Cyanide-bridged iron(II,III) cube with multistepped redox behavior
Cyanide-bridged iron(II,III) cube with multistepped redox behavior
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DOI：
10.1021/ic7024582
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发表时间：
2008-07-21
影响因子：
4.6
通讯作者：
Oshio, Hiroki
中科院分区：
文献类型：
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作者：
Nihei, Masayuki;Ui, Mayumi;Oshio, Hiroki
普鲁士蓝的结构单元被分离为[（Fe_4Fe_4III）-Fe-II（CN）（12）（tP）（8）]中心点12 DMF中心点2 Et（2）O中心点4 H（2）O [tp（-）=水合（吡唑基）硼酸盐]的氰化物桥连铁立方体。循环伏安图显示准可逆的四阶氧化还原波，其对应于[（Fe 4Fe 4 II）-Fe-III]/ [（Fe 5 Fe 3 II）-Fe-III]（+）、[（Fe 5 Fe 3 II）-Fe-III]（+）/[（Fe 6 F2 II）-F-III]（2+）、[（Fe 6 Fe 2 II）-Fe-III]（2+）/[（Fe 7 Fe 1 II）-Fe-III]（3+）和[（Fe 7 Fe 1 II）-Fe-III]（3+）/[Fe-8（III）]（4+）过程。控制电位吸收光谱测量显示两个价间电荷转移带在816和1000 nm，这被分配到从Fe-II离子的电荷转移到相邻和远程Fe-III离子，分别在立方体。
A building unit of Prussian blue was isolated as a cyanide-bridged iron cube of [(Fe4Fe4III)-Fe-II(CN)(12)(tP)(8)]center dot 12DMF center dot 2Et(2)O center dot 4H(2)O [tp(-) = hydrosis(pyrazolyl)borate]. A cyclic voltammogram showed quasi-reversible four-stepped redox waves, which correspond to [(Fe4Fe4II)-Fe-III]/ [(Fe5Fe3II)-Fe-III](+), [(Fe5Fe3II)-Fe-III](+)/[(Fe6F2II)-F-III](2+), [(Fe6Fe2II)-Fe-III](2+)/[(Fe7Fe1II)-Fe-III](3+), and [(Fe7Fe1II)-Fe-III](3+)/[Fe-8(III)](4+) processes. Controlled potential absorption spectral measurements revealed two intervalence charge-transfer bands at 816 and 1000 nm, which were assigned to charge transfers from Fe-II ions to adjacent and remote Fe-III ions, respectively, in the cube.