Comparison of carbazole and fluorene donating effects on the two-photon absorption and nitric oxide photo-release capabilities in a ruthenium-nitrosyl complex

A ruthenium–nitrosyl derivative of formula [RuII(CzT)(bipy)(NO)](PF6)3 [CzT = 4′-(N-ethylcarbazol-3-yl)-2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine] has been synthesized and fully characterized, and compared with the previously reported [RuII(FT)(bipy)(NO)](PF6)3 complex [FT = 4′-(9,9-dihexyl-9H...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2018 (3-4), p.531-543
Main Authors: Enriquez-Cabrera, Alejandro, Lacroix, Pascal G., Sasaki, Isabelle, Mallet-Ladeira, Sonia, Farfan, N., Barba-Barba, Rodrigo M., Ramos-Ortiz, Gabriel, Malfant, Isabelle
Format: Article
Language:English
Subjects:
Chemical Sciences
Coordination chemistry
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Summary:A ruthenium–nitrosyl derivative of formula [RuII(CzT)(bipy)(NO)](PF6)3 [CzT = 4′-(N-ethylcarbazol-3-yl)-2,2′:6′,2′′-terpyridine, bipy = 2,2′-bipyridine] has been synthesized and fully characterized, and compared with the previously reported [RuII(FT)(bipy)(NO)](PF6)3 complex [FT = 4′-(9,9-dihexyl-9H-fluoren-2-yl)-2,2′:6′,2′′-terpyridine]. Additionally, the X-ray crystal structure of [RuII(CzT)(bipy)(NO2)](PF6), the precursor of [RuII(CzT)(bipy)(NO)](PF6)3, is reported. The presence of a tertiary amine in the carbazole unit leads to redshifted charge-transfer transitions towards the electron-withdrawing Ru–NO fragment and hence enhanced two-photon absorption (TPA) properties. In contrast, the quantum yield of the NO· photorelease process is lower for the carbazole-containing complex. The issue of optimization of the TPA versus NO·-release capabilities is addressed.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201700895