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@PHDTHESIS{Sarwar:819075,
      author       = {Sarwar, Sidra},
      othercontributors = {Kögerler, Paul and Oppel, Iris},
      title        = {{O}rganic-inorganic hybrid materials based on
                      phthalocyanine, calix[4]arene and polyoxometalate scaffolds},
      school       = {RWTH Aachen University},
      type         = {Dissertation},
      address      = {Aachen},
      publisher    = {RWTH Aachen University},
      reportid     = {RWTH-2021-04862},
      pages        = {1 Online-Ressource : Illustrationen},
      year         = {2021},
      note         = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
                      University; Dissertation, RWTH Aachen University, 2021},
      abstract     = {This doctoral thesis describes the synthesis and
                      characterization of discrete hybrid structures containing
                      organic and inorganic scaffolds covalently linked through a
                      single-metal ion. In the first part, we show how to combine
                      a phthalocyanine and a monolacunary Keggin phosphotungstate
                      into double-decker structures of 4f-centers (Tb(III) and
                      Dy(III)) that exhibit strong magnetic anisotropy in axial
                      ligand fields. Both tetradentate ligands, differing in their
                      electronic properties and charges, encapsulate 4f-ion in a
                      distorted square-antiprismatic coordination geometry. The
                      magnetic studies reveal marginal magnetic anisotropy of
                      terbium derivative, whereas the dysprosium analogue exhibit
                      significant slow magnetic relaxation. In addition, the
                      impact of electronic nature of phthalocyanine ring on the
                      properties of hybrid complexes has been studied by replacing
                      the peripheral protons with electron-donating
                      (2,6-di-iso-propylphenoxy) and electron-withdrawing
                      (fluorine) groups. UV-Vis spectra and cyclic voltammograms
                      of derivatized complexes show a shift in the signals due to
                      the changes in the electronic structure of complexes. The
                      magnetic ac-data of these complexes reveal the impact of
                      peripheral derivatization by preferring different pathways
                      to the magnetization reversal. The second part describes the
                      integration of a p-tert-butylcalix[4]arene and a
                      monolacunary Keggin phosphotungstate into heteroleptic
                      double-decker complexes of Ce(IV) and Zr(IV), representing
                      the first example of combining these scaffolds through a
                      single-metal ion. The cyclic voltammograms of these
                      complexes display two reversible redox waves at positive
                      potentials that could be attributed to the formation of
                      phenoxy radical and phenoxylium cation on the
                      p-tert-butylcalix[4]arene-skeleton. This represents the
                      first report in which a calix[4]arene shows redox-active
                      behavior upon coordination to metal, suggesting their
                      potential as electroactive materials in single-molecule
                      switches.},
      cin          = {151620 / 150000},
      ddc          = {540},
      cid          = {$I:(DE-82)151620_20140620$ / $I:(DE-82)150000_20140620$},
      typ          = {PUB:(DE-HGF)11},
      doi          = {10.18154/RWTH-2021-04862},
      url          = {https://publications.rwth-aachen.de/record/819075},
}