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|Title: ||Design, synthesis and photophysical study of luminescent tetra(iscyano) rhenium(I) complexes|
|Other Titles: ||Si yi qing ji lai (I) pei he wu de she ji, he cheng yu guang wu li yan jiu|
四異氰基錸 (I) 配合物的設計, 合成與光物理研究
|Authors: ||Siu, Wai Kit ( 蕭偉傑)|
|Department: ||Department of Biology and Chemistry|
|Degree: ||Master of Philosophy|
|Issue Date: ||2010|
|Publisher: ||City University of Hong Kong|
|Notes: ||CityU Call Number: QC476.8 .S58 2010|
vii, 171 leaves : ill. (some col.) 30 cm.
Thesis (M.Phil.)--City University of Hong Kong, 2010.
Includes bibliographical references.
|Abstract: ||This thesis presents the design, synthesis, characterization and photophysical
properties of new classes of luminescent tetraisocyano rhenium(I) complexes.
A new series of rhenium(I) tetra(isocyano) diimine complexes, [Re(CNR)4(N-N)]+, with various isocyanide and diimine ligands of different electronic nature
(where R = 4-IC6H4, 4-BrC6H4, 4-Br-2,6-(CH3)2C6H2, 2,4,6-Cl3C6H2, 2,4,6-Br3C6H2,
2,4-Cl2-6-CH3OC6H2; N-N = 2,2'-bipyridine, 1,10-phenanthroline, 4,4'-di-tertbutyl-
2,2'-bipyridine, 4,4'-dimethoxy-2,2-bipyridine and 1-methyl-2-(2'-pyridyl)imidazole) has been synthesized and characterized. These complexes were
characterized by 1H NMR, IR, mass spectrometry and elemental analysis. The X-ray
crystal structures of three of the complexes [Re(4-IC6H4NC)4(phen)]ClO4, [Re(4-
BrPhNC)4(bpy)]PF6 and [Re(2,6-(CH3)2PhNC)4(bpy)]PF6 were also determined.
These complexes were found to show orange to red photoluminescence, which
were assigned as derived from the 3MLCT [dπ(Re) → π*(N-N)] excited state origin.
It has also been demonstrated that the emission properties of these complexes could
be readily tuned through the substituents on the isocyanide and diimine ligands. The
photophysical properties, solvatochromic behaviour and the structure-property
correlation of these complexes were investigated in details by UV-vis and emission
spectroscopy. It is worth paying attention that some of these complexes are
extremely sensitive to the polarity and rigidity of the medium. The emissive excited
state was further studied by nano-second transient absorption spectroscopy. The
electrochemical properties of these complexes by cyclic voltammetry have also been
In addition to the complexes with neutral diimine ligands, another new classes of luminescent tetra(p-bromophenylisocyano) cyclometalated rhenium(I) complexes,
[Re(CNC6H4Br)4(R1-pyind)] (where R1-pyind are substituted 2-(2'-pyridyl)indoles,
which is prepared by the reaction of the corresponding facial tricarbonyl
cyclometalated rhenium(I) complexes fac-[Re(CO)3(H2O)(R1-pyind)] have been
developed. These complexes were characterized by 1H NMR, IR, mass spectrometry
and elemental analysis. The X-ray structure of one of the facial tricarbonyl
cyclometalated rhenium(I) complexes has also been determined. The UV-vis
absorption, emission and electrochemical properties of these tricarbonyl and tetra(pbromophenylisocyano) cyclometalated rhenium(I) complexes have also been studied.|
|Online Catalog Link: ||http://lib.cityu.edu.hk/record=b4086468|
|Appears in Collections:||BCH - Master of Philosophy |
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