The use of iron as a replacement for noble metals in photochemical and photophysical applications is challenging due to the typically fast deactivation short-lived catalytically active states. Recent success cyclometalated iron(III) complex utilizing bis-tridentate ligand motif inspired phenyl-1H-pyrazole bidentate ligand. Five complexes using tris(1-phenylpyrazolato-N,C2)iron(III) scaffold are...

In this article, we present a fragment model potential approach for the description of the crystalline environment as an extension of the use of embedding ab initio model potentials (AIMPs). The biggest limitation of the embedding AIMP method is the spherical nature of its model potentials. This poses problems as soon as the method is applied to crystals containing strongly covalently bonded st...

CaZnOS:Mn2+ is a rare-earth-free luminescent compound with an orange broadband emission at 612 nm, featuring pressure sensing capabilities, often explained by defect levels where energy can be stored. Despite recent efforts from experimental and theoretical points of view, the underlying luminescence mechanisms in this phosphor still lack a profound understanding. By the evaluation of thermolum...

The Rieske protein from Thermus thermophilus (TtRp) and a truncated version of the protein (truncTtRp), produced to achieve a low-pH crystallization condition, have been characterized using UV-visible and circular dichroism spectroscopies. TtRp and truncTtRp undergo a change in the UV-visible spectra with increasing pH. The LMCT band at 458 nm shifts to 436 nm and increases in intensity. The in...

To explore the principle of chiral induction in inorganic clusters, chiral organic cations with two stereocenters, R- and S-BPEA, are used to encapsulate a series of polyoxometalates (POMs) bearing different structures and transition absorption bands in aqueous solution, constructing a series of chiral supramolecular complexes. Due to the induction of chiral organic cations, POMs possessing bot...

The electronic spectra and the photochemistry of the uranyl complexes UO2 (salophen) and UO2 (oxinate)2 with H2salophen = N,N'-bis(salicylidene)-o-phenylenediamine and oxine = 8hydroxyquinoline were studied. The excited state behavior of both complexes is determined by a low-energy salophen / oxinateÿ to U(VI) ligand-to-metal charge transfer (LMCT) state which is not luminescent but can be reac...

A family of dinuclear neutral thiolate gold complexes of the type RPh2PAuS(C6H4)nSAuPPh2R (n = 2, 3), RPh2PAuS(C6H4)S(C6H4)SAuPPh2R, RPh2PAuSCH2(C6H4)2CH2SAuPPh2R where R represents a pyridine or a phenylene ring, has been prepared and fully characterized. X-ray crystallographic studies showed the presence of aurophilic interactions for those species bearing two phenylene spacers between the go...

The synthesis of a series of uranyl compounds via oxidation of [Li(THF)4][UX5(THF)] (X = Cl, Br, I) in the presence of Ph3PvO is described. The solid state structures of [Li(OvPPh3)(MeCN)2]2[UO2Cl4], [UO2Br2(OvPPh3)2] and [Li(OvPPh3)4][I3], formed as a by-product from the oxidation of [Li(THF)4][UI5(THF)], is reported. The electronic absorption spectra and photoluminescence spectra of [UO2X2(Ov...

A ligand field calculation of magnetic circular dichroism (MCD) spectra is described that provides new insights into the information contained in electronic spectra of copper sites in metalloenzymes and synthetic analogs. The ligand field model uses metal-centered p- and f-orbitals to model sigma, pi LMCT mixing mechanism for intensity, allowing the basic features of optical absorption, MCD, an...