In-Depth Studies of Ground- and Excited-State Properties of Re(I) Carbonyl Complexes Bearing 2,2′:6′,2″-Terpyridine and 2,6-Bis(pyrazin-2-yl)pyridine Coupled with π-Conjugated Aryl Chromophores

[Image: see text] In the current work, comprehensive photophysical and electrochemical studies were performed for eight rhenium(I) complexes incorporating 2,2′:6′,2″-terpyridine (terpy) and 2,6-bis(pyrazin-2-yl)pyridine (dppy) with appended 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl, and 1-pyrenyl groups. Naphthyl and phenanthrenyl substituents marginally affected the energy of the MLCT absorption and emission bands, signaling a weak electronic coupling of the appended aryl group with the Re(I) center. The triplet MLCT state in these complexes is so low lying relative to the triplet (3)IL(aryl) that the thermal population of the triplet excited state delocalized on the organic chromophore is ineffective. The attachment of the electron-rich pyrenyl group resulted in a noticeable red shift and a significant increase in molar absorption coefficients of the lowest energy absorption of the resulting Re(I) complexes due to the contribution of intraligand charge-transfer (ILCT) transitions occurring from the pyrenyl substituent to the terpy/dppy core. At 77 K, the excited states of [ReCl(CO)(3)(L(n)-κ(2)N)] with 1-pyrenyl-functionalized ligands were found to have predominant (3)IL(pyrene)/(3)ILCT(pyrene→terpy) character. The (3)IL/(3)ILCT nature of the lowest energy excited state of [ReCl(CO)(3)(4′-(1-pyrenyl)-terpy-κ(2)N)] was also evidenced by nanosecond transient absorption and time-resolved emission spectroscopy. Enhanced room-temperature emission lifetimes of the complexes [ReCl(CO)(3)(L(n)-κ(2)N)] with 1-pyrenyl-substituted ligands are indicative of the thermal activation between (3)MLCT and (3)IL/(3)ILCT excited states. Deactivation pathways occurring upon light excitation in [ReCl(CO)(3)(4′-(1-naphthyl)-terpy-κ(2)N)] and [ReCl(CO)(3)(4′-(1-pyrenyl)-terpy-κ(2)N)] were determined by femtosecond transient absorption studies.