Influences of Both N,N,N- and N,N,C-Coordination Modes of Tolyl-terpyridine on the Photophysical Properties of Cyclometalated Ru(II) Complexes: Combined Experimental and Theoretical Investigations on Acid/Base-Dependent Reversible Cyclometalation.

With the goal of developing a new strategy for the synthesis of luminescent Ru(II) complexes, we have prepared herein a new set of bis-tridentate complexes of the type [(py-bpy-Ph-X)Ru(tpy-PhCH 3 )]ClO 4 (X = -CH 3 , -CH 2 Br, and -CHO) incorporating both non-cyclometalated and cyclometalated coordination motifs of two isomeric forms of methylphenyl-terpyridine (tpy-PhCH 3 ). Thorough characterization of the synthesized complexes is carried out using standard analytical tools and single crystal X-ray diffraction. Detailed investigations on their photophysical and electrochemical behaviors are carried out in MeCN. The presence of a carbanionic center in the cyclometalating unit increases the absorption spectral window of the complexes into a longer-wavelength region. The complexes also exhibit room-temperature luminescence in the NIR domain with enhanced excited-state lifetimes (up to 20.1 ns) compared to their non-cyclometalated counterpart, [Ru(tpy-PhCH 3 ) 2 ] 2+ . In the presence of acid, the non-coordinated nitrogen atom in the secondary coordination sphere of the complexes allows fine-tuning of the absorption and emission spectral properties. Excess acid induces de-coordination of the Ru-C bond, which is signaled by a remarkable alteration of their spectral profiles. Cleavage of the Ru-C bond is also possible upon treating the acidified solution of the complexes with visible light. Restoration of the Ru-C bond is again feasible upon treating the solution with base at an elevated temperature (∼70 °C). In essence, "on-off" and "off-on" switching of emission is facilitated upon alternating treatment of the Ru(II) complexes with acid, base, and temperature. DFT and TD-DFT calculations are also performed for assignments of the spectral bands as well as to understand structural changes associated with the switching behaviors of the complexes.