Details

Autor(en) / Beteiligte

• Pashanova, Kira I
• Ershova, Irina V
• Trofimova, Olesya Yu
• Rumyantsev, Roman V
• Fukin, Georgy K
• Bogomyakov, Artem S
• Arsenyev, Maxim V
• Piskunov, Alexandr V

Titel

Charge Transfer Chromophores Derived from 3d-Row Transition Metal Complexes

Ist Teil von

• Molecules (Basel, Switzerland), 2022-11, Vol.27 (23), p.8175

Ort / Verlag

Switzerland: MDPI AG

Erscheinungsjahr

2022

Link zum Volltext

Quelle

Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals

Beschreibungen/Notizen

• A series of new charge transfer (CT) chromophores of "α-diimine-M -catecholate" type (where M is 3d-row transition metals-Cu, Ni, Co) were derived from 4,4'-di- -butyl-2,2'-bipyridyl and 3,6-di- -butyl- -benzoquinone ( ) in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric ( ) and ( ) chromophores, while dimeric complex ( ) units two substantially distorted heteroleptic D-M -A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores - undergo an effective photoinduced intramolecular charge transfer (λ = 500-715 nm, extinction coefficient up to 10 M ·cm ) with a concomitant generation of a less polar excited species, the energy of which is a finely sensitive towards solvent polarity, ensuring a pronounced negative solvatochromic effect. Special attention was paid to energetic characteristics for CT and interacting HOMO/LUMO orbitals that were explored by a synergy of UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT study. The current work sheds light on the dependence of CT peculiarities on the nature of metal centers from various groups of the periodic law. Moreover, the "α-diimine-M -catecholate" CT chromophores on the base of "late" transition elements with differences in d-level's electronic structure were compared for the first time.