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61.
Julio R. Pinzón Claudia M. Cardona Dr. Maria Ángeles Herranz Dr. Marta E. Plonska‐Brzezinska Dr. Amit Palkar Andreas J. Athans Dr. Nazario Martín Prof. Dr. Antonio Rodríguez‐Fortea Dr. Josep M. Poblet Prof. Dr. Giovanni Bottari Dr. Tomás Torres Prof. Dr. S. Shankara Gayathri Dr. Dirk M. Guldi Prof. Dr. Luis Echegoyen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(4):864-877
The first pyrrolidine and cyclopropane derivatives of the trimetallic nitride templated (TNT) endohedral metallofullerenes Ih‐Sc3N@C80 and Ih‐Y3N@C80 connected to an electron‐donor unit (i.e., tetrathiafulvalene, phthalocyanine or ferrocene) were successfully prepared by 1,3‐dipolar cycloaddition reactions of azomethine ylides and Bingel–Hirsch‐type reactions. Electrochemical studies confirmed the formation of the [6,6] regioisomers for the Y3N@C80‐based dyads and the [5,6] regioisomers in the case of Sc3N@C80‐based dyads. Similar to other TNT endohedral metallofullerene systems previously synthesized, irreversible reductive behavior was observed for the [6,6]‐Y3N@C80‐based dyads, whereas the [5,6]‐Sc3N@C80‐based dyads exhibited reversible reductive electrochemistry. Density functional calculations were also carried out on these dyads confirming the importance of these structures as electron transfer model systems. Furthermore, photophysical investigations on a ferrocenyl–Sc3N@C80‐fulleropyrrolidine dyad demonstrated the existence of a photoinduced electron‐transfer process that yields a radical ion pair with a lifetime three times longer than that obtained for the analogous C60 dyad. 相似文献
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Cover Picture: Probing Polyoxometalate–Protein Interactions Using Molecular Dynamics Simulations (Chem. Eur. J. 43/2016)
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Aitala EM Amato S Anjos JC Appel JA Ashery D Banerjee S Bediaga I Blaylock G Bracker SB Burchat PR Burnstein RA Carter T Carvalho HS Copty NK Costa I Cremaldi LM Darling C Denisenko K Fernandez A Gagnon P Gerzon S Gobel C Gounder K Halling AM Herrera G Hurvits G James C Kasper PA Kwan S Langs DC Leslie J Lundberg B MayTal-Beck S Meadows B de Mello Neto JR Milburn RH de Miranda JM Napier A Nguyen A d'Oliveira AB O'Shaughnessy K Peng KC Perera LP Purohit MV Quinn B Radeztsky S Rafatian A 《Physical review letters》1996,77(12):2384-2387
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Josep-M. Poblet Carles Bo Marie-Madeleine Rohmer Marc B nard 《Chemical physics letters》1996,260(5-6):577-581
The addition of Cl, NH3, CO, C6H6 to Ti8C12 has been investigated by means of ab initio RHF and DFT calculations. The metallocarbohedrene (met-car) molecule has been modelled as a structure of a tetracapped tetrahedron with Td symmetry and two distinct metal sites, found to be most stable from previous theoretical investigations. The addition of four molecules to the atoms of the external tetrahedron of metal atoms has been found to be exothermic for all ligands considered. The addition of four extra ligands leading to T8C12(L)8 appears easy for L = Cl, and also for L = NH3. It appears that π-bonding molecules, either non-polar like benzene or weakly polar like CO, have much less affinity for the inner tetrahedron of metal atoms, which makes adducts with eight ligands difficult or impossible to obtain in that case. Those results agree with the recently observed reactivity of met-cars. 相似文献