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The racemic ligand (±)-tris-(4-methylthiazolyl)cyclotriguaiacylene forms a homochiral crystalline Ag12L8 cube with spontaneous resolution. The ligand itself likewise crystallises in a chirally pure fashion in two clathrate complexes. Ag12L8 is the first example of a cyclotriguaiacylene-type coordination cube and a rare example of a M12L8-type metallo-cube.

A review of the emerging field of cyclotriveratrylene-derived coordination cages is presented. Ligand-functionalised cyclotriveratrylene (CTV) derivatives self-assemble with a range of metal cations to afford coordination cages, polymers and topologically non-trivial constructs, such as [2]catenanes and a self-entangled cube. Increased control over their self-assembly allows for the controlled and predictable formation of well-defined coordination cages for application in host-guest and recognition chemistry, with surfactant binding and single-crystal-to-single-crystal (SCTSC) uptake of small-molecule guests being observed.

Supramolecular chemistry of icosahedral main group cage molecules, fullerene C60 and the carboranes o-, m- , p-B2C10H12, is of interest in the purification of these molecules and in building up novel materials. The non-polarised, spherical like nature of C60 requires specific shape and electronic complementarity between the interacting supramolecular synthons which leads to polarisation of the fullerene, whereas for the carboranes, hydrogen bonding involving the C–H groups, including the formation of bifurcated hydrogen bonds [C–H‥(N,O)2], and C–H‥π interactions, along with shape complementarity, facilitate the self assembly process. Insight into future prospects in this field is presented.

A new bis(disulfide)-linked offset dimer is formed from a dithiolated analogue of cyclotriguaiacylene. Unlike a similar tris(disulfide)-linked example, this is not a true cryptophane as the offset nature of the dimerisation and intramolecular host-guest interactions preclude its use as a host.

p-Phenylcalix[5]arene shows a strong and selective binding of C60 in toluene resulting in crystallisation of a hemispherically inter-digitated 2∶1 complex; the receptor itself crystallises from toluene with self assembly through phenyl group inclusion.

Treatment of M[Co(C2B9H11)2], M = Na or K, with [2.2.2]cryptand and 5,7,12,14-tetramethyldibenzo[b,i]-1,4,8,11-tetraazacyclotetradeci nenickel(II) results in a 1∶1∶1 complex, assembled with the cobalticarborane anion snugly residing in the phenyl lined face of the Ni(II) macrocycle through C–H…N and C–H⋯π interactions, with the ensuing [M⊂[2.2.2]cryptand]+ supercation residing in the smaller methyl faced cavity of the macrocycle.

The complex {(Na[2.2.2]cryptate)[CTV][Co(C2B9H11 )2]}2- (MeCN) (CTV = cyclotriveratrylene) features (Na[2.2.2]cryptate)+∩CTV interplay as well as a closely packed chain of [Co(C2B9H11)2]− counter-anions exhibiting dihydrogen bonding, and a similar cation–CTV assembly is found in (Na[2.2.2]cryptate)[CTV](CHCl3)3[CB11H 12].

The crystalline supramolecular complex [Sr(H2O)8][(CH3CN) [symbol: see text] (CTV)]4(H2O)4[Co(C2B9H11)2]2 features [(CH3CN) [symbol: see text] (CTV)] host-guest interactions, back-to-back tetrameric clusters of CTV host molecules and an extensive hydrogen bonding giving a 3,12-connected net.

A combination of hydrogen bonding and metal coordination leads to the formation of the new solid state molecular capsule [{18-crown-6}⊂{(Y(H2O)73+ )1.33(p-sulfonatocalix[4]arene4− )}2] at pH between 1.0 and 4.0.

Self-assembled molecular capsules are formed on crystallisation of calix[5]arenesulfonic acid resulting from treating calix[5]arene with sulfuric acid; the calix[5]arenesulfonic acid molecules dimerise via hydrogen bonding through the sulfonic acid groups, shrouding two hydrogen-bonded sulfuric acid molecules as the supermolecule [(H2SO4)2}⊂{(calix[5]arenesulfonic acid)2].

Cyclam crystallised from CHCl3–hexane gives infinite, hydrogen bonded assembled columns; in acidic aqueous media (pH 2) in the presence of sodium p-sulfonatocalix[4]arene and the dichromium(III) aqua ion, the superanion or ionic capsule [[H4(cyclam)]4+ ⊂ {(p-sulfonatocalix[4]arene4–)2}]4– crystallises as the salt of [Cr2(OH)2(H2O)8]4+.

Excess octaphenylcyclotetrasiloxane [{SiPh2(µ-O)}4] and C60 in toluene affords the 1:1 supramolecular complex as a hemi-toluene solvate where the fullerenes are arranged in double columnar arrays shrouded by edge on, interlocking siloxanes.

Aqueous solutions of sodium p-sulfonatocalix[4]arene, 18-crown-6 and lanthanum(III) trichloride at pH 2.5 afford the ‘ferris wheel’ type supercation: [{Ln3+⊂(18-crown-6)(OH2)3}∩{(p-sulfonatocalix[4]arene4– + 2H+)}]+ isolated as the chloride with numerous waters of crystallisation.

A novel conformation of p-sulfonatocalix[5]arene has been established in the solid state with two calixarenes organised in a 'bis-molecular capsule' shrouding two di-protonated DABCO molecules and two water molecules within.