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Dinuclear Cyclometalated Pincer Nickel(II) Complexes with Metal-Metal-to-Ligand Charge Transfer Excited States and
Mengyue Gao1, Wai-Pong To1, Glenna So Ming Tong1
1Department of Chemistry, State Key Laboratory of Synthetic Chemistry, CAS-HKU Joint Laboratory on New Materials, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
Abstract:
Facile non-radiative decay of low-lying metal-centered (MC) dd excited states has been well documented to pose a significant obstacle to the development of phosphorescent NiII complexes due to substantial structural distortions between the dd excited state and the ground state. Herein, we prepared a series of dinuclear Ni2 II,II complexes by using strong σ-donating carbene-phenyl-carbene (CNHC Cphenyl CNHC) pincer ligands, and prepared their dinuclear Pt2 II,II and Pd2 II,II analogues. Dinuclear Ni2 II,II complexes bridged by formamidinate/α-carbolinato ligand exhibit short Ni-Ni distances of 2.947-3.054 Å and singlet metal-metal-to-ligand charge transfer (1MMLCT) transitions at 500-550 nm. Their 1MMLCT absorption energies are red-shifted relative to the Pt2 II,II and Pd2 II,II analogues at ~450 nm and ≤420 nm respectively. One-electron oxidation of these Ni2 II,II complexes produces valence-trapped dinuclear Ni2 II,III species, which are characterized by EPR spectroscopy. Upon photoexcitation, these Ni2 II,II complexes display phosphorescence (τ=2.6-8.6 μs) in the NIR (800-1400 nm) spectral region in 2-MeTHF and in the solid state at 77 K, which is insensitive to π-conjugation of the coordinated [CNHC Cphenyl CNHC] ligand. Combined with DFT calculations, the NIR emission is assigned to originate from the 3dd excited state. Studies have found that the dinuclear Ni2 II,II complex can sensitize the formation of singlet oxygen and catalyze the oxidation of cyclo-dienes under light irradiation.
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