Scheer, Manfred and Schindler, Andrea and Bai, Junfeng and Johnson, Brian P. and Merkle, Roger and Winter, Rainer and Virovets, Alexander V. and Peresypkina, Eugenia V. and Blatov, Vladislav 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. ISSN 0947-6539,
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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 Density functional calculations reveal that during oxidation and reduction the electrons are withdrawn or added to the surface of the spherical nanomolecules, and no Cu(2+) species are involved.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ANION-PI INTERACTIONS; GAUSSIAN-BASIS SETS; N-LIGAND COMPLEXES; CRYSTAL-STRUCTURES; COORDINATION CHEMISTRY; TRANSITION-METALS; CYCLO-E(5) LIGAND; BUILDING-BLOCKS; ATOMS LI; CLUSTER; copper; host-guest systems; iron; P ligands; self-assembly |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Aug 2020 10:07 |
| Last Modified: | 12 Aug 2020 10:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/25394 |
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