Use of Unprecedented Intramolecular 1, 3-Dipolar Cycloaddition Reaction in meso-Nitrile Oxide-Containing BODIPYs as a New Pathway for the Preparation of Fused NIR Platforms.

Meso-nitrile oxide group in 1,7-Diphenyl-containing BODIPYs can be involved in highly unusual [3+2] intramolecular cycloaddition reaction with the formation of the dihydrobenzo[d]isoxazole-containing BODIPYs. Oxidation of these compounds results in the formation of unprecedented either benzisoxazole- or benzo[b]azepine-fused fully conjugated NIR absorbing BODIPYs. The photophysical properties and electronic structures of the target compounds were studied by an array of experimental and theoretical methods.

Ternary alkali ion thiogallates, AGaS (A = Li and Na), with isolated tetrahedral building units and their ionic conductivities.

Two new ternary thiogallates in the A5GaS4 (A = Li (i) and Na (ii)) series have been synthesized for the first time employing a gas passing route using oxide precursors and a high temperature solid state route using stoichiometric combinations of elements, respectively. Li5GaS4 crystallizes in the P21/m space group and the structure is built up of layers of corner sharing tetrahedra of LiS4 and GaS4 stacked along the a-axis and the octahedrally coordinated Li ions residing in the interlayer space. Na5GaS4 crystallizes in the Pbca space group and the structure consists of isolated (GaS4)5- tetrahedra held together by charge balancing sodium ions in distorted tetrahedral and octahedral coordination geometries.

Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered.

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X-azulene ligands (X = H, Me, COEt, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)Cr(2-isocyano-1,3-X-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime "workhorse" aryl isocyanide ligand in coordination chemistry.

Nanomedicine-Assisted Combination Therapy of NSCLC: New Platinum-Based Anticancer Drug Synergizes the Therapeutic Efficacy of Ganetespib.

K-RAS is the most common mutated oncogene associated with Non-Small-Cell Lung Cancer (NSCLC). So far, there are no promising chemotherapies for the direct inhibition of K-RAS, and considered to be undruggable. In this work, we have introduced a new platinum-based cyanoximate complex, Pt(MCO) as an anti-cancer drug to enhance the therapeutic efficacy of Hsp90 inhibitor drug, ganetespib for the combination therapy of NSCLC.

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state.

Several complexes of "PtL" composition containing two cyanoxime anions - 2-oximino-2-cyano-N-piperidineacetamide (PiPCO) and 2-oximino-2-cyano-N-morpholylacetamide (MCO) - have been obtained and characterized both in solution and in the solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes and dark-green [PtL] 1D polymers, while for the MCO anion a red, solvent containing dimeric [Pt(MCO)·DMSO] complex has also been isolated. The interconversion of polymorphs was investigated.

Design and synthesis of C2-symmetric N-heterocyclic carbene precursors and metal carbenoids.

Chiral, C(2)-symmetric imidazolium and imidazolinium ions, as well as the corresponding copper- or silver-bound carbenoids, have been prepared. Structural study of these compounds by X-ray crystallography reveals a chiral pocket that surrounds the putative carbene site or the metal-carbene bond, at carbon 2, in three of the four ligands prepared. Preliminary investigation into the application of these complexes has shown one of them to be highly enantioselective in the hydrosilylation of acetophenone.

Unexpected fluorescence properties in an axially sigma-bonded ferrocenyl-containing porphyrin.

Molecular structure, redox, and unexpected fluorescence properties of a tetraphenylporphyrin tin(iv) complex axially sigma-bonded with two ferrocene substituents were investigated using UV-vis, MCD, electro- and spectroelectrochemical methods as well as DFT calculations and X-ray crystallography.

Reversible Cu(4) <--> Cu(6) core interconversion and temperature induced single-crystal-to-single-crystal phase transition for copper(I) carboxylate.

The first example of a reversible [Cu(4)] <--> [Cu(6)] interconversion for polynuclear copper(I) complexes under controlled experimental settings is reported. It illustrates the key role of specific crystal growth conditions for accessing the target cluster nuclearity that consequently determines physical properties of the resulting solid state products. Thus, when copper(I) benzoate crystallizes from a 1,2-dichlorobenzene solution at room temperature, it forms [Cu(4)]-core based crystalline material, [Cu(4)(O(2)CC(6)H(5))(4)] (1).

Synthesis and Characterization of Dimeric Mutually Coordinated Magnesium meso-2-Pyridylporphyrins.

The synthesis and characterization of a series of meso-2-pyridylporphyrins and their Mg(2+) complexes are reported. Condensation of 4-alkylbenzyl-2,2'-dipyrromethanes (alkyl = Me, n-Pr, or n-Bu) with 2-pyridinecarboxaldehyde yielded a series of free-base meso-2-pyridylporphyrins. Insertion of Mg(2+) into the free-base porphyrins yielded the respective magnesium complexes.