Transient absorption, time-resolved fluorescence, and resonance Raman spectroscopic studies of Zr(TPP)2 and Zr(TPP)2(SbCl6)

Minyung Lee, Ok Keun Song, Jung Chul Seo, Dongho Kim, Hee Joon Kim, Kimoon Kim

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Transient absorption, time-resolved fluorescence, and resonance Raman measurements are reported for Zr(TPP)2 and for the complex Zr(TPP)2(SbCl6) in which an electron is removed from the porphyrin π-system. The singlet excited-state lifetime of Zr(TPP)2 in dichloromethane was measured to be 1.9 ± 0.1 ns through the transient absorption technique and 1.95 ± 0.05 ns using the time-correlated single photon counting method, respectively. By contrast, the excited-state lifetime of Zr(TPP)2(SbCl6) was found to be 40 ± 10 ps, which is much shorter than that of the neutral species. The fast nonradiative deactivation of the cationic complex is likely caused by the rapid quenching of the initially excited doublet (π,π*) state via one or more of the states seen in the near-IR ground-state absorption spectrum. These low energy states correspond to transitions between the molecular orbitals derived from the a2u and a1u monomer orbitals through the π,π interaction of the two porphyrin subunits. In addition, resonance Raman spectroscopic data confirm that in Zr(TPP)2(SbCl6) one electron is removed from a dimer orbital derived from the monomer a2u orbital with a hole delocalized over the two porphyrin rings.

Original languageEnglish
Pages (from-to)8374-8377
Number of pages4
JournalJournal of Physical Chemistry
Volume96
Issue number21
Publication statusPublished - 1992 Dec 1

Fingerprint

Porphyrins
Excited states
porphyrins
Fluorescence
orbitals
fluorescence
monomers
Monomers
excitation
Rapid quenching
life (durability)
Electrons
Methylene Chloride
Dichloromethane
Molecular orbitals
Electron transitions
Dimers
deactivation
Electron energy levels
Ground state

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Lee, Minyung ; Song, Ok Keun ; Seo, Jung Chul ; Kim, Dongho ; Kim, Hee Joon ; Kim, Kimoon. / Transient absorption, time-resolved fluorescence, and resonance Raman spectroscopic studies of Zr(TPP)2 and Zr(TPP)2(SbCl6). In: Journal of Physical Chemistry. 1992 ; Vol. 96, No. 21. pp. 8374-8377.
@article{1309a6e19c5d44f59764a5cbcf7e5eaa,
title = "Transient absorption, time-resolved fluorescence, and resonance Raman spectroscopic studies of Zr(TPP)2 and Zr(TPP)2(SbCl6)",
abstract = "Transient absorption, time-resolved fluorescence, and resonance Raman measurements are reported for Zr(TPP)2 and for the complex Zr(TPP)2(SbCl6) in which an electron is removed from the porphyrin π-system. The singlet excited-state lifetime of Zr(TPP)2 in dichloromethane was measured to be 1.9 ± 0.1 ns through the transient absorption technique and 1.95 ± 0.05 ns using the time-correlated single photon counting method, respectively. By contrast, the excited-state lifetime of Zr(TPP)2(SbCl6) was found to be 40 ± 10 ps, which is much shorter than that of the neutral species. The fast nonradiative deactivation of the cationic complex is likely caused by the rapid quenching of the initially excited doublet (π,π*) state via one or more of the states seen in the near-IR ground-state absorption spectrum. These low energy states correspond to transitions between the molecular orbitals derived from the a2u and a1u monomer orbitals through the π,π interaction of the two porphyrin subunits. In addition, resonance Raman spectroscopic data confirm that in Zr(TPP)2(SbCl6) one electron is removed from a dimer orbital derived from the monomer a2u orbital with a hole delocalized over the two porphyrin rings.",
author = "Minyung Lee and Song, {Ok Keun} and Seo, {Jung Chul} and Dongho Kim and Kim, {Hee Joon} and Kimoon Kim",
year = "1992",
month = "12",
day = "1",
language = "English",
volume = "96",
pages = "8374--8377",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "21",

}

Transient absorption, time-resolved fluorescence, and resonance Raman spectroscopic studies of Zr(TPP)2 and Zr(TPP)2(SbCl6). / Lee, Minyung; Song, Ok Keun; Seo, Jung Chul; Kim, Dongho; Kim, Hee Joon; Kim, Kimoon.

In: Journal of Physical Chemistry, Vol. 96, No. 21, 01.12.1992, p. 8374-8377.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Transient absorption, time-resolved fluorescence, and resonance Raman spectroscopic studies of Zr(TPP)2 and Zr(TPP)2(SbCl6)

AU - Lee, Minyung

AU - Song, Ok Keun

AU - Seo, Jung Chul

AU - Kim, Dongho

AU - Kim, Hee Joon

AU - Kim, Kimoon

PY - 1992/12/1

Y1 - 1992/12/1

N2 - Transient absorption, time-resolved fluorescence, and resonance Raman measurements are reported for Zr(TPP)2 and for the complex Zr(TPP)2(SbCl6) in which an electron is removed from the porphyrin π-system. The singlet excited-state lifetime of Zr(TPP)2 in dichloromethane was measured to be 1.9 ± 0.1 ns through the transient absorption technique and 1.95 ± 0.05 ns using the time-correlated single photon counting method, respectively. By contrast, the excited-state lifetime of Zr(TPP)2(SbCl6) was found to be 40 ± 10 ps, which is much shorter than that of the neutral species. The fast nonradiative deactivation of the cationic complex is likely caused by the rapid quenching of the initially excited doublet (π,π*) state via one or more of the states seen in the near-IR ground-state absorption spectrum. These low energy states correspond to transitions between the molecular orbitals derived from the a2u and a1u monomer orbitals through the π,π interaction of the two porphyrin subunits. In addition, resonance Raman spectroscopic data confirm that in Zr(TPP)2(SbCl6) one electron is removed from a dimer orbital derived from the monomer a2u orbital with a hole delocalized over the two porphyrin rings.

AB - Transient absorption, time-resolved fluorescence, and resonance Raman measurements are reported for Zr(TPP)2 and for the complex Zr(TPP)2(SbCl6) in which an electron is removed from the porphyrin π-system. The singlet excited-state lifetime of Zr(TPP)2 in dichloromethane was measured to be 1.9 ± 0.1 ns through the transient absorption technique and 1.95 ± 0.05 ns using the time-correlated single photon counting method, respectively. By contrast, the excited-state lifetime of Zr(TPP)2(SbCl6) was found to be 40 ± 10 ps, which is much shorter than that of the neutral species. The fast nonradiative deactivation of the cationic complex is likely caused by the rapid quenching of the initially excited doublet (π,π*) state via one or more of the states seen in the near-IR ground-state absorption spectrum. These low energy states correspond to transitions between the molecular orbitals derived from the a2u and a1u monomer orbitals through the π,π interaction of the two porphyrin subunits. In addition, resonance Raman spectroscopic data confirm that in Zr(TPP)2(SbCl6) one electron is removed from a dimer orbital derived from the monomer a2u orbital with a hole delocalized over the two porphyrin rings.

UR - http://www.scopus.com/inward/record.url?scp=0001742375&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001742375&partnerID=8YFLogxK

M3 - Article

VL - 96

SP - 8374

EP - 8377

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 21

ER -