Dinuclear Cyclometalated Pincer Nickel(II) Complexes with Metal‐Metal‐to‐Ligand Charge Transfer Excited States and Near‐Infrared Emission

Abstract

Facile non‐radiative decay of low‐lying metal‐centered (MC) d‐d 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 d‐d excited state and the ground state. Herein, we prepared a series of dinuclear Ni2II,II complexes by using strong σ‐donors, carbene‐phenyl‐carbene (CNHC^Cphenyl^CNHC) pincer ligands, and prepared their dinuclear Pt2II,II and Pd2II,II analogues. Dinuclear Ni2II,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 Pt2II,II and Pd2II,II analogues at ~450 nm and ≤420 nm respectively. One‐electron oxidation of these Ni2II,II complexes produces valence‐trapped dinuclear Ni2II,III species, which are characterized by EPR spectroscopy. Upon photoexcitation, these Ni2II,II complexes display phosphorescence (τ=2.6‐8.6 μs) in the NIR (800‐1400nm) spectral region in 2‐MeTHF and in 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 Ni2II,II complex can sensitize the formation of singlet oxygen and catalyze the oxidation of cyclo‐dienes under light irradiation.