Wide-rim functionalization of calix[4]arene: The di- and tetraisocyanocalix[4]arene assembling ligands and their silver(I) polymers and oligomers

Abstract

The 5,11- and 5,17-diisocyano-25,26,27,28-tetra-n-propoxycalix[4]arene bridging ligands (calix(NC)2) have been prepared in four steps with 34 and 30% global yields, respectively. Their corresponding Ag(I) complexes have been prepared from the direct reaction of the ligand with AgBF4 and are characterized from various spectroscopic and physical techniques. The MALDI-TOF spectra indicate the presence of polymers or oligomers of the type {Ag(calix(NC)2)(BF4)}n. The compounds have been characterized further from TGA, DSC, and XRD and compared with the oligomeric species 5,11,17,23-tetraisocyano-25,26,27,28-tetra-n-propoxycalix[4]arene silver(I) (as a BF4– salt).Key words: silver, calix[4]arene, polymer, isocyanide, photosensitive, thermal gravimetric analysis.

Coordination and Organometallic Polymers and Oligomers of Upper-Rim Functionalized Calix[4]arenes by Transition Metals

“…The use of the di-1,3-(7) and 1,2-diisocyanide (8) ligands (with four n-propyl groups at the lower-rim) was also made in order to form the corresponding coordination polymers 9 and 10 with Ag(I) ions [18].…”

“…Raston and collaborators recently reported another interesting 2-D coordination polymer built with an early transition metal [29]. The reaction of tetra-p-sulfanatocalix [4]arene salts with scandium(III) triflate in the presence of [18] [30], where the Cu(OH 2 ) 2+ 4 unit bridges two calix [4]arene macrocycles via sulfanate-to-copper coordination bonds.…”

Ligands of biologically active compounds in the nanochemistry of silver and gold (A review)

“…Structures involving silver with di-and tetraisocyanocalix [4]arene ligands can be used as new potential sensors, selective receptors, and biomimetics; the two-coordinated structures are less stable than the tetracoordinated analogs [115].…”