Exceptionally stable, hollow tubular metal-organic architectures: synthesis, characterization, and solid-state transformation study

An effective solvothermal procedure has been developed to synthesize the new three-dimensional metal-organic framework, [ZnF(AmTAZ)].solvents, using either 3-amino-1,2,4-triazole (AmTAZ) or 3-amino-1,2,4-triazole-5-carboxylic acid (AmTAZAc) and a choice of several Zn(II) salts as starting materials. The three-dimensional structure displays open-ended, hollow nanotubular channels that are formed by hexanuclear metallamacrocyclic Zn(6)F(6)(AmTAZ)(6) rings. The framework integrity is maintained to 350 degrees C, at which point most of the guest solvent molecules have been removed, as evidenced by single-crystal X-ray analyses, (1)H solid-state NMR, and TGA measurements. At higher temperatures, the framework is converted either to zinc oxide (ZnO) when heated in air or to zinc cyanamide (ZnCN(2)) when heated in an inert atmosphere. In both cases, the as-grown, rodlike crystal shape is maintained during the solid-state transformation, suggesting a possible route for preparing one-dimensional crystalline nanomaterials.     

Polyformylation of copper(II) porphyrins

Vilsmeier formylation of copper(II) octaethylporphyrin (1) is shown to yield the copper(II) complexes of meso-monoformyloctaethylporphyrin, meso-α,β- and meso-α,γ-diformyloctaethylporphyrins, meso-α,β,γ-triformyloctaethylporphyrin, and meso-α,β,γ,δ-tetraformyloctaethylporphyrin. There is therefore no difference in regioselectivity of meso-diformylation between the octaethylporphyrin and etioporphyrin-I series.     

Synthesis of 1-acyloxyindolizines. Correction of a structure misassignment

The assignment by Lown of a 3-acyloxyindolizine structure to the product of the reaction of diphenylcyclopropenone and pyridine is shown to be in error. Both 1- and 3-acyloxyindolizines were prepared and their structures established by X-ray analysis.     

The preparation and crystal structure of bis(bis(diphenyl-phosphino)ethane)carbonylformylosmium(II) hexafluoroantimonatedichloromethane (1/1)

Reaction of trans[Os(CO)₂(dppe)₂]²⁺ with [KHB(OPrⁱ)₃] gives the formyl complex trans[Os(CHO)(CO)(dppe)₂][SbF₆] which is thermally very stable; the crystal structure shows it to have trans stereochemistry and a long Os-C bond.     

Nitrogen-15 NMR studies of 1,4-benzodiazepines: 2—The triazolobenzodiazepines

Nitrogen-15 NMR data for a series of 21 triazolobenzodiazepines are presented, including ¹⁵N chemical shifts and substituent effects. The line assignments made by correlation to other model compounds were confirmed by a shift reagent and protonation study. A Yb(dpm)₃ study on alprazolam showed that the molar shifts of the four nitrogens ranged from 35 to 150 ppm.