Scheer, Manfred and Schindler, Andrea and Bai, Junfeng and Johnson, Brian P. and Merkle, Roger and Winter, Rainer F. and Virovets, Alexander V. and Peresypkina, Eugenia V. and Blatov, V. A. and Sierka, Marek and Eckert, Hellmut (2010) Structures and Properties of Spherical 90-Vertex Fullerene-like Nanoballs. Chemistry-A European Journal 16 (7), pp. 2092-2107.
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By applying the proper stoichiometry of 1:2 to [CpRFe(η5-P5)] and CuX (X=Cl, Br) and dilution conditions in mixtures of CH3CN and solvents like CH2Cl2, 1,2-Cl2C6H4, toluene, and THF, nine spherical giant molecules having the simplified general formula [CpRFe(η5-P5)]@[1225(CH3CN)10] (CpR=η5-C5Me5 (Cp*); η5-C5Me4Et (CpEt); 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(η5-P5)], which reveals preferred orientations of π–π stacking between the cyclo-P5 rings of the guest and those of the host molecules. Moreover, π–π and σ–π 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 Ep=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 Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu2+ species are involved.
|Date:||15 February 2010|
|Institutions:||Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer|
|Keywords:||copper; host–guest systems; iron; P ligands; self-assembly|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Created at the University of Regensburg:||Yes|
|Deposited On:||23 Feb 2011 14:55|
|Last Modified:||31 Jan 2014 06:39|