(Ethylenediaminetetraacetic Acid)cerium(IV) [CeIV(EDTA)] Complexes with Dual Hydrophobic Binding Sites as Highly Efficient Catalysts for the Hydrolysis of Phosphodiesters

β‐Cyclodextrin (β‐CD) derivatives 1 with an amino group at C(6), C(3), or C(2) were homogeneously linked together by an ethylenediaminetetraacetic acid (EDTA) bridge (Scheme). Coordination of the linker to metal ions and cooperation of the dual cavities of 3 in binding hydrophobic guests were properly demonstrated by NMR techniques and a fluorescence‐based titration method, respectively. The hydrolysis of bis(4‐nitrophenyl) phosphate (BNPP) in the presence of Ce^IV complexes of β‐CD dimers 3 was tens of millionfold faster than that in the absence of the Ce^IV complexes. Hydrophobic binding of the β‐CD cavities was estimated to contribute to the catalysis by a factor of up to 520, and the type of modified sugar unit and the bridging positions influenced this cooperation between the β‐CD moieties and the catalytic metal center.