors: (1) reduced spin–orbit coupling between the ^1A_(2u) state and the mediating triplet(s), owing to increases of LMCT energies relative to the excited singlet; and (2) diminished access to solvent, which for Pt(pop) facilitates dissipation of the excess energy into solvent vibrational modes. The dramatic increase in E_a is attributed to increased P-O-P framework rigidity, which impedes symmetry-lowering distortions, in particular asymmetric vibrations in the Pt_2(P-O-P)_4 core that would allow direct ^1A_(2u)–^3A_(2u) spin–orbit coupling.

Item Type:Article
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URLURL TypeDescription
Lam, Yan-Choi0000-0001-7809-4471
Sýkora, Jan0000-0003-0936-9368
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2012 American Chemical Society. Received: June 15, 2012. Publication Date (Web): August 6, 2012. We thank Renske van der Veen for interesting discussions. Research at Caltech was supported by the NSF Center for Chemical Innovation (Powering the Planet CHE-0802907 and CHE-0947829) and CSER (Gordon and Betty Moore Foundation). Work at the J. Heyrovský Institute was funded by the Czech Ministry of Education program KONTAKT (grant ME10124).
Group:CCI Solar Fuels
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Caltech Center for Sustainable Energy ResearchUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Ministry of Education (Czech Republic)ME10124
Issue or Number:34
Record Number:CaltechAUTHORS:20120910-110255434
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Official Citation:Structural Control of 1A2u-to-3A2u Intersystem Crossing in Diplatinum(II,II) Complexes Alec C. Durrell, Gretchen E. Keller, Yan-Choi Lam, Jan Sýkora, Antonín Vlček, Jr., and Harry B. Gray pp 14201–14207 Publication Date (Web): August 6, 2012 (Article) DOI: 10.1021/ja305666b
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33960
Deposited By: Ruth Sustaita
Deposited On:10 Sep 2012 18:33
Last Modified:22 Jun 2021 17:31

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