Strongly luminescent iridium(III) complexes, [Ir(C,N)2 (S,S)]+ (1) and (O,O)] (2), containing C,N (phenylquinoline), O,O (diketonate), or S,S (dithione) chelating ligands, have been characterized by X-ray crystallography DFT calculations. Their long phosphorescence lifetimes in living cancer cells give rise to high quantum yields for the generation of 1 O2 , with large 2-photon absorption cross-sections. 2 is nontoxic cells, but potently cytotoxic upon brief irradiation low doses visible...

Cyclopropylamines, inhibitors of monoamine oxidases ( MAO ) and lysine‐specific demethylase LSD 1), provide a useful structural scaffold for the design mechanism‐based treatment depression cancer. For new compounds with less common cis relationship an alkoxy substituent at 2‐position cyclopropyl ring, apparent affinity determined from docking experiments revealed little difference between enantiomers. Using racemate, kinetic parameters reversible irreversible inhibition were determined. No 1...

Control of self-sorting regimes is achieved through adjustment steric interactions in self-assembled coordination cages. The self-assembly regime dynamic mixtures heteroleptic cages followed by HPLC to show that statistical or biased distributions can be selectively obtained, including isolation a single species.

A library of 26 electron donor-acceptor organophotocatalysts based on the benzo[ c ][1,2,5]thiadiazole (BTZ) group has been developed. These visible light were then used in a Minisci-type alkylation heteroarenes under both batch and continuous flow conditions.

A series of novel lanthanum amido complexes, supported by ligands designed around the salan framework (salan = N,N′-bis(o-hydroxy, m-di-tert-butylbenzyl)-1,2-diaminoethane) were synthesized and fully characterized in solid solution states. The incorporate benzyl or 2-pyridyl substituents at each tertiary amine center. complexes investigated as catalysts ring-opening homopolymerization lactide (LA) ε-caprolactone (ε-CL) copolymerization equimolar amounts LA ε-CL ambient temperature. Solvent...

The deprotonation of O6 within the S

Using BS-DFT (broken-symmetry density functional theory), the electronic and magnetic properties of S

In continuing to examine the interaction of actinide-ligand bonds with soft donor ligands, a comparative investigation phosphorus and arsenic was conducted. A reaction (C5Me5)2AnMe2, An = Th, U, 2 equiv H2AsMes, Mes 2,4,6-Me3C6H2, forms primary bis(arsenido) complexes, (C5Me5)2An[As(H)Mes]2. Both exhibit thermal instability at room temperature, leading elimination H2, formation diarsenido species, (C5Me5)2An(η2-As2Mes2). The analogous diphosphido (C5Me5)2An(η2-P2Mes2), could not be...

Abstract Strongly luminescent iridium(III) complexes, [Ir(C,N) 2 ( S , )] + 1 ) and (O,O)] ), containing C,N (phenylquinoline), O,O (diketonate), or S,S (dithione) chelating ligands, have been characterized by X‐ray crystallography DFT calculations. Their long phosphorescence lifetimes in living cancer cells give rise to high quantum yields for the generation of O with large 2‐photon absorption cross‐sections. is nontoxic cells, but potently cytotoxic upon brief irradiation low doses visible...

A regioselective one-pot, three-step phenylation strategy has been applied to 4,7-diarylbenzo[ c ][1,2,5]thiadiazoles restrict internal bond rotation and alter the molecules' fluorescence properties.

We compare the stabilities and bonding nature of [Eu/Am(BTPhen)2(NO3)]2+ complexes to those previously reported for [Eu/Am(BTP)3]3+, investigate whether more accurately reflecting reaction conditions separation process by considering [Eu/Am(NO3)3(H2O)x] (x = 3, 4) instead aquo increases selectivity ligands BTP BTPhen Am over Eu. The geometric electronic structures have been evaluated using density functional theory (DFT) used as basis analysis electron through application quantum atoms in...

Considering the broad scope covered by field of neuroscience, this study compares neuroscience undergraduate degree programmes across United Kingdom, with a focus on distribution core and optional neuroscience-specific modules. Data from 13 universities were analysed; revealed significant variation in proportion NS module credits acquired graduation, ranging 28% to 100% institutions. The findings highlight particularly low content Year 1, potentially affecting informed choice subsequent...

