In this work, efficient trans ⇌ cis photoswitchings of 4-(4-cyano)styrylpyridine (stpyCN) coordinated to organometallic bipyridyl tricarbonyl rhenium(I) complexes, fac-[Re(CO)(NN)( trans-stpyCN)], where NN = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmb), are described. For both complexes, the true trans-to- cis quantum yields determined by H NMR spectroscopy are similar at 313, 334, and 365 nm irradiations (Φ ∼ 0.45), with a small decrease at 404 nm (Φ ∼ 0.37). The investigated complexes also exhibit significant quantum yields for the reversible cis-to- trans photoreactions (Φ = 0.22). The luminescent properties of these complexes were also analyzed in different media to elucidate a key role of the IL state in photophysical and photochemical processes, giving new insights on their intriguing photobehavior.
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Molecular engineered rhenium(i) carbonyl complexes to promote photoisomerization of coordinated stilbene-like ligands in the visible region.
Dalton Trans
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Laboratory of Photochemistry and Energy Conversion, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo - USP, Av. Prof. Lineu Prestes, 748, 05508-000, São Paulo, SP, Brazil.
Novel fac-[Re(CO)3(dmcb)(trans-stpyR)]+ complexes, dmcb = 4,4'-dimethoxycarbonyl-2,2'-bipyridine, have been judiciously engineered to absorb at lower energies and sensitize trans-4-styrylpyridine (trans-stpy) or trans-4-(4-cyano)styrylpyridine (trans-stpyCN) photoisomerizable ligands up to 436 nm of irradiation. Moreover, these complexes exhibit remarkable photoreversibility, in particular fac-[Re(CO)3(dmcb)(trans-stpyCN)]+ (Φ255 nmcis→trans = 0.26 ± 0.
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J Phys Chem A
July 2018
Laboratory of Photochemistry and Energy Conversion, Departamento de Química Fundamental, Instituto de Química , Universidade de São Paulo - USP , Avenue Prof. Lineu Prestes, 748 , 05508-000 , São Paulo, SP , Brazil.
In this work, efficient trans ⇌ cis photoswitchings of 4-(4-cyano)styrylpyridine (stpyCN) coordinated to organometallic bipyridyl tricarbonyl rhenium(I) complexes, fac-[Re(CO)(NN)( trans-stpyCN)], where NN = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmb), are described. For both complexes, the true trans-to- cis quantum yields determined by H NMR spectroscopy are similar at 313, 334, and 365 nm irradiations (Φ ∼ 0.45), with a small decrease at 404 nm (Φ ∼ 0.
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Dalton Trans
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Laboratory of Photochemistry and Energy Conversion, Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo - USP, Av. Prof. Lineu Prestes, 748, 05508-900, São Paulo, SP, Brazil.
In our search for light powered molecular devices, a novel fac-[Re(CO)(phphen)(trans-stpyCN)] complex was synthesized to show switchable trans-cis configurations of the coordinated stpyCN ligand through efficient and reversible photoassisted isomerizations. Controlled photolyses of acetonitrile solutions led to spectral changes ascribed to reversible trans⇌cis photoisomerization processes. A remarkable quantum yield for the back cis-to-trans isomerization was obtained, with the same magnitude of the trans-to-cis photoprocess, and curiously, both trans- and cis-isomers are emissive at room temperature.
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