Ultrafast Excited-State Processes in Re(I) Carbonyl-Diimine Complexes: From Excitation to Photochemistry

Quantitative wave function analysis for excited states of transition metal complexes

“…The imidazole (im) derivative [Re(CO) 3 (im)(phen)] + is employed in the study of electron transfer in proteins [18,173,182,183]. In this particular complex, it has been often noted that the optical orbitals are delocalized over the metal and the carbonyls, thus giving rise to mixed MLCT/LLCT states [29,57]. As this situation is very similar to that encountered in [Re(Cl)(CO) 3 (bipy)] in section 3.3, this molecule seems very suitable to challenge wave function analysis.…”

“…The speci c interaction between the metal and the di erent ligands leads to several distinct "textbook" classes of excited states in TMCs-metal-centered states (MC), intra-ligand states (IL), metal-to-ligand charge transfer states (MLCT), ligand-to-metal charge transfer states (LMCT), and ligand-to-ligand charge transfer states (LLCT)-whose properties and interplay are of central importance [24][25][26][27][28]. Actually, most of the above-mentioned applications are based on achieving some favorable properties of particular excited states [16,29,30]. For example, redox photocatalysis exploits the fact that MLCT states can be both better electron acceptors and electron donors than the ground state [9].…”

“…In this context, it should be remembered that these orbitals are simply a way to represent the many-electron wave function, whereas it is "fallacious to con ate the molecular orbitals with anything in the real world" [16]. Moreover, a given computed state might be a non-trivial linear combination of the "textbook" classes of excited states [29], making assignment di cult. Also, the comparison between excited-state properties computed using wave function methods and DFT is not an easy task and encounters limitations, as, e.g., illustrated for third-row TMCs [58,60].…”

Photophysical properties of Re(I)(CO)3(phen) pendants grafted to a poly-4-vinylpyridine backbone. A correlation between photophysical properties and morphological changes of the backbone

“…Among the third row of transition metal compounds, Re(I) tricarbonyl complexes coordinated to mono or bidentate azines of the type fac-XRe(CO)3L (where X= halide and/or substituted azine and L= α-diimine) show exceptionally rich excited-state behavior and redox chemistry as well as thermal and photochemical stability [1]. Broad structural variations of the L ligand allowed to utilize them in electron transfer studies [2], solar energy conversion [3][4][5], catalysis [6], as luminescent sensors [7][8][9], molecular materials for non-linear optics [10][11] and optical switching [12].…”

On the mechanism of formation and spectral properties of radical anions generated by the reduction of –[ReI(CO)3(5-nitro-1,10-phenanthroline)]+ and –[ReI(CO)3(3,4,7,8-tetramethyl-1,10-phenanthroline)]+ pendants in poly-4-vinylpyridine polymers

“…Interest in their photochemical and photophysical properties is driven by their potential applications in catalysis and optical devices [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. The properties in the solution phase of the polymers {(vpy) 2 -vpy[Re I (CO) 3 (phen)] + } n$200 and {(vpy) 2 -vpy[Re I (CO) 3 (bpy)] + } n$200 (see Schemes 1 and 2) were investigated in previous works [1,9,12].…”