一种基于三重 Dawson 型多金属氧酸盐和 3d-4f 异金属簇的新型超分子组装体。

A new supramolecular assembly based on triple-Dawson-type polyoxometalate and 3d-4f heterometallic cluster.

机构信息

Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Renmin Street No.5268, Changchun, Jinlin, 130024, People's Republic of China.

出版信息

Inorg Chem. 2009 Jul 20;48(14):6452-8. doi: 10.1021/ic9001362.

DOI:10.1021/ic9001362

PMID:20507107

Abstract

The introduction of hexavacant Dawson-type precursor K(12)[H(2)P(2)W(12)O(48)] x 24 H(2)O into a HOAc/NaOAc (OAc(-) = acetate) buffer system containing (NH(4))(2)[Ce(IV)(NO(3))(6)] and Mn(II)(OAc)(2) x 4 H(2)O led to the isolation of a new compound, Na(20)Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9)Mn(III)(2)P(2)W(16)O(60) x 21 H(2)O (1). Compound 1 contains unusual triple-Dawson-type polyoxoanions Mn(III)(2)P(2)W(16)O(60)(24-) and bipyramid-like 3d-4f heterometallic clusters Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9), which are arranged in a 3-D supramolecular assembly with 1-D channels. The Na(+) cations and solvent water molecules reside in the channels. Crystal data for 1 are as follows: hexagonal, P6(3)/mcm (No. 193), a = 24.959(4) A, c = 26.923(5) A, gamma = 120 degrees, V = 14525(4) A(3), and Z = 2. The electrochemical and electrocatalytic properties of compound 1 have been investigated.

摘要

引入六缺位 Dawson 型前体 K(12)[H(2)P(2)W(12)O(48)] x 24 H(2)O 到含有 (NH(4))(2)[Ce(IV)(NO(3))(6)]和 Mn(II)(OAc)(2) x 4 H(2)O 的 HOAc/NaOAc (OAc(-) = 醋酸根)缓冲体系中，得到了一种新化合物，Na(20)Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9)Mn(III)(2)P(2)W(16)O(60) x 21 H(2)O (1)。化合物 1 包含不寻常的三重 Dawson 型多氧阴离子 Mn(III)(2)P(2)W(16)O(60)(24-) 和双锥型 3d-4f 异金属簇 Ce(IV)(3)Mn(IV)(2)O(6)(OAc)(6)(H(2)O)(9)，它们以 3-D 超分子组装排列，具有 1-D 通道。Na(+)阳离子和溶剂水分子位于通道中。1 的晶体数据如下：六方，P6(3)/mcm (No. 193)，a = 24.959(4) A, c = 26.923(5) A, gamma = 120 度，V = 14525(4) A(3)，Z = 2。已经研究了化合物 1 的电化学和电催化性质。