Tuning PtII-Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals,Redox Potentials,UV/Vis/NIR Absorptions,Electrochromism, and Photocatalysis

Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q²⁻)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q²⁻=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q²⁻)] with Q²⁻=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.     

trans‐Selective Insertional Dihydroboration of a cis‐Diborene: Synthesis of Linear sp3‐sp2‐sp3‐Triboranes and Subsequent Cationization

The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐trans‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis‐1,2‐μ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B₃H₄⁺ analogues.     

OVID and SUPER: Two overlap programs for drug design

Summary Two programs, OVID and SUPER, for exploring the similarity of molecules with respect to their action at a receptor are described. OVID accepts two molecules as input and optimizes the three-dimensional overlap of specified atoms in one molecule with specified atoms in the second molecule. The result is expressed as a percent of the theoretical maximum. OVID gives a quantitative measure of the extent of a guessed correspondence between two molecules based on volume overlap of selected atoms. The Achilles' heel of OVID is that the correspondence between the two molecules has to be guessed. We realized that it would be better to systematically examine all possible correspondences of two structures to minimize the chance of overlooking a superior correspondence. We created SUPER to satisfy this need. SUPER accepts two molecules as input and finds the top twenty correspondences of their surfaces and charge distributions, giving a quantitative measure of the extent of each correspondence. An instructive example of the application of OVID and SUPER to the design of leukotriene D₄ receptor antagonists is described. SUPER appears to be a practical brainstorming tool for the medicinal chemist trying to understand how molecules whose structures may not resemble one another in an obvious way can bind to the same site.     

Orbital Polarization and Magnetization for Independent Particles in Disordered Media

Formulas for the contribution of the conduction electrons to the polarization and magnetization are derived for disordered systems and within a one-particle framework. These results generalize known formulas for Bloch electrons and the presented proofs considerably simplify and strengthen prior justifications. The new formulas show that orbital polarization and magnetization are of geometric nature. This leads to quantization for a periodically driven Piezo effect as well as the derivative of the magnetization w.r.t. the chemical potential. It is also shown how the latter is connected to boundary currents in Chern insulators. The main technical tools in the proofs are an adaption of Nenciu’s super-adiabatic theory to C*-dynamical systems and Bellissard’s Ito derivatives w.r.t. the magnetic field.     

The maximal ideal space of with respect to the Hadamard product

It is shown that the space of all regular maximal ideals in the Banach algebra with respect to the Hadamard product is isomorphic to The multiplicative functionals are exactly the evaluations at the -th Taylor coefficient. It is a consequence that for a given function in and for a function holomorphic in a neighborhood of with and for all the function is in