Peculiar Differences between Two Copper Complexes Containing Similar Redox-Active Ligands: Density Functional and Multiconfigurational Calculations.

Transition metal complexes featuring redox-active ligands often exhibit multiple redox states, influenced by the interplay between the metal center and the ligand. This study delves into the electronic structures of two mononuclear complexes of copper with two similar redox-active urea azine ligands. The ligands differ by the replacement of an NCH3 moiety by an S atom in the ligand backbone. Experimental analysis yields pronounced electronic structural disparities between these complexes, observable in both the solution and solid phases. Conventional quantum chemical methods, such as density functional theory using different functionals (B3LYP, TPSSh, and CAM-B3LYP), remain inadequate to rationalize the observed spectroscopic anomalies. However, a multiconfigurational approach elucidates the disparate behaviors of these complexes. Multireference perturbation theory, based on complete active space self-consistent field computations, identifies Cu(I) in the case of the complex with the NCH3 containing ligands and a state with substantial Cu(II) contributions in the case of the complex with the S atom containing ligands. In contrast, DFT indicates Cu(I) in both scenarios.

Interplay and Competition Between Two Different Types of Redox-Active Ligands in Cobalt Complexes: How to Allocate the Electrons?

The field of molecular transition metal complexes with redox-active ligands is dominated by compounds with one or two units of the same redox-active ligand; complexes in which different redox-active ligands are bound to the same metal are uncommon. This work reports the first molecular coordination compounds in which redox-active bisguanidine or urea azine (biguanidine) ligands as well as oxolene ligands are bound to the same cobalt atom. The combination of two different redox-active ligands leads to mono- as well as unprecedented dinuclear cobalt complexes, being multiple (four or six) center redox systems with intriguing electronic structures, all exhibiting radical ligands. By changing the redox potential of the ligands through derivatisation, the electronic structure of the complexes could be altered in a rational way.

A Copper(I) Complex with Two Unpaired Electrons, Synthesised by Oxidation of a Copper(II) Complex with Two Redox-Active Ligands.

Two homoleptic copper(II) complexes [Cu(L1)2 ] and [Cu(L2)2 ] with anionic redox-active ligands were synthesised, one with urea azine (L1) and the other with thio-urea azine (L2) ligands. One-electron oxidation of the complexes initiates an unprecedented redox-induced electron transfer process, leading to monocationic copper(I) complexes [Cu(L1)2 ]+ and [Cu(L2)2 ]+ with two oxidised ligands. While [Cu(L1)2 ]+ is best described as a CuI complex with two neutral radical ligands that couple antiferromagnetically, [Cu(L2)2 ]+ is a CuI complex with two clearly different ligand units in the solid state and with a magnetic susceptibility close to a diamagnetic compound. Further one-electron oxidation of the complex with L1 ligands results in a dication [Cu(L1)2 ]2+ , best described as a CuI complex with a twofold oxidised, monocationic ligand and a neutral radical ligand. The stability in at least three redox states, the accumulation of spin density at the ligands and the facile ligand-metal electron transfer make these complexes highly attractive for a variety of applications; here the catalytic aerobic oxidation of alcohols to aldehydes is tested.

Hetero Diels-Alder Reactions with a Dicationic Urea Azine Derived Azo Dienophile and Their Use for the Synthesis of an Electron-Rich Pentacene.

Herein, the first hetero Diels-Alder (DA) reactions with a stable, dicationic urea azine derived azo dienophile, synthesized by two-electron oxidation of a neutral urea azine are reported. Several charged DA products were synthesized in good yield and fully characterized. The DA adduct of anthracene is in thermal equilibrium with the reactants at room temperature, and the reaction enthalpy and entropy were determined from the temperature-dependent equilibrium constant. Furthermore, base addition to solutions of the pentacene DA product led to deprotonation, cleavage of the N-N bond, and formation of an electron-rich 6,13-bisguanidinyl-substituted pentacene. The redox and optical properties of this new pentacene derivative were studied. Furthermore, the dication resulting from its two-electron oxidation was synthesized and fully characterized. The results disclose a new elegant route to electron-rich pentacene derivatives.

Tuneable Redox Chemistry and Electrochromism of Persistent Symmetric and Asymmetric Azine Radical Cations.

Molecular organic radicals have been intensively studied in the last decades, due to their interesting optical, magnetic and redox properties. Here we report the synthesis and characterisation of persistent organic radicals from one-electron oxidation of redox-active azines (RAAs), composed of two guanidinyl or related groups. By connecting two different groups together, asymmetric compounds result. In this way a series of compounds with varying redox potential is obtained that could be oxidised reversibly to the mono- and the dicationic charge states. The accessible redox states were fully determined by chemical redox reactions. The standard Gibbs free energy change for disproportionation of the radical monocation into the dication and the neutral molecule in solution, estimated from cyclovoltammetric measurements, varies between 43 and 71 kJ mol-1 . While the neutral RAAs absorb predominately UV light, the radical monocations display strong absorptions covering almost the entire visible region and extending for some compounds into the NIR region. A detailed analysis of this highly reversible electrochromism is presented, and the fast switching characteristics are demonstrated in an electrochromic test device.