DFT calculations with the well-tested OLYP and B3LYP* exchange-correlation functionals (along with D3 dispersion corrections and all-electron ZORA STO-TZ2P basis sets) and careful use of group theory have led to significant insights into the question of metal- versus ligand-centered redox in Co and Ni B,C-tetradehydrocorrin complexes. For the cationic complexes, both metals occur in their low-spin ...

A scalar-relativistic DFT study of isoelectronic, quadruple-bonded Group 6 metalloporphyrins (M = Mo, W) and Group 7 metallocorroles (M = Tc, Re) has uncovered dramatic differences in ionization potential (IP) and electron affinity (EA) among the compounds. Thus, both the IPs and EAs of the corrole derivatives are 1 eV or more higher than those of the porphyrin derivatives. These differences ...

We have reported herein the data to understand the nature and number of non-covalent interactions that stabilize the structures of the thiophene clusters. In addition, we have also provided the optimized Cartesian coordinates of all the structures of the investigated thiophene clusters. Initially, the geometries have been generated using the ABCluster code which performs a global optimization to ...

The cyclic voltammograms of a series of substituted terpyridine ligands are presented, showing that reduction occur generally below −2 V versus the redox potential of ferrocene. Density functional theory (DFT) calculated energies and the theoretically calculated reduction potentials of a large series of substituted oligo(aza)pyridine ligands (terpyridine, bipyridine and phenanthroline) are determined ...

Nearly a half-century after Gouterman classified the UV–vis–NIR spectra of porphyrin derivatives as normal, hyper, or hypso, we propose a heretofore unsuspected “mechanism” underlying hypso spectra. Hypsoporphyrins, which exhibit blueshifted optical spectra relative to normal porphyrins (such as Zn porphyrins), typically involve dn transition metal ions, where n > 6. The spectral blueshifts have ...

In the present study, electronic effects on the mechanism of the NAD+ coenzyme reduction in the presence of formate, catalysed by a non-organometallic ruthenium(II) polypyridyl amine complex, were investigated. The [RuII(terpy)(ampy)Cl]Cl (terpy ¼ 2,20 :60 ,200-terpyridine, ampy ¼ 2-(aminomethyl)pyridine) complex was employed as the catalyst. The reactions were studied in a water/ethanol mixture ...

Free-base corroles have long been known to be acidic, readily undergoing deprotonation by mild bases and in polar solvents. The conjugate base, however, has not been structurally characterized until now. Presented here is a first crystal structure of a freebase corrole anion, derived from tris(p-cyanophenyl)corrole, as the tetrabuylammonium salt. The low-temperature (100 K) structure reveals ...

Understanding of clusters of dimethylsulfoxide (DMSO) is important in several applications in Chemistry. Despite its importance, very few studies of DMSO clusters, (DMSO)<i>_n</i> , have been reported in comparison to systems such as water clusters or methanol clusters. In order to provide further understanding of DMSO clusters, we investigated the structures and non-covalent interactions ...

Density functional theory calculations of magnetically induced current densities have revealed high diatropic ring currents in unsubstituted isocorrole consistent with homoaromatic character. An examination of the Kohn-Sham molecular orbitals showed clear evidence of homoconjugative interactions in four occupied π-type molecular orbitals as well as in the LUMO. Remarkably, substituents at the saturated ...

A careful density functional theory reexamination of the geometric and electronic structures of reduced main-group porphyrin complexes E(Por)L2 (E = Si or Ge; L = pyridine or tetrahydrofuran), B2(Por), and C2(Por) has confirmed these as pure isophlorin derivatives with normal-valent coordinated central atoms. Only axially unligated Ge(Por) and the dications [B2(Por)]2+ and [C2(Por)]2+ feature aromatic ...