Hytteballe, Sophie: Synthesis of ligands for self-assembly of discrete metallo-supramolecular complexes. - Bonn, 2016. - Dissertation, Rheinische Friedrich-Wilhelms-Universität Bonn.
Online-Ausgabe in bonndoc: https://nbn-resolving.org/urn:nbn:de:hbz:5n-42739
@phdthesis{handle:20.500.11811/6717,
urn: https://nbn-resolving.org/urn:nbn:de:hbz:5n-42739,
author = {{Sophie Hytteballe}},
title = {Synthesis of ligands for self-assembly of discrete metallo-supramolecular complexes},
school = {Rheinische Friedrich-Wilhelms-Universität Bonn},
year = 2016,
month = feb,

note = {Different aspects of self-assembly and self-sorting of metallo-supramolecular have been investigated in this thesis. Starting with self-sorting, four different 9,9'-spirobifluorene derivatives substituted with pyridine were synthesized as racemates as well as in enatiomerically pure form and used to investigate self-discrimination and self-recognition during the assembly of two different rhombic systems consisting of two ligands and two metal ions; Pd- or Pt-corner (M2L2). The two systems differ in the lengths of the spacer between the spirobifluorene and the metal-binding pyridine, the smaller one having no spacer and the long one having an ethynylspacer.
For the ligand with the shorter spacer a crystal structure of the homochiral complex was obtained, confirming the preference for self-recognition of the system, which was also observed in the NMR- and mass spectra. In the case of the larger ligand no self-sorting behavior was observed. The ability of the larger ligand to form a catenane was established by mass, 1H-NMR-spectroscopy and crystallography.
The small spirobifluorene based ligand was used with Pd(II)to form a M6L12-sphere, and several attempts were made to confirm the presence of the M6L12-species. A smaller M2L4- cage was formed with a third synthesized spirobifluorene derivative and confirmed by mass spectroscopy.
Two ligands with both a soft and a hard metal-binding site were synthesized and used in complexation experiments with Ti(IV), Pd(II) and Pt(II) in order to obtain a self-assembled supramolecular multicomponent complex. We succeeded in performing the first complexation steps with both ligands, preparing for the final complexation event.
Lastly, a ligand based on a thiophene core with bipyridine as the metal binding unit was synthesized and tested for its ability to form a triple helix with Fe(II) and undergo spin crossover.},

url = {http://hdl.handle.net/20.500.11811/6717}
}

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