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Title: Complexes of ligands containing the Methylenediphenol Unit
Authors: Ma, Xiaomei
Issue Date: 2010
Publisher: © Xiaomei Ma
Abstract: A range of phenol-based pseudocalixarene macrocycles and non-macrocyclic complexes derived from the precursor MHMP [2,2 -methylene-bis(6-(hydroxymethyl)-4-methylphenol)] were synthesised and their properties were investigated. The synthesis of MHMP and methods of oxidation to MFMP [2,2 -methylene-bis(6-(formyl)-4-methylphenol)] were developed and are discussed. Several literature methods of oxidation were investigated and it was found that the best method of oxidation is using activated MnO2. A range of di- and tetranuclear pseudocalixarene macrocycles were synthesised and characterised by analytical techniques, particularly mass spectrometry. Two dinuclear complexes were obtained as suitable crystals for structure determination. X-ray crystallography showed that the structures are controlled by two strong hydrogen bonds which resulted from mono-deprotonation of the methylenediphenol units. The hydrogen bonding can be controlled by the charge on the metal ion and the pH of the solvent, UV-visible spectroscopy was used to investigate the pH-dependence of the hydrogen bonding. An intermediate in the synthesis of heteronuclear Cu4Ba [4+4] pseudocalixarene macrocycles, [Cu4Ba(MFMP)4(EtOH)4](ClO4)2.4EtOH, has been isolated, from MFMP with barium and copper salts in the presence of a base. This complex was structurally characterised and the core is similar to the [4+4] macrocycle. The complex provides good evidence of a possible route to formation of large membered macrocyclic heteronuclear complex and suggests a mechanism for controlling the formation of the [4+4] heteronuclear macrocyclic complexes. Non-macrocyclic compartmental complexes of the free ligands H2A4PY [2,2 -methylene-bis(6-(bis(pyridine-2-ylmethyl)aminomethyl))-4-methylphenol)], H2A2PY [2,2 -methylene-bis(6-(pyridine-2-ylmethyl)aminomethyl))-4-methylphenol)] and H2AMEN [2,2 -methylene-bis(6-(N,N- dimethylaminethyl)aminomethyl))-4-methylphenol) were synthesised. Since the complexes were not crystallised, their precise formula and the extent of deprotonation of the phenol oxygen atoms is difficult to judge, but possible structures are suggested by comparison with known structures and by mass spectrometry, IR and magnetic measurements.
Description: Closed access. If you are the author of this thesis and would like to make it available on open access please contact the library. A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.
URI: https://dspace.lboro.ac.uk/2134/7243
Appears in Collections:Closed Access PhD Theses (Chemistry)

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