New dendrimers containing a single cobaltocenium unit covalently attached to the apical position of Newkome dendrons: Electrochemistry and guest binding interactions with cucurbit[7]uril

Two new dendrimer series were prepared and characterized. These dendrimers contain a single bis(cyclopentadienyl)-cobalt(III) (cobaltocenium, Cob(+)) unit covalently attached to the apical ( focal) position of Newkome-type dendrons, ranging in size from first to third generation. The dendrimers in the first series (1ECob(+)-3ECob(+)) are hydrophobic and have 3, 9, and 27 tert-butyl esters on their peripheries, whereas the dendrimers in the second series (1Cob(+)-3Cob(+)) are hydrophilic with 3, 9, and 27 carboxylic acid groups on their surfaces, respectively. In voltammetric experiments, all dendrimers showed the expected one-electron reversible reduction of the cobaltocenium center, and the heterogeneous rate of electron transfer decreased with generation in both dendrimer series. The host-guest binding interactions between water-soluble dendrimers 1Cob(+)-3Cob(+) and the cucurbit[7]uril (CB7) host were investigated using H-1 NMR spectroscopy, MALDI-TOF mass spectrometry, and electrochemical techniques. The association equilibrium constants ( K) for all dendrimer guests were significantly lower than that measured for the inclusion complex between underivatized Cob(+) and CB7 (K=5.7x10(9) M-1). Nonetheless, among the three dendrimers surveyed, the second-generation dendrimer, 2Cob(+), afforded optimum stabilization for the CB7 inclusion complex.