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New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications. [ABSTRACT FROM AUTHOR]

Co, Ni and Cu complexes with a non-innocent ortho -aminophenol were synthesized by the reaction of metal(II)acetates with a ligand precursor. • Metal complexes with redox-active non-innocent ligands. • Structurally analogous square-planar complexes of Co, Ni and Cu. • High near-IR absorption. Bench top stable transition metal (M = Co, Ni, Cu) complexes with a non-innocent ortho -aminophenol derivative were synthesized by the reaction of metal(II)acetates with a ligand precursor in 2:1 ratio. The solid-state structures reveal the formation of neutral molecular complexes with square planar coordination geometries. The Co(II) and Cu(II) complexes are paramagnetic, whereas the Ni complex is a diamagnetic square planar low-spin Ni(II) complex. All complexes, and Ni(II) complex in particular, show strong absorption in the near-IR region. [ABSTRACT FROM AUTHOR]