Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]

Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]

Bibliographic Details
Main Author: Yarnell, James E.
Language:English
Published: Bowling Green State University / OhioLINK 2010
Subjects:
Chemistry
Physics
Rhenium(I) carbonyl
thermal equilibrium
photophysics
transient absorption
infrared
Re(I)
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1269261887
id ndltd-OhioLink-oai-etd.ohiolink.edu-bgsu1269261887
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-bgsu12692618872021-08-03T05:29:13Z Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl] Yarnell, James E. Chemistry Physics Rhenium(I) carbonyl thermal equilibrium photophysics transient absorption infrared Re(I) This thesis describes the synthesis and photophysics of a new Re(I)-carbonyl diimine complex, [Re(PNI-phen)(CO)<sub>3</sub>Cl], where the PNI-phen is N-(1,10-phenanthroline)-4-nitronaphthalene-1,8-dicarboximide. The PNI chromophore effectively sensitizes the metal-to-ligand charge transfer (MLCT) state through efficient Förster-type singlet energy transfer. This complex exhibits extended MLCT emission lifetimes as a result of having triplet ligand-centered (<sup>3</sup>LC) states nearly isoenergetic to the <sup>3</sup>MLCT states. Once the excited-state is in the triplet manifold, a thermal equilibrium is achieved between the <sup>3</sup>LC and the <sup>3</sup>MLCT states. This equilibrium increases the MLCT emission lifetime approximately 3000-fold at room temperature relative to the MLCT model complex, [Re(phen)(CO)<sub>3</sub>Cl]. Thermal equilibrium is lost at 77 K since the emission decays independently from both the <sup>3</sup>LC and <sup>3</sup>MLCT states. Temperature dependent photoluminescence experiments estimate the energy gap between the two triplet excited states to be about 1500 to 1600 cm<sup>-1</sup> at room temperature. The evolution of excited-states formed following the original Frank-Condon state excitation are studied using a number of techniques including transient absorption, time-resolved infrared, and time-resolved photoluminescence spectroscopy. These instrumental techniques allow us to monitor the excited-state dynamics ranging from the femtosecond to the millisecond time domain. 2010-06-02 English text Bowling Green State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1269261887 http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1269261887 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Chemistry
Physics
Rhenium(I) carbonyl
thermal equilibrium
photophysics
transient absorption
infrared
Re(I)
spellingShingle Chemistry
Physics
Rhenium(I) carbonyl
thermal equilibrium
photophysics
transient absorption
infrared
Re(I)
Yarnell, James E.
Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
author Yarnell, James E.
author_facet Yarnell, James E.
author_sort Yarnell, James E.
title Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
title_short Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
title_full Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
title_fullStr Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
title_full_unstemmed Exploring the Photophysics of [Re(PNI-Phen)(CO)<sub>3</sub>Cl]
title_sort exploring the photophysics of [re(pni-phen)(co)<sub>3</sub>cl]
publisher Bowling Green State University / OhioLINK
publishDate 2010
url http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1269261887
work_keys_str_mv AT yarnelljamese exploringthephotophysicsofrepniphencosub3subcl
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