多金属氧酸盐（POM）基多功能无机-有机杂化化合物：接枝于单和三缺位 Keggin POM 上的含硅醇和/或硅氧烷键的物种的合成和分子结构。

Polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds: syntheses and molecular structures of silanol- and/or siloxane bond-containing species grafted on mono- and tri-lacunary Keggin POMs.

机构信息

Department of Materials Science (present name Department of Chemistry), Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan.

出版信息

Dalton Trans. 2011 Feb 14;40(6):1243-53. doi: 10.1039/c0dt01185a. Epub 2010 Dec 22.

DOI:10.1039/c0dt01185a

PMID:21180696

Abstract

Using 3-mercaptopropyltrimethoxysilane (HS(CH₂)₃Si(OMe)₃) as a silane-coupling agent (SCA), mono- and tri-lacunary Keggin polyoxometalate (POM)-based, multi-functional, inorganic-organic, hybrid compounds, (Et₄N)₃[α-PW₁₁O₃₉{(HS(CH₂)₃Si)₂O}] EtN-1 (the 1 : 2 complex of a POM unit and organosilyl groups), (Bu₄N)₃[A-PW₉O₃₄(HS(CH₂)₃SiOH)₃] BuN-2 (the 1 : 3 complex) and (Bu₄N)₃[A-α-PW₉O₃₄(HS(CH₂)₃SiO)₃(Si(CH₂)₃SH)] BuN-3 (the 1 : 4 complex) were synthesized and unequivocally characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state (²⁹Si and ³¹P) CPMAS NMR, solution (²⁹Si, ³¹P, ¹H and ¹³C) NMR, and X-ray crystallography. [Note: The moieties of their polyoxoanions are abbreviated simply as 1-3, respectively.] The X-ray molecular structures of EtN-1 and BuN-3 were determined. In EtN-1, two organic groups connected through a siloxane bond (-Si-O-Si- bond) were grafted on a mono-lacunary site of a Keggin POM, whereas in BuN-3 four organic groups connected through siloxane bonds were grafted on a tri-lacunary site of a Keggin POM. In BuN-2, three organic groups were grafted in the form of silanol (-SiOH) on a tri-lacunary site, i.e., in BuN-2 there was no siloxane bond. BuN-3 was synthesized as BuN-3a and BuN-3b by two methods, respectively; (1) BuN-3a was obtained by a 1 : 1 molar-ratio reaction of BuN-2 and an SCA in CH₃CN, and (2) BuN-3b was prepared by a direct 1 : 4 molar-ratio reaction of a tri-lacunary Keggin POM and SCA in water-CH₃CN. X-Ray crystallography revealed that BuN-3a is the same as BuN-3b. It is probable that BuN-2 is an intermediate in the formation of BuN-3. Terminal -SH groups in 1-3, as well as -OH groups in 2, can be utilized for immobilization of POMs and, also, as building blocks for the formation of novel hybrid compounds.

摘要

使用 3-巯基丙基三甲氧基硅烷（HS（CH₂）₃Si（OMe）₃）作为硅烷偶联剂（SCA），合成了单和三缺位 Keggin 多金属氧酸盐（POM）基多功能无机-有机杂化化合物（Et₄N）₃[α-PW₁₁O₃₉{（HS（CH₂）₃Si）₂O}] EtN-1（POM 单元和有机硅基团的 1:2 配合物），（Bu₄N）₃[A-PW₉O₃₄（HS（CH₂）₃SiOH）₃] BuN-2（1:3 配合物）和（Bu₄N）₃[A-α-PW₉O₃₄（HS（CH₂）₃SiO）₃（Si（CH₂）₃SH）] BuN-3（1:4 配合物），并通过元素分析、热重和差示热分析（TG/DTA）、FTIR、固态（²⁹Si 和 ³¹P）CPMAS NMR、溶液（²⁹Si、³¹P、¹H 和 ¹³C）NMR 和 X 射线晶体学进行了明确的表征。[注：它们的多氧阴离子部分简称为 1-3。]确定了 EtN-1 和 BuN-3 的 X 射线分子结构。在 EtN-1 中，通过硅氧烷键（-Si-O-Si- 键）连接的两个有机基团接枝在 Keggin POM 的单缺位上，而在 BuN-3 中，四个通过硅氧烷键连接的有机基团接枝在 Keggin POM 的三缺位上。在 BuN-2 中，三个有机基团以硅醇（-SiOH）的形式接枝在三缺位上，即 BuN-2 中没有硅氧烷键。BuN-3 通过两种方法分别合成 BuN-3a 和 BuN-3b；（1）BuN-3a 通过 BuN-2 和 SCA 在 CH₃CN 中的 1:1 摩尔比反应获得，（2）BuN-3b 通过三缺位 Keggin POM 和 SCA 在水-CH₃CN 中的直接 1:4 摩尔比反应制备。X 射线晶体学表明 BuN-3a 与 BuN-3b 相同。BuN-2 可能是 BuN-3 形成的中间体。1-3 中的末端 -SH 基团以及 2 中的-OH 基团可用于固定 POM，并且还可用作形成新型杂化化合物的构建块。