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首页> 外文期刊>Chemistry: A European journal >Hybrid molecular systems containing tetrathiafulvalene and iron-alkynyl electrophores: Five-component functional molecules obtained from C-H bond activation
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Hybrid molecular systems containing tetrathiafulvalene and iron-alkynyl electrophores: Five-component functional molecules obtained from C-H bond activation

机译：包含四硫富瓦烯和铁炔基电泳的杂化分子系统：通过C-H键活化获得的五组分功能分子

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Treatment of [Cp*(dppe)Fe-C≡C-TTFMe_3] (1) with Ag[PF_6] (3equiv) in DMF provides the binuclear complex [Cp*(dppe)Fe=C=C=TTFMe_2=CH-CH=TTFMe_2=C=C=Fe(dppe) Cp*][PF_6]_2 (2[PF_6]_2) isolated as a deep-blue powder in 69 % yield. EPR monitoring of the reaction and comparison of the experimental and calculated EPR spectra allowed the identification of the radical salt [Cp*(dppe)Fe=C=C=TTFMe _2=CH][PF_6]_2 ([1-CH][PF_6]) an intermediate of the reaction, which results from the activation of the methyl group attached in vicinal position with respect to the alkynyl-iron on the TTF ligand by the triple oxidation of 1 leading to its deprotonation by the solvent. The dimerization of [1-CH][PF_6] through carbon-carbon bond formation provides 2[PF_6]_2. The cyclic voltammetry (CV) experiments show that 2[PF_6]_2 is subject to two sequential well-reversible one-electron reductions yielding the complexes 2[PF_6] and 2. The CV also shows that further oxidation of 2[PF_6] _2 generates 2[PF_6]_n (n=3-6) at the electrode. Treatment of 2[PF_6]_2 with KOtBu provides 2[PF_6] and 2 as stable powders. The salts 2[PF_6] and 2[PF_6] _2 were characterized by XRD. The electronic structures of 2 ~(n+) (n=0-2) were computed. The new complexes were also characterized by NMR, IR, M?ssbauer, EPR, UV/Vis and NIR spectroscopies. The data show that the three complexes 2[PF_6]_n are iron(II) derivatives in the ground state. In the solid state, the dication 2~(2+) is diamagnetic and has a bis(allenylidene-iron) structure with one positive charge on each iron building block. In solution, as a result of the thermal motion of the metal-carbon backbone, the triplet excited state becomes thermally accessible and equilibrium takes place between singlet and triplet states. In 2[PF_6], the charge and the spin are both symmetrically distributed on the carbon bridge and only moderately on the iron and TTFMe_2 electroactive centers. Power of five: A five-component functional molecule was prepared by C-H bond activation. This multifunctional molecule appears as a hybrid system not only because it contains inorganic and organic electrophores, but mainly because the electronic properties of the resulting "device" originate from the closely intertwined combination between the two Fe centers, the two TTFMe_2 moieties, and the carbon bridge (see figure; TTFMe_2=3,4-dimethyltetrathiafulvalene).
机译：在DMF中用Ag [PF_6]（3equiv）处理[Cp *（dppe）Fe-C≡C-TTFMe_3]（1）可提供双核络合物[Cp *（dppe）Fe = C = C = TTFMe_2 = CH-CH = TTFMe_2 = C = C = Fe（dppe）Cp *] [PF_6] _2（2 [PF_6] _2）以深蓝色粉末的形式分离，产率为69％。对反应进行EPR监测并比较实验和计算出的EPR光谱，可以鉴定出自由基盐[Cp *（dppe）Fe = C = C = TTFMe _2 = CH] [PF_6] _2（[1-CH] [PF_6 ]）反应的中间体，其是通过1的三重氧化作用导致相对于TTF配体上炔基-铁邻位连接的甲基的活化，导致其被溶剂去质子化。 [1-CH] [PF_6]通过碳-碳键形成的二聚提供2 [PF_6] _2。循环伏安法（CV）实验表明2 [PF_6] _2经历了两次连续可逆的单电子还原，生成了络合物2 [PF_6]和2。CV还显示了2 [PF_6] _2的进一步氧化电极上为2 [PF_6] _n（n = 3-6）。用KOtBu处理2 [PF_6] _2可得到2 [PF_6]和2的稳定粉末。盐2 [PF_6]和2 [PF_6] _2通过XRD表征。计算出2〜（n +）（n = 0-2）的电子结构。新的配合物还通过NMR，IR，Msssbauer，EPR，UV / Vis和NIR光谱进行表征。数据表明，三个配合物2 [PF_6] _n是基态的铁（II）衍生物。在固态时，指示2〜（2+）是抗磁性的，具有双（亚烯基-铁）结构，每个铁结构单元上带有一个正电荷。在溶液中，由于金属-碳骨架的热运动，三重态激发态变得热可及，并且在单重态和三重态之间发生平衡。在2 [PF_6]中，电荷和自旋均对称分布在碳桥上，仅适度分布在铁和TTFMe_2电活性中心上。五次幂：通过C-H键活化制备五组分功能分子。这个多功能分子表现为杂化系统，不仅因为它包含无机和有机电泳，而且还主要是因为所得“装置”的电子特性源自两个Fe中心，两个TTFMe_2部分和碳之间紧密缠结的组合。桥（见图; TTFMe_2 ＝ 3，4-二甲基四硫富瓦烯）。

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