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

(1)尝试了以结构调谐客体(STG)、金属络合物为催化活性物种、(III)无机层状化合物为主体的纳米复合材料制备自响应型催化剂(智能催化剂).(2)不同类型的主体化合物被用来控制蒙脱石(TN)、氢托石(HT)等蒙脱石(TN、HT型阳离子交换剂)和沸石类化合物(Ni-ZnAc为阴离子交换剂)的层间距。将不同的Rh(I)配合物插层到这些阳离子和阴离子层间化合物中，制备了不同层间距的Rh(I)负载催化剂。用所得到的催化剂对二烯烃、炔烃、酮的加氢反应进行了评价。得到以下结果：(1)通过STG和阳离子交换剂&GT来控制层间距；通过STG(烷基胺)与C10、C14和Cl18形成的I蒙脱石的层间距在2.51~3.72 nm之间。(Ii)&lt；通过STG和阳离子交换剂&GT控制层间距：通过STG(羧酸)与C10、C14和Cl18形成的Ni-ZAc的层间距为2.51~3.27 nm。将Rh-TPPTS(三苯磺酸膦)阴离子插层到Ni-ZnAc中，制备负载型催化剂。(Iii)&lt；利用结构调谐配体(STL)和GT的Rh(I)配合物控制层间空间；用4-烷基吡啶(CnPy)和4，4‘-二烷基-2，2’-联吡啶(Cnibpy)(n=1，5，9)合成了Rh(I)-STL配合物。这些Rh(I)STL络合物被插入到TN中，得到了1.9~2.72 nm的层间距。催化剂的活性明显依赖于负载型催化剂的层间距，这些催化剂表现出分子尺寸、区域和手性选择性。由于缺乏电离官能团，没有观察到PVME等聚合物凝胶的插层。

(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.