Synthesis and properties of diiron complexes with heteroaromatic linkers: An approach for modulation of organometallic molecular wire
Synthesis and properties of diiron complexes with heteroaromatic linkers: An approach for modulation of organometallic molecular wire
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具有杂芳族连接基的二铁配合物的合成和性能：有机金属分子线的调制方法
DOI：
10.1016/j.poly.2014.05.080
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发表时间：
2015
期刊：
影响因子：
2.6
通讯作者：
Munetaka Akita.
中科院分区：
文献类型：
--
作者：
Yuya Tanaka;Takuya Ishisaka;Takashi Koike;Munetaka Akita.
合成了具有两个氧化还原活性的金属有机化合物Cp（dppe）Fesingle键C三键C单键单元与N-甲基吡咯（3）、呋喃（4）和二吡咯乙烯（6）的金属配合物，并用~ 1H和~（31）P NMR、IR、ESI-MS和X-射线衍射对其结构进行了表征。3和4的循环伏安图显示了两个可逆的氧化还原波，属于铁中心氧化还原过程，其混合价态的平衡常数（KC）分别为5.8 × 106和1.0 × 106。3+和4+的UV-Vis-NIR光谱在近红外区含有强烈的吸收带，这归因于价间电荷转移过程。电子耦合（Vab）值为2950（3）和2665 cm−1（4）的配合物根据Robin-Day分类法被归类为III类化合物。这些数据表明，两个铁中心之间的电子相互作用强于对苯撑和噻吩撑衍生物。配合物6是二噻吩基乙烯类光致变色化合物的吡咯类似物，但没有表现出光致变色行为，表明杂芳环组分对光致变色行为有显著影响。
Metal complexes with two redox active organometallic Cp∗(dppe)Fesingle bondCtriple bondCsingle bond units bridged with N-methylpyrrole (3), furan (4) and dipyrrolylethene (6) have been synthesized and characterized by1H and31P NMR, IR and ESI-MS spectroscopy as well as X-ray diffraction study (for3). Cyclic voltammograms of3and4show two reversible redox waves ascribed to iron centered redox processes, and the comproportionation constants (KC) of their mixed valence species were determined to be 5.8 × 106and 1.0 × 106, respectively. UV–Vis–NIR spectra of3+and4+contain intense absorption bands in the NIR region ascribed to intervalence charge transfer processes. The complexes with electronic coupling (Vab) values of 2950 (3) and 2665 cm−1(4) were classified as class III compounds according to the Robin–Day classification. These data suggest that the electronic interaction between the two iron centers is stronger than those of thep-phenylene and thienylene derivatives. Complex6, a pyrrole analogue of the photochromic dithienylethene complexes, turns out not to show photochromic behavior, indicating that the heteroaromatic component influenced significantly on photochromic behavior.