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Full-Text Articles in Physical Sciences and Mathematics
Data From: Structure And Bonding In [Sb@In8sb12]3− And [Sb@In8sb12]5−, Alexander I. Boldyrev, Nikolay Tkachenko
Data From: Structure And Bonding In [Sb@In8sb12]3− And [Sb@In8sb12]5−, Alexander I. Boldyrev, Nikolay Tkachenko
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We report the characterization of the compound [K([2.2.2]crypt)]4[In8Sb13], which proves to contain a 1:1 mixture of [Sb@In8Sb12]3− and [Sb@In8Sb12]5−. The tri-anion displays perfect Th symmetry, the first completely inorganic molecule to do so, and contains eight equivalent In3+ centers in a cube. The gas-phase potential energy surface of the penta-anion has eight equivalent minima where the extra pair of electrons is localized on one In+ center, and these minima are linked by low-lying transition states where the electron pair is delocalized over two adjacent centers. The best fit to the electron density is obtained from a model where the structure …
Data From: All-Metal Σ-Antiaromaticity In Dimeric Cluster Anion {[Cuge9mes]2}4−, Alexander I. Boldyrev, Nikolay Tkachenko
Data From: All-Metal Σ-Antiaromaticity In Dimeric Cluster Anion {[Cuge9mes]2}4−, Alexander I. Boldyrev, Nikolay Tkachenko
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In this work, we report a dimeric cluster anion, {[CuGe9Mes]2}4−, which was isolated as the [K(2,2,2-crypt)]+ salt and characterized by using single-crystal X-ray diffraction and ESI mass spectroscopy. The title cluster represents the first locally σ-antiaromatic compound in the solid state, as well as the first heteroatomic antiaromatic compound.
New Ideas From An Old Concept: The Hydrogen Bond, Steve Scheiner
New Ideas From An Old Concept: The Hydrogen Bond, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Ongoing studies of the hydrogen bond (HB), in which a hydrogen (H) atom acts as a bridge between a pair of chemical groups, continues to offer new ideas about this interaction that have applications to biochemical processes. The ability of a proton to transfer within a HB can be controlled by conformational changes that cause small alterations to the HB geometry. The CH group, widely prevalent in biological systems, participates in HBs and contributes to the structure and stability of commonly occurring protein secondary structures such as the β-sheet. The concept of the HB has been extended to systems where …
Electronic Structure And Bonding In Metal Porphyrins, Metal=Fe, Co, Ni, Cu, Zn, M.-S. Liao, Steve Scheiner
Electronic Structure And Bonding In Metal Porphyrins, Metal=Fe, Co, Ni, Cu, Zn, M.-S. Liao, Steve Scheiner
Steve Scheiner
A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP]x ions (x = 2+, 1+, 1−, 2−, 3−, 4−), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as 3A2g, which arises from the configuration (dxy)2(dz …
Electronic Structure And Bonding In Unligated And Ligated Feii Porphyrins, M.-S. Liao, Steve Scheiner
Electronic Structure And Bonding In Unligated And Ligated Feii Porphyrins, M.-S. Liao, Steve Scheiner
Steve Scheiner
The electronic structure and bonding in a series of unligated and ligated FeII porphyrins (FeP) are investigated by density functional theory (DFT). All the unligated four-coordinate iron porphyrins have a 3A2g ground state that arises from the (dxy)2(dz2)2(dπ)2 configuration. The calculations confirm experimental results on Fe tetraphenylporphine but do not support the resonance Raman assignment of Fe octaethylporphine as 3Eg, nor the early assignment of Fe octamethyltetrabenzporphine as 5B2g. For the six-coordinate Fe–P( …
Electronic Structure And Bonding In Metal Porphyrins, Metal=Fe, Co, Ni, Cu, Zn, M.-S. Liao, Steve Scheiner
Electronic Structure And Bonding In Metal Porphyrins, Metal=Fe, Co, Ni, Cu, Zn, M.-S. Liao, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
A systematic theoretical study of the electronic structure and bonding in metal meso-tetraphenyl porphines MTPP, M=Fe, Co, Ni, Cu, Zn has been carried out using a density functional theory method. The calculations provide a clear elucidation of the ground states for the MTPPs and for a series of [MTPP]x ions (x = 2+, 1+, 1−, 2−, 3−, 4−), which aids in understanding a number of observed electronic properties. The calculation supports the experimental assignment of unligated FeTPP as 3A2g, which arises from the configuration (dxy)2(dz …
Electronic Structure And Bonding In Unligated And Ligated Feii Porphyrins, M.-S. Liao, Steve Scheiner
Electronic Structure And Bonding In Unligated And Ligated Feii Porphyrins, M.-S. Liao, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The electronic structure and bonding in a series of unligated and ligated FeII porphyrins (FeP) are investigated by density functional theory (DFT). All the unligated four-coordinate iron porphyrins have a 3A2g ground state that arises from the (dxy)2(dz2)2(dπ)2 configuration. The calculations confirm experimental results on Fe tetraphenylporphine but do not support the resonance Raman assignment of Fe octaethylporphine as 3Eg, nor the early assignment of Fe octamethyltetrabenzporphine as 5B2g. For the six-coordinate Fe–P( …
Electronic Structure And Bonding In Metal Phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg, M.-S. Liao, Steve Scheiner
Electronic Structure And Bonding In Metal Phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg, M.-S. Liao, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Electronic structure and bonding in metal phthalocyanines (Metal=Fe, Co, Ni, Cu, Zn, Mg) is investigated in detail using a density functional method. The metal atoms are strongly bound to the phthalocyanine ring in each case, by as much as 10 eV. The calculated orbital energy levels and relative total energies of these D4h structures indicate that Fe and Co phthalocyanines have 3A2g and 2Eg ground states, respectively, but that these states are changed upon interaction with strong-field axial ligands. The valence electronic structures of Fe and Co phthalocyanines differ significantly from those of …