Photochemistry and photocatalysis of rhenium(I) diimine complexes

Synthesis, characterization, photophysical and electrochemical properties of fac-tricarbonyl(4,7-dichloro-1,10-phenanthroline)rhenium(I) complexes

“…To meet this energy need, transition metal complexes, especially those with d 6 electron configuration, have been receiving great attention in investigations related to solar energy conversion 1-2 , photocatalysis [3][4][5] , and electroluminescent devices such as LECs [6][7][8] and OLEDs 9-12 , among others. The reasons for the great interest in this class of compound are various and include absorption of radiation in a lower region of the spectrum than observed in organic counterparts; strong spin-orbit coupling, especially for the second and third transition metal, which eliminates the spin-forbidden T 1 →S 0 radiative transition; excited states with intense redox activity allowing the occurrence of a series of electron transfer reactions and/or energy, among others [13][14] .…”

“…In particular, the rhenium(I) tricarbonyl polypyridyl complexes have been widely investigated due to their interesting triplet emissive properties 3,[14][15][16] . Additionally, intense effort has been dedicated to better understand the effect of the position and attachment of electron withdrawing/donating groups to ligands on the mechanistic events after excitation 15,[17][18][19][20][21] , which can contribute to a deeper comprehension of their emissive properties.…”

Using the Alkynyl-Substituted Rhenium(I) Complex (4,4′-Bisphenyl-Ethynyl-2,2′-Bipyridyl)Re(CO)3Cl as Catalyst for CO2 Reduction—Synthesis, Characterization, and Application

“…Suitable modifications of the ligand sphere in derivatives of (3) led to the development of improved systems with quantum yields (Φ CO ) up to 0.59, making this type of materials the most efficient CO 2 reduction photocatalysts known by now [7,12]. Additionally, variations of the substitution pattern of the bipyridyl ligand should have a strong influence on the relative ordering of the lowest-lying excited states in such rhenium carbonyl complexes [19].…”

“…As the IR absorption bands of the C≡O vibrations are dominant in the spectra and reside in the frequency region where no other absorption bands exist, these bands are useful to probe the electronic exited states of these compounds. Additionally, these band frequencies are greatly influenced by the electron density on the central rhenium(I) atom, which is considered to be the driving force for catalytic CO 2 reduction [12]. In a very recent study, Kubiak and his group reported on the shift of the ν CO stretching vibration upon reaction of [Re(bipy)(CO) 3 [22,23].…”

“…Studies show that these catalysts yield CO as the main reduction product with almost no hydrogen and formic acid formed as side products [7][8][9][10]. It has been shown that the metal-centered and the metal-to-ligand charge-transfer (MLCT) electronic states can be altered by ligand modification [11,12]. Recently, our group reported the synthesis, structure, photophysics, spectroscopic characterization, and catalytic activity of the modified rhenium complex (5,5′-bisphenylethynyl-2,2′-bipyridyl)Re(CO) 3 Cl, carrying additional phenylethynyl substituents at the acceptor ligand on the 5,5′-position compared to the well-studied (2,2′-bipyridyl)-Re(CO) 3 Cl [11,13].…”