Synthesis of Oligophenylene-Substituted Calix[4]crown-4s and Their Silver(I) Ion-Induced Nanocones Formation

A novel series of oligophenylene OPP(n)-substituted calix[4]crown-4s bearing up to three phenylene units, 1a-d, has been efficiently synthesized by means of either microwave-assisted or silver(I) ion-assisted Pd-catalyzed Suzuki cross-coupling of tetraiodocalix[4]crown-4 and the corresponding oligophenylboronic acids. Complexation of OPP(n)-substituted calix[4]crown-4s with silver (I) ion was substantiated by ¹H NMR spectroscopic and high-resolution ESI- or MALDI-TOF- MS studies. The weak binding affinities of OPP(n)-substituted calix[4]crown-4s for silver (I) ion, which were estimated from ¹H NMR titrations with binding association in the range of 30-90 M^-1, allows reversible disassembling in the presence of KI at ambient temperature. Remarkably, the single-crystal X-ray structures of OPP(n)-calix[4]crown-4-Ag⁺ complexes indicate the atypical silver (I) ion-crown ether binding mode resulting in the formation of rigid nanocones with volume created up to ∼1500 ų. Our results suggested that despite the weak binding affinity of crown ether ligands for silver (I) ion, this weak interaction is still be useful as a tool to construct supramolecular architectures.