Bidimensional Polyiodide Netting Stabilized by a Cu(II) Macrocyclic Complex

Iodine-dense polyiodide phases are interesting materials for a number of potential uses, including batteries and solid-state conductors. The incorporation of transition metal cations is considered a promising way to enhance the stability, tune the properties, and influence the architecture of polyiodides. However, several interesting metals, including Cu(II), may suffer redox processes, which generally make them not compatible with the I2/I− redox couple. Herein L, a simple derivative of cyclen, is proposed as a Cu(II) ligand capable of protecting the +2 oxidation state of the metal even in the presence of polyiodides. With a step by step approach, we report the crystal structure of free L; then we present spectrophotometric verification of Cu(II) complex stability, stoichiometry, and formation kinetic in DMF solution, together with Cu(II) binding mode elucidation via XRD analysis of [Cu(L)Cl]ClO4∙CH3CN crystals; afterwards, the stability of the CuL complex in the presence of I− is demonstrated in DMF solution, where the formation of a Cu:L:I− ternary complex, rather than reduction to Cu(I), is observed; lastly, polyiodide crystals are prepared, affording the [Cu(L)I]2I3I5 crystal structure. This layered structure is highly peculiar due to its chiral arrangement, opening further perspective for the crystal engineering of polyiodide phases.

Copper macrocyclic complex with trans-di[benzo]-porphyrazine and two oxo ligands: DFT quantum-chemical design

Based on the results of a quantum chemical calculation using the DFT method in the OPBE/TZVP and B3PW91/TZVP, the possibility of the existence of a copper heteroligand complex with trans-di[benzo]derivative of 3,7,11,15-tetraazaporphine (trans-di[benzo]porphyrazine) and two oxygen (O[Formula: see text] ions that is still unknown for this element was shown. In addition, the data on the structural parameters, the multiplicity of the ground state, NBO analysis and standard thermodynamic parameters of formation (standard enthalpy [Formula: see text], entropy [Formula: see text] and Gibbs’s energy [Formula: see text] for this complex are presented.

Электрохимический контроль электронной проводимости тонких пленок металлоорганических полимеров

The dependence of the conductivity in thin films of polymer complexes of nickel with N4 ligands with macrocyclic and chelate structure on the doping level has been studied by the electrochemical in-situ conductance method. The electrochemical conductivity window of polymers depends on the structure of the monomers and approached 1.2 V for the macrocyclic complex. Electrochemical doping changes the electrical resistance of the investigated materials by 4 orders of magnitude

A square-shaped complex with an electron-acceptor ligand: unique cubic crystal symmetry and similarity to inorganic mineral katoite

Square macrocyclic complexes have attracted significant attention due to their unique structure and molecular recognition property. Here we report a square macrocyclic complex using an electron-acceptor ligand N,N’-di(4-pyridyl)-1,4,5,8-naphthalenediimide (dpndi), [Pt(en)(dpndi)]4(SO4)4·20H2O...

Electrocatalytic oxidation of water using self-assembled copper(ii) tetraaza macrocyclic complexes on a 4-(pyridine-4′-amido)benzene grafted gold electrode

Gold surface anchored copper(ii)tetraaza macrocyclic complex showed an excellent electrocatalytic activity towards water oxidation with an overpotential of 284 mV at a current density of 1.31 mA cm−2 and a Tafel slope of 48 mV decade−1 in neutral pH.