Pyridazine-bridged cationic diiridium complexes as potential dual-mode bioimaging probes

Abstract

A novel diiridium complex [(N^C^N)₂Ir(bis-N^C)Ir(N^C^N)₂Cl]PF₆ (N^C^N = 2-[3-tert-butyl-5-(pyridin-2-yl)phenyl]pyridine; bis-N^C = 3,6-bis(4-tert-butylphenyl)pyridazine) was designed, synthesised and characterised. The key feature of the complex is the bridging pyridazine ligand which brings two cyclometallated Ir(III) metal centres close together so that Cl also acts as a bridging ligand leading to a cationic complex. The ionic nature of the complex offers a possibility of improving solubility in water. The complex displays broad emission in the red region (λ_em = 520–720 nm, τ = 1.89 μs, Φ_em = 62% in degassed acetonitrile). Cellular assays by multiphoton (λ_ex = 800 nm) and confocal (λ_ex = 405 nm) microscopy demonstrate that the complex enters cells and localises to the mitochondria, demonstrating cell permeability. Further, an appreciable yield of singlet oxygen generation (Φ_Δ = 0.45, direct method, by ¹O₂ NIR emission in air equilibrated acetonitrile) suggests a possible future use in photodynamic therapy. However, the complex has relatively high dark toxicity (LD₅₀ = 4.46 μM), which will likely hinder its clinical application. Despite this toxicity, the broad emission spectrum of the complex and high emission yield observed suggest a possible future use of this class of compound in emission bioimaging. The presence of two heavy atoms also increases the scattering of electrons, supporting potential future applications as a dual fluorescence and electron microscopy probe.