Abstract
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.
Highlights
In coordination chemistry, a ligand is referred as ‘non-innocent’ when it forms complexes where the oxidation state of the central atom cannot be absolutely defined [1]
The foremost motivation for research on such redox-active ligands has been in the development of new homogenous catalysts, which could utilize these ligands as electron reservoirs during the catalytic cycle
There are many metal-organic transition metal complexes with redox-active ligands which are studied for their potential applicability for strongly near-infrared (NIR)-absorbing dyes [9,10,11,12,13,14,15,16,17,18,19] or as single molecule magnets [20,21,22,23] (SMMs)
Summary
A ligand is referred as ‘non-innocent’ when it forms complexes where the oxidation state of the central atom cannot be absolutely defined [1]. There are many metal-organic transition metal complexes with redox-active ligands which are studied for their potential applicability for strongly near-infrared (NIR)-absorbing dyes [9,10,11,12,13,14,15,16,17,18,19] or as single molecule magnets [20,21,22,23] (SMMs). Lis aAs redox-active ligand that can have, in can certain protonation delocalized π-conjugated systems, it can form stable radicals upon complexation with transition metal ions [8]. Systems, it can form stable radicals upon complexation with transition metal ions.[8] Stable radicals, Stable radicals, i.e., compounds carrying unpaired electrons, may have strong interactions with photons i.e., compounds carrying unpaired electrons, may have strong interactions with photons and and exhibit strong absorption at UV-Vis-NIR this study, weused haveHused. L (adapted fromfrom the reference [8])
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