A novel non-centrosymmetric π-expanded diketopyrrolopyrrole was designed and synthesized. Strategic placement of tert-butyl groups at the periphery of a diketopyrrolopyrrole allowed us to selectively fuse one moiety via tandem Friedel–Crafts-dehydration reactions, resulting in a non-centrosymmetric dye. The structure of the dye was confirmed by X-ray crystallography, revealing that it contains a ...

The experimental UV and CV of five substituted 2-hydroxybenzophenones in solvents acetonitrile, n-dimethylformamide and dimethylsulfoxide are presented. Results obtained were used to determine their experimental highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) and the results were compared to their theoretical model. The derivatives with an electron withdrawing ...

When 2-bromo-2-cyclopentenone is treated with various carbon nucleophiles containing active methylenes, it undergoes a conjugate addition initiated-ring closure (CAIRC) reaction. This leads to the formation of carboand heterocyclic compounds in a regioselective fashion with good to high yield. Several bases and phase transfer catalysts were investigated. CsF-Si(OEt)4 as base together with ...

The electronic circular dichroism (ECD) properties of the green fluorescent protein and other fluorescent proteins have been calculated with density functional theory. The influence of different embedding models on the ECD signal of the chromophore has been investigated by modeling the protein environment by the polarizable continuum model (QM/PCM), by the polarizable embedding model (PE-QM/MM), by ...

The insertion of carbon dioxide into metal element σ-bonds is an important elementary step in many catalytic reactions for carbon dioxide valorization. Here, the insertion of carbon dioxide into a family of group 10 alkyl complexes of the type (^RPBP)M(CH₃) (^RPBP = B(NCH₂PR₂)₂C₆H₄⁻; R = Cy or ^tBu; ...

QM/MM calculations of electronic excitations with diffuse basis sets often have large errors due to spill-out of electrons from the quantum subsystem. The Pauli repulsion of the electrons by the environment has to be included to avoid this. We propose transferable atomic all-electron pseudopotentials that can readily be combined with most MM force fields to avoid electron spill-out. QM/MM excitation ...

We discuss the characteristic factors that determine the electrochemical potentials in a metal-organic framework used as cathode for Li-ion batteries via density functional theory-based simulations. Our focus is on MIL-101(Fe) cathode material. Our study gives insight into the role of local atomic environment and structural deformations in generating electrochemical potential.

CONSPECTUS: Porphyrin chemistry is Shakespearean: over a century of study has not withered the field’s apparently infinite variety. Heme proteins continually astonish us with novel molecular mechanisms, while new porphyrin analogues bowl us over with unprecedented optical, electronic, and metal-binding properties. Within the latter domain, corroles occupy a special place, exhibiting a unique ...

The simulation of X-ray absorption spectra requires both scalar and spin–orbit (SO) relativistic effects to be taken into account, particularly near L- and M-edges where the SO splitting of core p and d orbitals dominates. Four-component Dirac–Coulomb Hamiltonian-based linear damped response time-dependent density functional theory (4c-DR-TDDFT) calculates spectra directly for a selected frequency ...

We present a benchmark study of density functional approximation (DFA) performances in predicting the two-photon-absorption strengths in π-conjugated molecules containing electron-donating/-accepting moieties. A set of 48 organic molecules is chosen for this purpose, for which the two-photon-absorption (2PA) parameters are evaluated using different DFAs, including BLYP, PBE, B3LYP, PBE0, CAM-B3LYP, ...