Guests inducing p-sulfonatocalix[4]arenes into nanocapsule and layer structure

2010 
Reaction of sodium p-sulfonatocalix[4]arene and TbCl{sub 3} in the presence of 2,2'-bipyridine-N,N'-dioxide (bpdo) gives the 2:1 supramolecular nanocapsule [[Tb(bpdo){sub 2}.4H{sub 2}O]{sup 3+} intersection {l_brace}p-sulfonatocalix[4]arene{sup 4-{r_brace}}{sub 2}], which further interacts with the [Tb(bpdo){sub 4}]{sup 3+} through charge-assisted {pi}-stacking interactions forming a channel structure 1. In further investigation, we tried to use the terpyridine-1,1',1'-trisoxide (tpto) instead of bpdo. Although we failed to isolate a supramolecular capsules based on the tpto, lanthanide and p-sulfonatocalix[4]arene, a layer structure derived from p-sulfonatocalix[4]arene with an unusual [Cu(tpto){sub 2}]{sup 2+} incorporation into the cavity of the calixarene and an outside [Cu(tpto){sub 2}]{sup 2+} balancing the charge, has been obtained. Fluorescence spectra show clearly that compound 1 possesses the luminescence characteristics of Tb{sup 3+} and the ligand bpdo can sensitize Tb{sup 3+} ion. Gas sorption experiment shows the channel structure 1 has highly selective gas sorption properties for water and methanol. - Graphical abstract: In the presence of different guests, a nanochannel architecture based on the p-sulfonato[4]calixarene capsule and a layered structure based on the p-sulfonato[4]calixarene tecton have been synthesized, and the luminescence properties and guest sorption of porous structure have been investigated.
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