A ruthenium(II)-catalyzed, highly selective, quantitative radical addition of an alkene, methacrylic acid (MAA), has been achieved by using a template halide (2) containing a built-in amine group as a recognition site for the carboxyl group of the substrate. The specific ionic binding of MAA by the amine template (1:1 molar ratio) led to preferential formation of the 1:1 MAA-2 adduct, whereas a similar halide without a template induced MAA oligomerization even in the presence of an externally added amine. A competitive radical addition of MAA versus its ester form [methyl methacrylate (MMA)] on the halide further demonstrated that the substrate selectivity [k'(MAA)/k'(MMA)] for 2 is enhanced more than 10 times by the intramolecular introduction of the template relative to the result for the nontemplate halide. These specificities are most likely triggered by the specific interaction (recognition) of the carboxyl group in MAA via the acid-selective template amine, which is implanted in the close vicinity of the radical addition site in 2. These results intimate possibility of control over the repeat-unit sequence in precision polymerization.

Surprisingly high monomer selectivity was demonstrated in competitive radical addition with two kinds of methacrylates carrying sodium and ammonium cation. Crucial is size-specific recognition by a lariat crown ether embedded close to the reactive halide in a designer template initiator. Especially, a combination with an active ruthenium catalyst led to outstanding selectivity at low temperature. This template system will open the way to unprecedented sequence-regulated polymerization.

"Template initiator"' platforms (1) have been designed for expressing the sequence information in a template in radical polymerization. Thus, we demonstrated the structural adequacy of 1 consisting of two initiating sites placed ortho to each other in benzene: one for living cationic polymerization to introduce a template carrying substrate-recognition tags, and the other for metal-catalyzed living radical polymerization to achieve sequence regulation. For example, for two positional isomers with an amine template for an acid monomer, only the ortho initiator induced selective radical addition of MAA (recognizable) over MMA (non-recognizable). Another version was an oligo(vinyl ether) with a multiple amine template, which demonstrated template effects for MAA recognition over BzMA in copolymerization.

Thermoresponsive conetworks with crosslinked domain structures were designed by the crosslinking of triblock polymers for responsive gel functioning without external water.