Photoswitchable and pH responsive organoplatinum(ii) complexes with azopyridine ligands

Abstract

Several platinum(II) complexes with ligands containing azo groups have been prepared and structurally characterised, and their photoswitching between trans and cis azo group isomers has been studied. The azo groups in the cationic complexes [PtMe(bipy)(4-NC₅H₄-NN-4-C₆H₄X)][PF₆], X = H, OH or NMe₂, and in the dicationic complex [Pt(bipy)(4-H₂NC₆H₄-NN-C₆H₅)₂][OTf]₂ undergo trans to cis photoswitching on irradiation at 365 nm. The complex [PtMe(bipy)(4-NC₅H₄-NN-4-C₆H₄NMe)₂][PF₆] also exhibits a reversible halochromic effect on protonation to give the dicationic complex [PtMe(bipy)(4-NC₅H₄-NHN-4-C₆H₄NMe₂]²⁺. The nature of the frontier orbitals in the platinum(II) complexes depends on the charge on the complex and on the degree of metal–ligand π-bonding.