Two heteroleptic Ni^II complexes combined the redox-active catecholate and 2,2′- bipyridine ligand platforms were synthesized to observe a photoinduced intramolecular ligand-to-ligand charge transfer (LL’CT, HOMO_catecholate → LUMO_α-diimine). A molecular design of compound [Ni^II(3,6-Cat)(bipy)]∙CH₃CN (1) on the base of bulky 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) was an annelation of the ligand with an electron donor glycol fragment, producing derivative [Ni^II(3,6-Cat^gly)(bipy)]∙CH₂Cl₂ (2), in order to influence the energy of LL’CT transition. A substantial longwave shift of the absorption peak was observed in the UV-Vis-NIR spectra of 2 compared with those in 1. In addition, the studied Ni^II derivatives demonstrated a pronounced negative solvatochromism, which was established using a broad set of solvents. The molecular geometry of both compounds can be ascribed as an insignificantly distorted square-planar type, and the π–π intermolecular stacking of the neighboring α-diimines is realized in a crystal packing. There is a lamellar crystal structure for complex 1, whereas the perpendicular T-motifs with the inter-stacks attractive π–π interactions form the packing of complex 2. The redox-active nature of ligand systems was clearly shown through the electrochemical study: a quasi-reversible one-electron reduction of 2,2′-bipyridine and two reversible successive one-electron oxidative conversations (“catecholate dianion—o-benzosemiquinonato radical anion—neutral o-benzoquinone”) were detected.

A series of new charge transfer (CT) chromophores of “α-diimine-M^II-catecholate” type (where M is 3d-row transition metals—Cu, Ni, Co) were derived from 4,4′-di-tert-butyl-2,2′-bipyridyl and 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) in accordance with three modified synthetic approaches, which provide high yields of products. A square-planar molecular structure is inherent for monomeric [Cu^II(3,6-Cat)(bipy^tBu)]∙THF (1) and Ni^II(3,6-Cat)(bipy^tBu) (2) chromophores, while dimeric complex [Co^II(3,6-Cat)(bipy^tBu)]₂∙toluene (3) units two substantially distorted heteroleptic D-M^II-A (where D, M, A are donor, metal and acceptor, respectively) parts through a donation of oxygen atoms from catecholate dianions. Chromophores 1–3 undergo an effective photoinduced intramolecular charge transfer (λ = 500–715 nm, extinction coefficient up to 10⁴ M⁻¹·cm⁻¹) 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^II-catecholate” CT chromophores on the base of “late” transition elements with differences in d-level’s electronic structure were compared for the first time.

A series of chromophoric complexes Ni^II(3,6-Cat)(Phen) (1), Ni^II(3,6-Cat)(DPQ) (2), and Ni^II(3,6-Cat)(DPPZ) (3) (where 3,6-Cat is 3,6-di-tert-butylcatecholate dianion) has been synthesized using 1,10-phenanthroline (Phen), dipyrido[3,2-d:2',3'-f]quinoxaline (DPQ), and dipyrido[3,2-a:2',3'-c]phenazine (DPPZ). Chromophores 1–3 have a slightly distorted planar structure of the coordination environment and undergo photoinduced ligand-to-ligand intramolecular charge transfer (HOMO_donor → LUMO_acсeptor), thus demonstrating strong light absorption in visible and near-IR regions. Complexes 1–3 are characterized by high thermostability and complete transition to the vapor phase under reduced pressure conditions. Compound 1 has high volatility, which makes it a suitable candidate for further testing in the fabrication of optoelectronic devices by “evaporation–deposition” technology.