Layered Calcium Structures of p-Phosphonic Acid O-Methyl-Calix[6]arene.

Hexamethoxy-calix[6]arene has been fully functionalized with p-phosphonic acid groups on the upper rim in 57% yield over three steps, and has been authenticated in the solid state by X-ray diffraction as either a nitrate salt or one of two calcium complexes. The latter differ by the ratio of calcium ions per calixarene, either 3:1 or 4:1. In both structures the coordination sphere of the calcium ions is made up of oxygen atoms from the phosphonic acid groups and from water of crystallization, as part of extended polymeric layers in the extended 3D packing.

Organization of lower rim O-alkylated p-phosphonic acid calix[4]arenes.

Lower rim O-methyl, -n-butyl, and n-octadecyl calix[4]arenes bearing p-phosphonic acid groups on the upper rim have been prepared in high yield, compounds 12-14. Where possible the compounds have been characterized in the solid state using X-ray diffraction, or as the precursor phosphate esters or a cesium salt. The cone conformation ethyl phosphate ester for the octadecyl compound crystallizes in a bi-layer 39.

Carborane inclusion chemistry for the uncommon calix[7,9]arenes.

The inclusion of o-carborane by p-Bu(t)-calix[7,9]arenes has been investigated by solid state and solution studies, with both resulting complexes in the solid state being rich in carborane with the ratio of calixarene to carborane at 1 : 7 and 2 : 7 respectively. The carboranes reside in clefts within the calixarenes which arise from specific local conformations of adjacent phenolic groups, or are included in the extended structure through other interplay of the calixarenes and carboranes in such clefts.

Calix[5]arene: a versatile sublimate that displays gas sorption properties.

Varied temperature sublimation of calix[5]arene results in the formation of two distinctly different crystal structures or polymorphs alpha and beta, the latter of which is based on both 'self-included' and 'back-to-back' helical arrangements of the molecule, while also being active towards CO2 sorption at room temperature and 1 atmosphere pressure.

Engineering nanorafts of calixarene polyphosphonates.

The water-soluble calix[4]arene bearing p-substituted phosphonic acid groups is accessible in five steps in overall 62 % yield, with the hydrogen-bonding prowess of the acidic groups dominating its self-assembly processes. These include the formation of 3.0(3) nm and 20(2) nm nanorafts of the calixarene in water using spinning disc processing, stabilized by acetonitrile, and nanorafts in the gas phase ( View Article and Find Full Text PDF

Solution and solid state studies on the binding of isomeric carboranes C2B10H12 by p-Bu(t)-calix[5]arene.

p-Bu(t)-calix[5]arene forms crystalline inclusion complexes with o- and m-carboranes in toluene or dichloromethane-hexane, but not with the p-isomer, the extended structures being based on 1 : 1 host-guest supermolecules, with the p-Bu(t)-substituents creating a snug fit for o- and m-carborane; p-carborane forms a highly hexane soluble complex, induced by grinding, which crystallizes as fibres. Solution phase studies showed the presence of a 1 : 1 host-guest stoichiometry with all three isomeric carboranes as determined from Job plots. The association constants for the o- and m-carborane complexes are 6.