Towards panchromatic Fe(ii) NHC sensitizersviaHOMO inversion

Abstract

A combined experimental and theoretical study of iron(II) complexes with pyridyl N-heterocyclic carbene ligands is presented, with a new focus on the effect of extending the ligands with thiophenes in...

CDs “inserted” abundant FeB-based electrode via “local photothermal effect” strategy toward efficient overall seawater splitting

“…24 Compared to FeB x @TiO 2 electrodes, the characteristic peaks of CDs-FeB x @TiO 2 exhibit small displacement and lattice expansion due to the strain effects caused by FeB. 25 The prepared CDs-FeB x @TiO 2 electrodes have more unpaired electrons and random orientation bonds, which help accelerate charge transfer between abundant active sites and reaction intermediates. 26 The microstructure of CDs-FeB x @TiO 2 can be observed via the field emission scanning electron microscopy (FESEM) image; spherical nanosheets are found on TiO 2 (Fig. 1b), and the surface of titanium dioxide is uniformly and firmly loaded with catalytic materials.…”

Improved transition metal photosensitizers to drive advances in photocatalysis

“…3b). 38 In the same vein as the terpyridine analogues (5-10), extending the p-conjugation of the thiophene substituents resulted in a red shi of the absorption spectrum.…”

“…3b ). 38 In the same vein as the terpyridine analogues (5–10), extending the π-conjugation of the thiophene substituents resulted in a red shift of the absorption spectrum. Another recent representative example of HOMO inversion is found in iron complexes with benzannulated amido pincer-like ligands developed by Braun and co-workers.…”

Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+

“…Theoretical chemistry-based ligand design can be a great asset for such efforts, yet high-level wave function-based computations are too expensive for applying them routinely to systems as large as transition-metal complexes. However, DFT offers a viable alternative, and the recent developments in understanding and designing certain properties of similar complexes computationally − as well as the vast accumulated knowledge on the Fe­(II) spin state transition systems ,− provide us with a great opportunity to use such complexes as a testing ground in evaluating the impact of different ligand modifications. We selected a prototypical Fe­(II) polypyridine complex to assess how electronic substitution effects can modify the potential energy landscape, in particular the singlet–quintet energy gap and the transition rate between these states.…”