Abstract
Tailored heteroleptic trivalent chromium complexes combine kinetic inertness and structural control with tuneable photophysical properties, all aspects which are crucial for the design of a next gereneration of cheap (supra)molecular light-converting assemblies and devices. • Photoactive Cr(III) complexes as an alternative to precious Ru(II) complexes. • Lability-induced Cr(III) complexes as precursors for heteroleptic complexes. • Inert Cr(III)N 6 complexes might be exploited in metallo-supramolecular structures. • Cr(III)N 6 sensitizers can be programmed for providing long NIR excited state lifetimes. Although less famous than low-spin trivalent cobalt found in [Co III (NH 3 ) 6− x Cl x ]Cl 3− x ( x ≤ 3), which was exploited by Alfred Werner during the early part of the 20th century for establishing the basic rules of coordination chemistry, related trivalent chromium complexes exhibit comparable kinetic inertness, a rare property along the 3d-transition series. The associated slow isomerisation processes are compatible with the isolation of well-defined heteroleptic complexes. Some subtle energetic differences between Cr III -X (X = halide, pseudo-halide, cyanide, solvent) and Cr-N bonds can be exploited for preparing stable and inert cis / trans -[Cr(N ∩ N) 2 X 2 ] + and fac / mer -[Cr(N ∩ N ∩ N)X 3 ] primary heteroleptic complexes incorporating multidentate nitrogen-containing chelate ligands. The use of these building blocks within the frame of the ‘complex-as-ligand’ strategy, or via the labilization of the remaining Cr-X bonds pave the way for the design of discrete polymetallic assemblies in which the photophysically appealing [Cr III N 6 ] chromophores could find applications as functional light-converting devices.
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