Structural, Spectroscopic, and Computational Analysis of Halogen- and Hydrogen-Bonding Effects within a Series of Uranyl Fluorides with 4-Halopyridinium.

Reported are the syntheses and characterization of five compounds containing one-dimensional uranyl fluoride chains charge balanced by 4-X-pyridinium (X = H, F, Cl, Br, I) cations. Structural analysis reveals molecular assembly via noncovalent interactions in the second coordination sphere with the X···O interaction distances ranging from 2.987(7) to 3.

Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl-Organic Hybrid Materials.

A series of compounds of the form [HAr] [UO X ] is reported here, wherein Ar is systematically varied between pyridine (1-X), quinoline (2-X), acridine (3-X), 2,5-dimethylpyrazine (4-X), quinoxaline (5-X), and phenazine (6-X), and X=Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr] cations and [UO Cl ] anion in the crystalline state, and of the assembly.

Bandgap modification in 0D tellurium iodide perovskite derivatives incorporation of polyiodide species.

Halide perovskites provide a versatile platform for exploring the effect of non-covalent interactions, including halogen bonding, on material properties such as band gap, luminescence, and frontier orbital landscape. Herein we report six new zero-dimensional tellurium iodide perovskite derivatives, consisting of [TeI] octahedra charge balanced by one of several X-Py cations (X = H, Cl, Br, I, and Py = pyridinium). These compounds also feature robust halogen bonding between [TeI] octahedra and polyiodides in the form of I (1-4), I (5), or adjacent octahedra (4 and 6).

Phenylene as an efficient mediator for intermetallic electronic coupling.

The new compound [(NC)Ru(ap)](μ-1,4-CH) (ap = 2-anilinopyridinate) was prepared to address the open question of whether a 1,4-phenylene bridge can mediate intermetallic electronic coupling. As a manifestation of strong coupling, hole delocalization between the Ru centers on the IR time scale (10 s) was established using spectroelectrochemistry. An orbital mechanism for coupling was elaborated with DFT analysis.

Macrocyclic Chromium(III) Catecholate Complexes.

The synthesis and structural, electrochemical, spectroscopic, and magnetic characterizations of Cr(HMC) catecholate and semiquinonate complexes are reported herein, where HMC is 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. [Cr(HMC)(Cat)] complexes (Cat = catecholate, []; tetrachlorocatecholate, []; and 3,5-di--butylcatecholate, []) were prepared from the reaction between appropriate catechol and [Cr(HMC)Cl]Cl reduced by zinc. Chemical oxidation of [] by FcPF resulted in -[Cr(HMC)(SQ)] ([], SQ = 3,5-di--butylsemiquinonate).

Insight into geometric preferences in uranium(VI) mixed tris(imido) systems.

Uranium tris(imido) species have been synthesized using different imido groups in the axial and equatorial positions by treating [(MesPDIMe)U(THF)]2 (1-THF), which is a uranium(iv) dimer that is supported by MesPDIMe tetraanions, with mixed organoazide solutions. While the origin of the geometric preference isn't clear, both steric and electronic factors are likely at play.

Drastic Tuning of the Electronic Structures of Diruthenium Aryl Complexes by Isoelectronic Axial Ligands.

Reported herein is the use of aryls as axial ligands to manipulate reactivity at the distal metal site through metal-metal-ligand interactions in diruthenium paddlewheel complexes. The vacant ruthenium site in Ru(ap)(Ar) (; ap = 2-anilinopyridinate and Ar = CH-4-NMe), thus rendered reactive, is able to bind a series of isoelectronic ligands to afford three complexes of the form (Y)[Ru(ap)](Ar) [Y = CN (), HC≡C (), CO ()], each of which exhibits a distinct electronic structure. While reactions with anionic ligands subsequently result in oxidation of the diruthenium core from Ru(II,III) to Ru(III,III), the reaction with CO yields a rare example of a Ru(II,III)-CO adduct.

Forging Ru-C Bonds in Paddlewheel Complexes Using the Lithium-Halogen Exchange Reaction.

Reported herein are the first examples of the formation of Ru-C bonds in paddlewheel diruthenium species. A series of six Ru( ap)(CH-4-X) type compounds ( ap = 2-anilinopyridinate; X = NMe (1), N,N-(CH-4-OMe) (2), Bu (3), H (4), Br (5), CF (6)) was synthesized by employing the lithium-halogen exchange reaction with a variety of para-substituted aryl halides. These compounds have been characterized via electronic absorption spectroscopy, cyclic voltammetry, mass spectrometry, and magnetism studies, and their molecular structures have been established by single-crystal X-ray diffraction studies.

Heptamolybdate: a highly active sulfide oxygenation catalyst.

The sulfide oxygenation activities of both heptamolybdate ([Mo7O24]6-, [1]6-) and its peroxo adduct [Mo7O22(O2)2]6- ([2]6-) were examined in this contribution. [Mo7O22(O2)2]6- was prepared in a yield of 65% from (NH4)6[Mo7O24] (1a) upon treatment of 10 equiv. of H2O2 and structurally identified through single crystal X-ray diffraction study.