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Synthesis and chiroptical studies of...

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Synthesis and chiroptical studies of luminescent transition metal complexes.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Synthesis and chiroptical studies of luminescent transition metal complexes./
Author:	Coughlin, Frederick John.
Description:	165 p.
Notes:	Adviser: Stefan Bernhard.
Contained By:	Dissertation Abstracts International69-10B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3333844
ISBN:	9780549863038

Synthesis and chiroptical studies of luminescent transition metal complexes.
Coughlin, Frederick John.

Synthesis and chiroptical studies of luminescent transition metal complexes. - 165 p.

Adviser: Stefan Bernhard.

Thesis (Ph.D.)--Princeton University, 2008.

Circularly polarized luminescence (CPL) has recently become a focus of research, with applications in 3D display technologies and biological probes. Partially due to the lack of commercial CPL detectors, little work has been done to correlate structural properties of the emitting molecule to the circular polarized light emission. This dissertation will demonstrate the ability to measure circular dichroism (CD) and CPL of transition metal complexes, and the ability of density functional theory (DFT) to predict their chiroptical properties. As discussed in Chapter 2, chirality about the metal center can be controlled through the use of an enantiopure hemicage ligand. Three metals, Fe(II), Ru(II), and Zn(II), were complexed with this ligand, and their electronic spectra recorded. The CD spectra of the Ru and Fe complexes contained two regions, a low energy 1MLCT transition and a higher energy 1LC transition. The Zn analog only contains the 1LC transitions, due to the filled 3d shell. Time-dependent density functional theory (TD-DFT) was subsequently used to correctly identify the transitions in these spectra, as well as to reproduce the experimental absorption and CD spectra accurately.

ISBN: 9780549863038Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis and chiroptical studies of luminescent transition metal complexes.
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020 $a 9780549863038
035 $a (UMI)AAI3333844
035 $a AAI3333844
040 $a UMI $c UMI
100 1 $a Coughlin, Frederick John. $3 1036445
245 1 0 $a Synthesis and chiroptical studies of luminescent transition metal complexes.
300 $a 165 p.
500 $a Adviser: Stefan Bernhard.
500 $a Source: Dissertation Abstracts International, Volume: 69-10, Section: B, page: .
502 $a Thesis (Ph.D.)--Princeton University, 2008.
520 $a Circularly polarized luminescence (CPL) has recently become a focus of research, with applications in 3D display technologies and biological probes. Partially due to the lack of commercial CPL detectors, little work has been done to correlate structural properties of the emitting molecule to the circular polarized light emission. This dissertation will demonstrate the ability to measure circular dichroism (CD) and CPL of transition metal complexes, and the ability of density functional theory (DFT) to predict their chiroptical properties. As discussed in Chapter 2, chirality about the metal center can be controlled through the use of an enantiopure hemicage ligand. Three metals, Fe(II), Ru(II), and Zn(II), were complexed with this ligand, and their electronic spectra recorded. The CD spectra of the Ru and Fe complexes contained two regions, a low energy 1MLCT transition and a higher energy 1LC transition. The Zn analog only contains the 1LC transitions, due to the filled 3d shell. Time-dependent density functional theory (TD-DFT) was subsequently used to correctly identify the transitions in these spectra, as well as to reproduce the experimental absorption and CD spectra accurately.
520 $a Chapter 3 focuses on the chiroptical properties of several enantiopure Ir(III) complexes, separated into enantiomers by chiral chromatography. CD and CPL spectra were measured for these complexes, and TD-DFT calculations matched the experimental spectra very well. The emission dissymmetries for these complexes ranged in absolute value from 6.0x10-4 to 3.3x10 -3, demonstrating the effect of electronic structure on CPL. Using TD-DFT calculations, a model was developed for the prediction of emission dissymmetry; this model proved accurate and was used to design the synthesis of a new target ligand which had the highest reported emission dissymmetry currently published.
590 $a School code: 0181.
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0488
710 2 $a Princeton University. $3 645579
773 0 $t Dissertation Abstracts International $g 69-10B.
790 $a 0181
790 1 0 $a Bernhard, Stefan, $e advisor
791 $a Ph.D.
792 $a 2008
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3333844