Abstract We present herein the first comprehensive study of one‐ and two‐photon absorption Fe(CO) 5 utilising a hierarchy linear‐ quadratic‐response coupled cluster (LR‐ QR‐CC) methodologies to provide an in‐depth characterisation, as well potential energy curves for axial equatorial bond dissociations, highlighting state crossings leading from bright 1A 2 ′′ through dissociative 1E′ state. have characterised range metal‐to‐ligand charge transfer (MLCT) ligand field (LF) states that are in...

In this investigation, we considered both the scalar and 3-D vector-based measures of bonding using next generation quantum theory atoms in molecules (QTAIM), constructed from preferred direction electronic charge density accumulation, to better understand photochemical reaction associated with formation benzvalene benzene. The benzene resulted two additional C-C bonds forming compared creation was explained terms an increasing favorability process by maximizing density. topological...

Suitability of single-reference density functional theory (DFT) methods for the calculation redox potentials copper-containing macrocycle complexes was confirmed by use T1 diagnostics along with a verification negligible spin contamination or wave function instability. When examining effect improvement in cc-pVnZ basis set series on calculated potentials, results readily converged at cc-pVTZ level. The all-electron Def2-TZVPP is shown to be suitable choice when utilizing geometry....

Given the prevalence of fluorescence spectroscopy in biological systems, and pterin derivatives throughout presented here is an assessment two-photon absorption as it applies to a range most commonly studied derivatives. QR-CAMB3LYP//ccpVTZ calculations suggest that use spectroscopic methods would enable more capable differentiation between closely related comparison one-photon spectra, which show minimal qualitative deviation. Study short tail shows that, cases, accessible states solely...

[MFe3S4] cubanes have for some time been of interest their ability to mimic the electronic and geometric structure active site nitrogenase, enzyme responsible fixing N2 NH3. Nitrogenase naturally occurs in three forms, with major difference being that metal ion present cofactor is either molybdenum (FeMoco), vanadium (FeVco), or iron. The versions these cofactors are more closely studied, owing larger abundance rate catalysis. In this study, we compare free energy profiles properties Mo/V at...

Selective tailoring of the pore in expanded porphyrinoids is presented as a novel approach for separation lanthanide ions.

Pierre-François Loos opened the discussion of paper by Katarzyna Pernal: At very end your paper, you say "One should note, however, that there are several outliers for which CASΠDFT errors exceed 0.5 eV. Some them could be explained possible inaccuracy chosen

In this work, the dithiolene complex iron(III) bis-maleonitriledithiolene [Fe(mnt)

Time dependent density functional theory (TDDFT) calculations have been performed on a series of symmetry-preserving excited states the uranyl dication, UO22+. The simulated state electronic structures are compared to that ground at both and state-optimised geometries. For first time, Quantum Theory Atoms in Molecules (QTAIM) has applied order quantify variation bond covalency upon excitation. QTAIM analysis vertical excitations geometry demonstrated an inverse relationship between orbital...

Time-resolved photoelectron imaging and supporting ab initio quantum chemistry calculations were used to investigate non-adiabatic excess energy redistribution dynamics operating in the saturated thioethers diethylsulfide, tetrahydrothiophene thietane. In all cases, 200 nm excitation leads molecular fragmentation on an ultrafast (<100 fs) timescale, driven by evolution of Rydberg-to-valence orbital character along S-C stretching coordinate. The C-S-C bending angle was also found be a key...

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Nitrogenase is the enzyme primarily responsible for reducing atmospheric nitrogen to ammonia. There are three general forms of nitrogenase based on metal ion present in cofactor binding site, namely, molybdenum-dependent nitrogenases with iron–molybdenum (FeMoco), vanadium-dependent FeVco, and iron-only nitrogenases. It has been shown that tend have a lesser efficacy dinitrogen but higher carbon monoxide. In biomimetic chemistry, [MFe3S4] (M = Mo/V) cubanes synthesized, studied, be promising...