Structures and properties of spherical 90-vertex fullerene-like nanoballs.
Structures and properties of spherical 90-vertex fullerene-like nanoballs.
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DOI：
10.1002/chem.200902554
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发表时间：
2010-02
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通讯作者：
M. Scheer;Andrea Schindler;J. Bai;Brian P. Johnson;R. Merkle;R. Winter;A. Virovets;E. Peresypkina;V. Blatov;M. Sierka;H. Eckert
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作者：
M. Scheer;Andrea Schindler;J. Bai;Brian P. Johnson;R. Merkle;R. Winter;A. Virovets;E. Peresypkina;V. Blatov;M. Sierka;H. Eckert
在CH(3)CN与CH(2)Cl(2)、1,2-Cl(2)C(6)H(4)、甲苯和THF等溶剂的混合物中，采用适当的1:2的化学计量比[Cp(R)Fe(eta(5)-P(5))]和CuX （X=Cl, Br）的稀释条件，得到9个球形大分子，其简化通式为[Cp(R)Fe(eta(5)-P(5))]@[{Cp(R)Fe(eta(5)-P(5))}(12){CuX}(25)(CH(3)CN)(10)] (Cp(R)=eta(5)-C(5)Me(5) (Cp*)；埃塔(5)- c(5)我(4)等(Cp (Et));X=Cl, Br)已合成并进行了结构表征。产物由非碳原子组成的90顶点框架组成，形成类似富勒烯的结构基序。除了大多数中性产物外，还分离出了一些带电衍生物。这些球形大分子的外径为2.24 （X=Cl）至2.26 nm (X=Br)，内腔大小分别为1.28 （X=Cl）和1.20 nm （X=Br）。在大多数情况下，这些纳米球的内部空隙封装了一个[Cp*Fe(eta(5)-P(5))]分子，这揭示了客体分子和宿主分子环-P(5)环之间pi-pi堆叠的首选方向。此外，在晶格中球的填充基元中也发现了π和σ - π相互作用。在E(p)=0.615 V时发生了不可逆的多电子氧化反应，在-1.10和-2.0 V处发生了两个还原步骤，其中第一个步骤约对应12个电子。密度泛函计算表明，在氧化和还原过程中，电子被撤回或添加到球形纳米分子的表面，并且不涉及Cu（2+）物质。
By applying the proper stoichiometry of 1:2 to [Cp(R)Fe(eta(5)-P(5))] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH(3)CN and solvents like CH(2)Cl(2), 1,2-Cl(2)C(6)H(4), toluene, and THF, nine spherical giant molecules having the simplified general formula [Cp(R)Fe(eta(5)-P(5))]@[{Cp(R)Fe(eta(5)-P(5))}(12){CuX}(25)(CH(3)CN)(10)] (Cp(R)=eta(5)-C(5)Me(5) (Cp*); eta(5)-C(5)Me(4)Et (Cp(Et)); X=Cl, Br) have been synthesized and structurally characterized. The products consist of 90-vertex frameworks consisting of non-carbon atoms and forming fullerene-like structural motifs. Besides the mostly neutral products, some charged derivatives have been isolated. These spherical giant molecules show an outer diameter of 2.24 (X=Cl) to 2.26 nm (X=Br) and have inner cavities of 1.28 (X=Cl) and 1.20 nm (X=Br) in size. In most instances the inner voids of these nanoballs encapsulate one molecule of [Cp*Fe(eta(5)-P(5))], which reveals preferred orientations of pi-pi stacking between the cyclo-P(5) rings of the guest and those of the host molecules. Moreover, pi-pi and sigma-pi interactions are also found in the packing motifs of the balls in the crystal lattice. Electrochemical investigations of these soluble molecules reveal one irreversible multi-electron oxidation at E(p)=0.615 V and two reduction steps (-1.10 and -2.0 V), the first of which corresponds to about 12 electrons. Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu(2+) species are involved.