HOMO–LUMO energy gap control in platinum(ii) biphenyl complexes containing 2,2′-bipyridine ligands

A series of platinum(II) biphenyl 2,2’-bipyridine complexes containing electron-donating and electron-withdrawing moieties on the 4 and 4’ positions of the bipyridine ligand exhibit emission from excited states in the 600 nm region of the spectrum upon excitation in the metal-to-ligand charge transfer transition located near 450 nm. These complexes are distorted from planarity based on both single crystal structure determinations and density functional theory (DFT) calculations of isolated molecules in acetonitrile. The DFT also reveals the geometry of the lowest-lying triplet state (LLTS) of each complex that is important for emission behavior. The LLTS are assigned based on the electron spin density distributions and correlated with the singlet excited states to understand the mechanism of electronic excitation and relaxation. Timedependent DFT calculations are performed to compute the singlet excited state energies of these complexes so as to help interpret their UV-Vis absorption spectra. Computational and experimental results, including absorption and emission energy maxima, electrochemical reduction potentials, LLTS, singlet excited states, and LUMO and HOMO energies, exhibit linear correlations with the Hammett constants for para-substituents σp. These correlations are employed to screen complexes that have not yet been synthesized. The correlation analysis indicates that electronic structure and the HOMO-LUMO energy gap in Pt(II) complexes can be effectively controlled using electron-donating and electron-withdrawing moieties covalently bonded to the ligands. The information presented in this paper provides analysis and better understanding of the fundamental electronic and thermodynamic behavior of these complexes and could be used to design systems with specific applications

(2,2′-Bipyrazine-κ2N1,N1′)[1,2-bis(diphenylphosphanyl)methane-κP]tricarbonylrhenium(I) trifluoromethanesulfonate monohydrate

The title compound, [Re(C8H6N4)(C25H22P2)(CO)3]CF3SO3·H2O, crystallizes with one [Re(C8N4H6){P(Ph)2CH2P(Ph)2}(CO)3]+ cation, where Ph is a phenyl group, one CF3SO3− anion and one water molecule of hydration. The three C atoms of the facial oriented carbonyl groups, two N atoms from the bipyrazine ligand and one P atom from the (bis)diphenylphosphanylmethane ligand define a distorted octahedral coordination environment about the central ReI atom. The Re—Ccarbonyl bond length trans to the P atom is longer than the the two Re—Ccarbonyl bond lengths in the plane with the bipyrazine ligand. Hydrogen-bonding interactions between the solvent water molecule and the cation, as well as weak C—H...O interactions, consolidate a three-dimensional network structure

Acid monolayer functionalized iron oxide nanoparticles as catalysts for carbohydrate hydrolysis

Superparamagnetic iron oxide nanoparticles were functionalized with a quasi-monolayer of 11-sulfoundecanoic acid and 10-phosphono-1-decanesulfonic acid ligands to create separable solid acid catalysts. The ligands are bound through carboxylate or phosphonate bonds to the magnetite core. The ligand-core bonding surface is separated by a hydrocarbon linker from an outer surface with exposed sulfonic acid groups. The more tightly packed monolayer of the phosphonate ligand corresponded to a higher sulfonic acid loading by weight, a reduced agglomeration of particles, a greater tendency to remain suspended in solution in the presence of an external magnetic field, and a higher catalytic activity per sulfonic acid group. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), and dynamic light scattering (DLS). In sucrose catalysis reactions, the phosphonic–sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic–sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. The activity of the acid-functionalized nanoparticles was compared to the traditional solid acid catalyst Amberlyst-15 for the hydrolysis of starch in aqueous solution. Catalytic activity for starch hydrolysis was in the order PSNPs > CSNPs > Amberlyst-15. Monolayer acid functionalization of iron oxides presents a novel strategy for the development of recyclable solid acid catalysts