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@PHDTHESIS{Sturm:854946,
      author       = {Sturm, Lisa},
      othercontributors = {Oppel, Iris Marga and Albrecht, Markus},
      title        = {{E}influss von {P}seudohalogeniden und {C}arboxylaten auf
                      die {K}omplexierung zweiwertiger {M}etallionen durch
                      {T}ris(2-pyridinylen-{N}-oxid)triaminoguanidin},
      school       = {RWTH Aachen University},
      type         = {Dissertation},
      address      = {Aachen},
      publisher    = {RWTH Aachen University},
      reportid     = {RWTH-2022-09881},
      pages        = {1 Online-Ressource : Illustrationen},
      year         = {2022},
      note         = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
                      University; Dissertation, RWTH Aachen University, 2022},
      abstract     = {C3-symmetric triaminoguanidine based ligands are
                      established as triangular building blocks in supramolecular
                      compounds like polymers or discrete monomers, dimers, and
                      polyhedra. The reaction of
                      tris(2-pyridinylene-N-oxide)triaminoguanidine with zinc(II)
                      carboxylates in presence of (pseudo)halides results in
                      protein-sized metallocycles consisting of twelve ligands
                      linked by octahedrally coordinated zinc(II) centers. Besides
                      crystals of the metallocycles, the crystallization of
                      carboxylate-bridged coordination di/polymers is observed in
                      the same reaction vessel. To address this issue, the
                      influence of the solvent, the chain length of the
                      carboxylate, the co-ligands and their stoichiometry is
                      investigated, while other factors are kept as constant as
                      possible. In this way, a sensitive dependence of the binding
                      motif on the stoichiometric pseudohalide-carboxylate ratio
                      was revealed. Small or no amounts of pseudohalide combined
                      with sufficient equivalents of carboxylate lead to the
                      formation of carboxylate-bridged di/polymers. Increasing the
                      pseudohalide stoichiometry results in the crystallization of
                      mixed compounds and finally of metallocycles. By adjusting
                      the co-ligand stoichiometry, crystallization of a desired
                      compound can be predicted and selectively induced. Applying
                      this principle to the chemically related cadmium(II) yields
                      in a series of carboxylate-bridged di/polymers, whereas the
                      addition of thiocyanate gives a cadmium(II)-bridged
                      structure, which can be considered as metallocycle fragment.
                      Cadmium(II) prefers coordination numbers of six and higher
                      due to its ionic radius, which inhibits the formation of a
                      metallocycle. Cobalt(II) ions instead built up polymers and
                      metallocycles showing the same co-ligand dependence as
                      zinc(II). Magnetic measurements revealed predominantly
                      antiferromagnetic behavior of these compounds due to short
                      Co(II)-Co(II) distances. In heterometallic metallocycles,
                      zinc(II) ions may isolate the cobalt(II) centers, which
                      could probably result in very large discrete molecules with
                      interesting magnetic properties.},
      cin          = {151520 / 150000},
      ddc          = {540},
      cid          = {$I:(DE-82)151520_20140620$ / $I:(DE-82)150000_20140620$},
      typ          = {PUB:(DE-HGF)11},
      doi          = {10.18154/RWTH-2022-09881},
      url          = {https://publications.rwth-aachen.de/record/854946},
}