Formation Process of SiF(6)@Cu(2)L(4) Chiral Cage Pairs in a Glass Vessel: Catechol Oxidation Catalysis and Chiral Recognition

[Image: see text] Self-assembly of CuX(2) (X(–) = BF(4)(–), PF(6)(–), and SbF(6)(–)) with a pair of chiral bidentate ligands, (1R,2S)-(+)- and (1S,2R)-(−)-1-(nicotinamido)-2,3-dihydro-1H-inden-2-yl-nicotinate (r,s-L or s,r-L), in a mixture solvent including ethanol in a glass vessel gives rise to SiF(6)(2–)-encapsulated Cu(2)L(4) chiral cage products. The SiF(6)(2–) anion from the reaction of X(–) with SiO(2) of the glass-vessel surface acts as a cage template or cage bridge. One of the products, [SiF(6)@Cu(2)(SiF(6))(s,r-L)(4)]·3CHCl(3)·4EtOH, is one of the most effective heterogeneous catalysts for the oxidation of 3,5-di-tert-butylcatechol. Furthermore, an l-DOPA/d-DOPA pair is recognizable by the cyclic voltammetry (CV) signals of its combination with chiral cages [SiF(6)@Cu(2)(BF(4))(2)(s,r- or r,s-L)(4)]·4CHCl(3)·2EtOH pair and [SiF(6)@Cu(2)(SiF(6))(s,r- or r,s-L)(4)]·3CHCl(3)·4EtOH pair.