Fine-Tuning the Dimerization of Tetraureacalix[4]arenes

Calix[4]arenes substituted by four urea residues at their wide rim form hydrogen-bonded homo- and heterodimeric capsules in apolar solvents. If urea groups are covalently connected to loops or substituted by bulky residues, the dimerization may be restricted to those pairs in which the loops do not overlap and for which the residues are small enough to pass the loops. In the present study, we describe the dimerization properties of tetraureas with one, two (adjacent or opposite), three, or four loops and those bearing (additionally) up to four residues of different size: a=tolyl, b=3,5-di-tert-butylphenyl, c=4-propyloxy-3,5-di-(tert-butylphenyl)phenyl, and d=4- [tris-(4-tert-butylphenyl)methyl]phenyl. For compounds with four loops of different size (-O-(CH2)(n)-O-chains with n=10, 14, and 20 connecting the in-positions of the urea phenyl residues) a clear stepwise sorting scheme could be established, in which the bulkiest residue d is excluded by all tetraloop compounds and the smallest residue a can pass only the smallest loops (n=10). The medium-sized residues b or c are tolerated by n=14 and 20 or only by n=20. Selectivities can be built up also on geometrical factors. A trisloop compound, for instance, combines only with a tetraurea bearing a single bulky residue and tetraureas with two bulky substituents in adjacent or opposite position are distinguished by the bisloop derivatives with adjacent or opposite loops. The impossibility to form a homodimer of a monoloop compound containing two bulky residues leads to its selective heterodimerization with a derivative bearing three bulky groups. Subtle effects for borderline cases, in which the dimerization or reorganization takes a longer time, are also discussed.