Full-electron ligand-to-ligand charge transfer in a compact Re(I) complex.
Ligand-to-ligand charge transfer (LLCT) states in transition metal complexes are often characterized by fractional electron transfer due to coupling of the LLCT state with many other states via the metal. We designed and characterized a compact Re(I) complex that displays essentially full-electron charge transfer in the LLCT excited state. The complex, [Re(DCEB)(CO)3(L)](+) (DCEB = 4,4'-dicarboxyethyl-2,2'-bipyridine), referred to as ReEBA, features two redox active ligands with strong electron accepting (DCEB) and electron donating (L is 3-dimethylaminobenzonitrile (3DMABN)) properties. The lowest energy excited state formed with a ca. 10 ps time constant and was characterized as the full-electron 3DMABN → DCEB LLCT state using time-resolved infrared spectroscopy (TRIR), transient absorption spectroscopy, and DFT computations. Analysis of a range of vibrational modes helped to assign the charge transfer characteristics of the complex. The LLCT state lifetime in ReEBA shows a strong dependence on the solvent polarity and features solvent dependent frequency shifts for several vibrational reporters. The formation of a full-electron LLCT state (∼92%) was enabled by tuning the redox properties of the electron accepting ligand (DCEB) and simultaneously decoupling the redox active group of the electron donating ligand (3DMABN) from the metal center. This strategy is generally applicable for designing compact transition metal complexes that have full-electron LLCT states.
Yue, Y; Grusenmeyer, T; Ma, Z; Zhang, P; Schmehl, RH; Beratan, DN; Rubtsov, IV
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