Emission Switching in the Near-Infrared by Reversible Trans-Cis Photoisomerization of Styrylbenzene-Conjugated Osmium Terpyridine Complexes.

A new array of homoleptic osmium(II) complexes based on styrylbenzene-conjugated terpyridine ligands (tpy-pvp-X) were synthesized and their photophysical, electrochemical, and photoisomerization behaviors thoroughly investigated in this work. Both electron-donating and -withdrawing substituents were incorporated onto a tpy-pvp-X (X = H, Me, Cl, NO, and Ph) moiety to tune the optical properties and also the rate of photoisomerization behaviors in the complexes. All complexes display strong spin-allowed singlet metal-to-ligand charge-transfer bands in the visible (495-506 nm) and weak singlet ground state to triplet metal-to-ligand charge-transfer (MLCT) broad bands within the 600-700 nm range. The complexes also exhibit strong phosphorescence emission from their MLCT state in the near-infrared domain (737-752 nm) at room temperature with excited-state lifetimes spanning between 107 and 165 ns. Two styrylbenzene units promote reversible trans-trans to trans-cis/cis-cis isomerization induced by light. The rate constants and quantum yields of photoisomerization were found to vary linearly with the Hammett σ parameters of the substituents. The rate and quantum yields were also found to decrease with increasing polarity of the solvents. Considerable modulation of the optical behavior along with luminescence switching in the complexes has been achieved upon photoisomerization. Moreover, the optical outputs as a function of two photonic stimuli inputs were used to demonstrate the binary function of a two-input IMPLICATION logic gate. In conjunction with the experimental study, computational investigations were also carried out in all three conformations of the complexes (trans-trans, trans-cis, and cis-cis) to have a perception of their electronic structures and for correct assignment of their absorption and emission spectral bands.