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@ARTICLE{Gasevic:602305,
      author       = {Gasevic, Thomas and Bamberg, Marcel and Wicke, Julius and
                      Bolte, Michael and Virovets, Alexandr and Lerner,
                      Hans-Wolfram and Grimme, Stefan and Hansen, Andreas and
                      Wagner, Matthias and Bursch, Markus},
      title        = {{C}onfined {L}ewis {P}airs: {I}nvestigation of the ${X}^−
                      →$ {S}i$_{20}$ {I}nteraction in
                      {H}alogen‐{E}ncapsulating {S}ilafulleranes},
      journal      = {Angewandte Chemie / International edition},
      volume       = {63},
      number       = {6},
      issn         = {1433-7851},
      address      = {Weinheim},
      publisher    = {Wiley-VCH},
      reportid     = {PUBDB-2024-00580},
      pages        = {e202314238},
      year         = {2024},
      abstract     = {A joint theoretical and experimental study on 32 endohedral
                      silafullerane derivatives [X@Sii$_{20}$Yi$_{20}$] (X = F-I;
                      Y = F-I, H, Me, Et) and Th-[Cl@Sii$_{20}$Hi$_{12}$Y$_8$] (Y
                      = F-I) is presented. First, we evaluated the structure
                      determining template effect of Cl in a systematic series of
                      concave silapolyquinane model systems. Second, we
                      investigated the X$^- \to$ Si$_{20}$ interaction energy
                      (Eint) as a function of X and Y and found the largest Eint
                      values for electron-withdrawing exohedral substituents Y.
                      Given that X ions can be considered as Lewis bases and empty
                      Sii$_{20}$Yi$_{20}$ clusters as Lewis acids, we classify our
                      inseparable host–guest complexes [X@Sii$_{20}$Yi$_{20}$]
                      as “confined Lewis pairs”. Third, $^{35}$Cl NMR
                      spectroscopy proved to be highly diagnostic for an
                      experimental assessment of the Cl$^- \to$ Sii$_{20}$
                      interaction as the paramagnetic shielding and, in turn,
                      delta($^{35}$Cl) of the endohedral Cl ion correlate
                      inversely with Eint. Finally, we disclose the synthesis of
                      [PPN][Cl@Sii$_{20}$Yi$_{20}$](Y = Me, Et, Br) and provide a
                      thorough characterization of these new silafulleranes.},
      cin          = {DOOR ; HAS-User},
      ddc          = {540},
      cid          = {I:(DE-H253)HAS-User-20120731},
      pnm          = {6G3 - PETRA III (DESY) (POF4-6G3) / DFG project 506550642 -
                      Siladodecahedrane: Untersuchungen zu Reaktivität,
                      Bindungssituation und optoelektronischen Eigenschaften
                      (506550642)},
      pid          = {G:(DE-HGF)POF4-6G3 / G:(GEPRIS)506550642},
      experiment   = {EXP:(DE-H253)P-P24-20150101},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:38059423},
      UT           = {WOS:001138626400001},
      doi          = {10.1002/anie.202314238},
      url          = {https://bib-pubdb1.desy.de/record/602305},
}