A metal-organic framework (MOF) for reversible alteration of guest molecule adsorption, here carbon dioxide, upon photochemical or thermal treatment has been discovered. An azobenzene functional group, which can switch its conformation upon light irradiation or heat treatment, has been introduced to the organic linker of a MOF. The resulting MOF adsorbs different amount of CO2 after UV or heat treatment. This remarkable stimuli-responsive adsorption effect has been demonstrated through experiments.

A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

Several N-alkyl and N,N-dialkylaminomethanesulfonic acids were synthesized (as zwitterions and/or sodium salts) to be tested for utility as biological buffers at lower pH levels than existing Good buffer compounds (aminoalkanesulfonates with a minimum of two carbons between amine and sulfonic acid groups as originally described by Norman Good, and in common use as biological buffers). Our hypothesis was that a shorter carbon chain (one carbon) between the amino and sulfonic acid groups should lower the ammonium ion pK(a) values. The alkylaminomethanesulfonate compounds were synthesized in aqueous solution by reaction of primary or secondary amines with formaldehyde/sodium hydrogensulfite addition compound. The pK(a) values of the ammonium ions of this series of compounds (compared to existing Good buffers) was found to correlate well with the length of the carbon chain between the amino and sulfonate moeties, with a significant decrease in amine basicity in the aminomethanesulfonate compounds (pK(a) decrease of 2 units or more compared to existing Good buffers). An exception was found for the 2-hydroxypiperazine series which shows only a small pK(a) decrease, probably due to the site of protonation in this compound (as confirmed by X-ray crystal structure). X-ray crystallographic structures of two members of the series are reported. Several of these compounds have pK(a) values that would indicate potential utility for buffering at pH levels below the normal physiological range (pK(a) values in the range of 3 to 6 without aqueous solubility problems)- a range that is problematic for currently available Good buffers. Unfortunately, the alkylaminomethanesulfonates were found to degrade (with loss of their buffering ability) at pH levels below the pK(a) value and were unstable at elevated temperature (as when autoclaving)- thus limiting their utility.

A NbO-type metal-organic framework, PCN-46, was constructed based on a polyyne-coupled di-isophthalate linker formed in situ. Its lasting porosity was confirmed by N(2) adsorption isotherm, and its H(2), CH(4) and CO(2) adsorption capacity was examined at 77 K and 298 K over a wide pressure range (0-110 bar).

Two common radical anion reductants, potassium benzophenone ketyl (K(Ph(2)CO)) and potassium naphthalenide (K(2)(C(10)H(8))(2)(THF)), have been isolated and characterized for the first time in solvent-free form or with low solvent content, allowing their use as pure solid reactants in preparative redox chemistry in accurate stoichiometric amounts.

Heterocyclic privileged medicinal scaffolds involving pyridine, 1,4-dihydropyridine, chromeno[2,3-b]pyridine, and dihydro-1,4-dithiepine frameworks are prepared via a single-step multicomponent reaction of structurally diverse aldehydes with various thiols and malononitrile. Mechanistic studies of the synthetic pathway leading to pyridines reveal that 1,4-dihydropyridines undergo oxidation by the intermediate Knoevenagel adducts rather than by air oxygen. The use of o,o'-disubstituted aromatic aldehydes leads to the corresponding 1,4-dihydropyridines, whereas salicylic aldehydes result in chromeno[2,3-b]pyridines. Reactions of ethanedithiol as a thiol component produce dimeric pyridines with sterically unencumbered aldehydes, while o,o'-disubstituted aromatic aldehydes give dihydro-1,4-dithiepines. Thus, depending on the aldehyde and thiol types, diverse libraries of medicinally relevant compounds can be prepared by a simple one-step process involving no chromatography.

Bisurea calix[4]arenes 1 and 2 possessing l-amino acid moieties at the lower rim were synthesized by reaction of the methyl esters of glycine, l-alanine, or l-isoleucine with the appropriate isocyanate (12 or 13), obtained with a safe and efficient Curtius rearrangement from the corresponding carboxylic acid derivatives. The conformational properties of the ligands 1 and 2 were investigated by means of a combined NMR and molecular modeling study which evidences that they are deeply influenced by strong intramolecular H-bonds between the urea NH groups and the vicinal phenolic oxygen atoms or the opposite urea C=O group. Complexation studies performed by ESI-MS and NMR spectroscopy in acetone solution show that the binding ability of these bisurea hosts decreases by increasing the side chain size of the amino acid. Host 2b has a remarkable binding ability for the N-acetyl-d-phenylalaninate anion with an interesting enantioselectivity (%@mt;sys@%%@ital@%K%@rsf@%%@sx@%ass%@be@%D%@sxx@%%@mx@%/%@mt;sys@%%@ital@%K%@rsf@%%@sx@%ass%@be@%L%@sxx@%%@mx@%= 4.14), which is explained on the basis of a three-point interaction mode of binding.

A diastereomeric mixture of chiral 25-(1S)-camphorsulfonyloxy-26-isopropoxycalix[4]arene 2a (de 15%) and 25-isopropoxy-26-((1S)-10-camphorsulfonyl)calix[4]arene 2b has been obtained by asymmetrical lower rim (1S)-camphorsulfonylation of the monoisopropoxycalix[4]arene. Pure diastereomer 2a has been obtained by simple crystallization, and its absolute configuration has been determinated by X-ray analysis. Enantiomerically pure inherently chiral 5,11-dibromo-26-isopropoxycalix[4]arene 4 has been synthesized by the upper rim dibromination of the diastereomer 2a followed by hydrolytical removal of the auxiliary camphorsulfonyl group.

Hexaferrocenylbenzene has been synthesized by six-fold Negishi type ferrocenylation of hexabromo- or hexaiodobenzene.