Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of ...

This review covers the latest developments in the synthesis of cryptophane host molecules since the publication of the last extensive review by Brotin and Dutasta in 2009. The literature has been categorized according to the synthetic method for generating the cryptophane core and we also emphasize emerging late-stage functionalization approaches. The synthetic strategies towards cryptophanes ...

The boracarboxylation reaction has potential for the production of natural products and drug candidates, but the development of an asymmetric version of this transformation is challenging. We report an enantioselective boracarboxylation of styrenes, enabled by a copper catalyst containing chiral phosphines. Our experimental conditions provide yields between 31–76% and enantiomeric ratios from ...

A recent reinvestigation of the gas-phase photoelectron spectra of Group 6 metal−metal quadruple-bonded complexes with scalar-relativistic DFT calculations showed that common exchange-correlation functionals reproduce the lowest ionization potentials in a semiquantitative manner. The finding encouraged us to undertake a DFT study of metal− metal quintuple bonds in a set of bisamidinato complexes ...

We have revisited the gas-phase photoelectron spectra of quadruplebonded dimolybdenum(II,II) and ditungsten(II,II) paddlewheel complexes with modern density functional theory methods and obtained valuable calibration of four well-known exchange−correlation functionals, namely, BP86, OLYP, B3LYP*, and B3LYP. All four functionals were found to perform comparably, with discrepancies between calculated ...

Relativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP = tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP = tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those calculated for analogous silver(II) porphyrins, reflecting much greater relativistic destabilization of ...

The synthesis, identification and electrochemical behaviour iron(III) complexes containing different 2-hydroxybenzophenone ligands are reported. The first reduction of the tris(2-hydroxybenzophenone)iron(III) complexes follow the same trend as that of the free, uncoordinated ligands and bis(2-hydroxybenzophenone)copper(II) complexes. The first reduction of the iron(III) complexes occur at a potential ...

Carbon isotope labelling of bioactive molecules is essential for accessing the pharmacokinetic and pharmacodynamic properties of new drug entities. Aryl carboxylic acids represent an important class of structural motifs ubiquitous in pharmaceutically active molecules and are ideal targets for the installation of a radioactive tag employing isotopically labelled CO₂. However, direct isotope ...

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 ...

We present a composite framework for calculating the rates of non-radiative deactivation processes, namely internal conversion (IC) and intersystem crossing (ISC), on an equal footing by explicitly computing the non-adiabatic coupling (NAC) and spin–orbit coupling (SOC) constants, respectively. The stationary-state approach uses a time-dependent generating function based on Fermi's golden rule. We ...