Статья

Atomic Nitrogen Encapsulated in Fullerenes: Effects of Cage Variations

Elke DietelContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyAndreas HirschContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyB. PietzakContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyM. WaiblingerContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyK. LipsContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyA. WeidingerContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyAndrea GrußContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, GermanyKlaus‐Peter DinseContribution from Organic Chemistry II, Universität Erlangen, Henkestrasse 42, D-91054 Erlangen, Germany, Hahn-Meitner Institut Berlin, Glienickerstrasse 100, D-14109 Berlin, Germany, Hahn-Meitner Institut Berlin, Rudower Chaussee 5, D-14109 Berlin, Germany, and Physical Chemistry III, TU Darmstadt, Petersenstrasse 20, D-64287 Darmstadt, Germany

1999en

ABI

Аннотация

The synthesis and EPR spectroscopic investigations of a family of six endohedral fullerenes, namely, N@C60 (1), N@C61(COOC2H5)2 (2), N@C66(COOC2H5)12 (3), N@C66(COOC2D5)12 (4), N@C61(COOC2D5)2 (5), and N@C70 (6), containing atomic nitrogen in the 4S3/2 ground state is described. The parent systems N@C60 (1) and N@C70 (6) were synthesized by nitrogen ion implantation. The syntheses of the C2v-symmetric monoadducts 2 and 5 and the Th symmetric hexaadducts 3 and 4 exhibiting well-defined cage distortions were accomplished via cyclopropanation with the corresponding malonates. With respect to these additions the reactivity of 1 is indistinguishable from that of empty C60. The quartet electronic spin of the encapsulated N-atoms is a very sensitive probe for cage modifications. In the monoadducts 2 and 5 a permanent zero field splitting (ZFS) tensor with rigidly aligned axes was revealed reflecting the intrinsic droplet like cage distortion. In contrast, no fine structure due to intrinsic distortions was monitored in the ESR spectra of the highly symmetric hexaadducts 3 and 4. In these cases only matrix-induced distortions of the cage lead to ZFS interactions. In solution fluctuations of the ZFS tensor are the major source of spin relaxation. The root-mean-square value of this collision-induced fluctuating ZFS interaction as estimated from relaxation data for N@C60 (1) and the hexaadduct 3 is in the range of the ZFS interaction measured for the monoadduct 2.

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Идентификаторы

DOI: 10.1021/ja983812s

Цитирования и источники

Цитирований: 2Использованных источников: 0

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