Chromium(III) Bis-Arylterpyridyl Complexes with Enhanced Visible Absorption via Incorporation of Intraligand Charge-Transfer Transitions

A series of chromium(III) bis-arylterpyridyl complexes containing intraligand charge-transfer (ILCT) excited states were prepared and characterized. These complexes show significant absorption in the visible region due to the ILCT bands. The ILCT bands are tunable across the UV and visible spectrum via incorporation of electron-withdrawing and electron-donating groups on the aryl ring. The absorption of Cr(4'-(4-methoxyphenyl)-2,2':6',2″-terpyridine)₂³⁺ (4) in particular is much stronger in the visible region (ε = 11 900 M^-1 cm^-1 at 450 nm and ε = 5090 M^-1 cm^-1 at 500 nm) than that of the parent complex Cr(tpy)₂³⁺ (tpy = 2,2':6',2″-terpyridine; ε = 2160 M^-1 cm^-1 at 450 nm, and ε = 170 M^-1 cm^-1 at 500 nm). Emission experiments on this series reveal Cr(III)-based phosphorescence with lifetimes from 140 to 600 ns upon excitation into the ILCT bands, which indicates funneling of the excitation energy from ligand-localized excited states to Cr(III)-based excited states. Cyclic voltammograms exhibit at least three reversible ligand-based reductions. The first reduction shows shifts of up to -160 mV compared to Cr(tpy)₂³⁺. The excited-state reduction potential of these complexes ranges from +0.95 to +1.04 V vs the ferrocene/ferrocenium couple, making them potent photooxidants.