To investigate dynamic solid-state complexation hitherto unexplored in nitrogen-bridged calixarene analogues, azacalix[6]arene hexamethyl ether has been prepared in three steps by applying a 5+1 fragment-coupling approach by using a Buchwald- Hartwig aryl amination reaction with the aid of our previously devised temporal N-silylation protocol. X-ray crystallographic analysis and NMR spectroscopic measurements have revealed that the azacalix[6]arene is well endowed with hydrogen-bonding ability, by which both the molecular and crystal structures are controlled. The azacalix[6]arene is conformationally flexible in solution on the NMR time scale, whereas it adopts a definite 1,2,3-alternate conformation with S2 symmetry in the solid state as a result of intramolecular bifurcated hydrogen-bonding interactions. In the crystal, molecules of the azacalix[6]arene are mutually interacted by intermolecular hydrogen bonds to establish one-dimensional hexane-filled nanochannel crystal architecture. Although the single crystal was broken after desolvation, the resultant polycrystalline powder material was capable of selectively adsorbing CO2 among the four main gaseous components of the atmosphere. In contrast, carbocyclic p-tert-butylcalix[6]arene hexamethyl ether, the crystal structure of which was also elucidated for the first time in the present study, gave rise to almost no uptake of CO2. Additional solid-gas adsorption experiments for another three gases, such as N2, O2, and Ar, suggested that quadrupole/induced-dipole interactions and/or hydrogen-bonding interactions played an important role in permitting the observed selective uptake of CO2 by this new azacalix[6]arene in the solid state.

To investigate the solid-state complexation of nitrogen-bridged calixarene analogues, azacalix[7]arene heptamethyl ether 1 has been prepared by applying a "5 + 2"-fragment coupling approach using Buchwald-Hartwig aryl amination reaction aided by our previously devised temporal N-silylation protocol. X-ray crystallographic analysis revealed that azacalix[7]arene 1 adopted a highly distorted 1,2-alternate conformation in the solid state as a result of intramolecular NH/O hydrogen bonding interactions and steric repulsion between the methoxy groups. In the crystal, molecules of 1 are mutually interacted by intermolecular NH/O and CH/pi interactions to establish one-dimensional (1D) hexane-filled nanochannel crystal architecture. Similarly to our recently reported azacalix[6]arene 2, the desolvated crystalline powder material of 1 was capable of selectively and rapidly adsorbing CO2 among the four main components of the atmosphere. The adsorption capacity of 1 for CO2 nearly doubled as compared to that of 2 because of the formation of the 1D nanochannel with almost twice the volume of the latter.

Electron paramagnetic resonance spectroscopy has unmasked for the first time the spin-delocalised doublet- and triplet-ground states of azacalix[4]arene cation radicals.

Conformational flexibility of exhaustively methylated azacalix[4]arene in solution has been investigated. Relaxation time measurements revealed that its 1,3-alternate conformation was inflexible even in solution. Intramolecular small annulus plays a central role in suppressing the conformational inversion by the small but yet sufficiently bulky O-methyl groups. Without regard to the small anulus, the azacalix[4]arene has a room to selectively accommodate potassium ion in the cavity.

[Structure: see text] A temporal N-silylation protocol in the catalytic aryl amination reaction has been devised to prepare nitrogen-bridged calixarene analogues. The protocol involves a smooth in situ N-silylation before aryl amination reaction, followed by spontaneous cleavage of the N-Si bond in the usual workup process, to furnish secondary aromatic amines as the cross-coupled product with no silyl group on the nitrogen atom. A successful application to the preparation of regioselectively N-methylated azacalix[8]arene is described, together with the crystallographic analysis.