5 years ago

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

Isabelle Sasaki, Rodrigo Barba-Barba, Alejandro Enriquez-Cabrera, Norberto Farfan, Sonia Malet-Ladeira, Gabriel Ramos-Ortiz, Pascal Georges Lacroix, Isabelle Malfant
A ruthenium nitrosyl derivative of formula [RuII(CzT)(bipy)(NO)](PF6)3, where CzT is the 4'-(N-ethyl-carbazol-3-yl)-2,2':6',2''-terpyridine, and bipy the 2,2'-bipyridine has been synthesized and fully characterized, and compared to the previously reported [RuII(FT)(bipy)(NO)](PF6)3 complex (FT = 4'-(9,9-dihexyl-9H-fluorene-2-yl)-2,2':6',2''-terpyridine). Additionally, the X-Ray crystal structure of [RuII(CzT)(bipy)(NO2)](PF6), precursor of [RuII(CzT)(bipy)(NO)](PF6)3, is reported. The presence of a tertiary amine on the carbazole unit leads to red-shifted charge transfer transitions towards the withdrawing Ru-NO fragment and hence enhanced two-photon absorption (TPA) properties. By contrast, the quantum yield of the NO· photo-release process appears lowered in the carbazole derivative. The issue of the optimization of the TPA vs NO· release capabilities is addressed.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700895

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