Preparative And Spectroscopic Studies Of Some Platinum And Palladium Complexes

Author : Charlotte Po
Publisher : Open Dissertation Press
ISBN 13 : 9781361031704
Total Pages : 392 pages
Book Rating : 4.0/5 (317 download)

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Download or read book DESIGN SYNTHESIS & SPECTROSCOP written by Charlotte Po and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 392 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis and Spectroscopic Studies of Amphiphilic Platinum(II) Complexes With Tridentate N-donor Ligands: From Simple Molecules to Supramolecular Assemblies and Nanostructures" by Charlotte, Po, 布珮樂, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN, SYNTHESIS AND SPECTROSCOPIC STUDIES OF AMPHIPHILIC PLATINUM(II) COMPLEXES WITH TRIDENTATE N-DONOR LIGANDS - FROM SIMPLE MOLECULES TO SUPRAMOLECULAR ASSEMBLIES AND NANOSTRUCTURES Submitted by PO Charlotte for the degree of Doctor of Philosophy at The University of Hong Kong in February 2014 Several series of amphiphilic platinum(II) complexes with tridentate N-donor ligands were synthesized and characterized. Their photophysical properties as well as the spectroscopic changes resulting from the supramolecular assemblies of the complexes were studied. Water-soluble platinum(II) bzimpy complexes have been shown to exhibit strong aggregation in water to give highly ordered nanostructures and by structural modification, various morphologies such as spherical and cylindrical micelles, vesicles and bilayer sheets were obtained. The differences in molecular packing and morphology have been found to give rise to an alteration of Pt---Pt interaction and hence a change in MMLCT absorption and MMLCT emission and such changes were utilized as a probe for the morphological transformation. - + Different hydrophilic groups of sulfonate (-SO ), trimethylammonium (-NMe ) and 3 3 triethylene glycol (TEG) were incorporated into the platinum(II) bzimpy complexes to render their water solubility. An interesting aggregation-partial deaggregation-aggregation process has been demonstrated by [Pt{bzimpy(PrSO ) }Cl]K and its alkynyl analogues via a change in the solvent 3 2 composition. A drastic rainbow-like color change from red to yellow to green and blue was observed via the increase in organic solvent content in the aqueous solution of [Pt{bzimpy(PrSO )}Cl]K. The color change and luminescence change were 3 2 monitored by UV-vis absorption and emission studies, and a change in the MMLCT absorption and emission due to the alteration in Pt---Pt interactions during the assembly and disassembly process was observed. Through microscopy studies, the spectroscopic changes were correlated to a morphological transformation from vesicle to rod. The degree of aggregation of the complexes with different hydrophilic groups was compared through their dimerization constant and the inferences of electrostatic interactions on assemblies were investigated through the modulation of salt content of the solution and via co-assembly studies of the highly charged complexes, [Pt{bzimpy(PrSO ) (OPrSO )}Cl]K and [Pt{bzimpy(C H -NMe ) }Cl]Cl . 3 2 3 2 10 20 3 2 3 Through the incorporation of hydrophilic alkynyl ligands, bolaamphiphilic complexes were also synthesized and their aggregation behavior in water was studied. The effect in tuning the hydrophobicity of the complexes was studied by varying the alkyl chain length of the sulfonate-pendant platinum(II) bzimpy (Pt{bzimpy(PrSO ) }) 3 2 complexes and an unexpected shift in the UV-vis absorption and emission was observed due to the formation of aggregates. The thermo-responsive behavior of a TEG-pendant alkynylplatinum(II) bzimpy complex, [Pt{bzimpy(TEG) }{C≡CC H - 2 6 3 (OC H )-3,5}]Cl, in aqueous solution was investigated and on increasing 12 25 2 temperature, a morphological transformation from bilayer sheet to spherical micelles was observed and a large hysteresis