Preparation of Self-Responsive Materials by Mean of Intercalation Compounds with Polymer Gels and Application to Intelligent Catalysts

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(1) The preparation of self-responsive catalysts (intelligent catalysts) was tried by means of nano composites composed of three components, i. e., (i) structural tuning guests(STG), (ii) metal complexes as catalytic active species, and (iii) inorganic layer compounds as host.(2) <Results>Various type of host compounds were used to control the interlayer space size such as smectites (taeniolite(TN), hectorite(HT) as cation exchangers) and botallackite type compounds (nickel-zinc acetate(Ni-ZnAc) as anion exchanger). Various Rh(I) complexes are intercalated into these cationic and anionic layer compounds to prepare the Rh(I)-supported catalysts with various interlayer space sizes. Various catalytic hydrogenation reactions such as hydrogenation of dienes, alkynes, and ketones were carried out by means of the obtained catalysts to evaluate the molecular recognition. The following results were obtained : (i)<Control of interlayer space by means of STG and cation exchangers> The basal spacing of I smectites ranged from 2.51〜3.72 nm by means of STG (alkyl ammoniums) with C10, C14, and CI18. (ii)< Control of interlayer space by means of STG and cation exchangers> The basal spacing of Ni-ZnAc ranged from 2.51〜3.27 nm by means of STG (carboxylic acids) with C10, C14, and CI18. Rh-TPPTS (phosphinetribenzenesulphonate) anion was intercalated into Ni-ZnAc to prepare the supported catalysts. (iii)<Control of interlayer space by means of Rh(I) complexes with structural tuning ligands (STL)> Rh(I)-STL complexes were prepared by means of 4-alkylpyridine(CnPy) and 4,4 '-dialkyl-2,2 '-bipyridine (Cnibpy)(n=1,5,9). These Rh(I)STL complexes are intercalated into TN to give the basal spacing ranging from l.9〜2.72 nm.The activity of catalysts clearly depended on the basal spacing of the supported catalysts and these catalysts showed molecular size, regio, and chiral selectivity.The intercalation of polymer gels such as PVME was not observed due to the lack of ionized functional groups.