Syntheses, Crystal Structures, and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrins
Syntheses, Crystal Structures, and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrins
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DOI：
10.1246/bcsj.79.1431
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发表时间：
2006-09
影响因子：
4
通讯作者：
J. Nakazawa;Maki Mizuki;J. Hagiwara;Y. Shimazaki;F. Tani;Y. Naruta
中科院分区：
文献类型：
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作者：
J. Nakazawa;Maki Mizuki;J. Hagiwara;Y. Shimazaki;F. Tani;Y. Naruta
合成了新型的胶囊状主体“空穴连接卟啉”金属配合物（Mcp：M = H2，Ni，Zn，Pd），以模拟细胞色素P-450 cam等金属酶的底物结合功能.研究了空穴配体1·MeOH·CHCl 3，[Zntpp（MeOH）]，[NiCp]·MeOH·2CHCl 3 ·3 H2O，[Zncp（MeOH）]·2CHCl 3的晶体结构. 3 H2 O和[Pdcp]·MeOH·2 CHCl3·3 H2 O。一个甲醇分子，源自结晶溶剂被封装在每个主机腔，并协调Zn在Zncp，但不是在Ni-和Pdcp。通过测定结合常数和~ 1H NMR滴定得到的热力学参数，评价了不同小烃分子在Mcps的CDCl 3溶液中的包封。在大气压下，所有Mcps都封装了比丙烷小的碳氢化合物。客体尺寸的选择性主要受空腔尺寸的影响，部分受金属插入的影响。金属离子半径不影响客体尺寸选择性。还研究了配位客体分子（MeOH、EtOH、MeCN和H2O）在Mcps中的包封.只有Zncp有利于非烃类客体如MeOH的配位。我们的结论是，不同大小的客人由Mcps的住宿取决于客户的大小和功能团的协调取决于两个身份的卟啉的金属离子和客户的大小。
New capsule-shaped hosts "cavitand-linked porphyrin" metal complexes (Mcp: M = H 2 , Ni, Zn, and Pd) have been synthesized to mimic the substrate binding functions of metalloenzymes such as cytochrome P-450 cam . Crystal structures of cavitand 1·MeOH·CHCl 3 , [Zntpp(MeOH)], [Nicp]·MeOH·2CHCl 3 ·3H 2 O, [Zncp(MeOH)]·2CHCl 3 . 3H 2 O, and [Pdcp]·MeOH·2CHCl 3 ·3H 2 O have been determined. One methanol molecule, originating from crystallization solvent is encapsulated in each host cavity, and coordinates to Zn in Zncp but not in Ni- and Pdcp. Encapsulation of various small hydrocarbon molecules in CDCl 3 solutions of Mcps have been evaluated by determining binding constants and thermodynamic parameters obtained from ' H NMR titrations. All Mcps encapsulate hydrocarbons smaller than propane under atmospheric pressure. The guest size selectivity is primarily influenced by cavity size, and partly by metal insertion. The metal ion radius does not affect guest size selectivity. Encapsulation of coordinating guest molecules (MeOH, EtOH, MeCN, and H 2 O) in Mcps has also been investigated. Only Zncp favors coordination of non-hydrocarbon guests such as MeOH. We concluded that accommodation of different size guests by Mcps depends upon guest sizes and coordination of functional groups depends upon both the identity of the porphyrin's metal ion and guest sizes.