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These selectivities were based on the formation kinetics, which solely depend on the size of the pseudostopper. The thermodynamic selectivities controlling the final distribution of products might be different, since they also depend on interactions of the CD with the binding site and the stopper. Examples are known where the CD rings changed their mind: they began by threading in one direction (kinetically controlled) but, in the end, they threaded in the other direction (thermodynamically controlled) [166, 168].

Recognition of Monomers and Polymers by Cyclodextrins 23 Fig. 4 A, for rotaxane synthesis. Therefore, only a few γ-CD rotaxanes are presently known. The Anderson group showed that m-terphenyl-4, 4 dicarboxylic acid is sufficiently large. They were able to synthesize a [2]-rotaxane from the IC of γ-CD and a stilbene derivative using this stopper. The [2]-rotaxane obtained had sufficient space remaining to accommodate another axis molecule that could be stoppered, as well to furnish the first [3]-rotaxane with two axes through one CD ring.

20 [212–215]. These molecular CD print boards may find very interesting applications for the assembly of molecular devices by ink jet printing or dip pen nanolithography. Recognition of Monomers and Polymers by Cyclodextrins 31 Fig. 19 Cyclodextrin vesicles stabilized by complexation of the guest polymer, tert-butylanilidPIBMA [210] Fig. 20 Schematic representation of different binding modes for guest polymers with planar CD arrays [213] 32 G. 1 General Considerations Complexation of a polymer main chain by CDs differs significantly from complexations of polymer side chains.

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