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

doi:10.1021/j100200a031

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

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 a_2u and a_1u 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 a_2u orbital with a hole delocalized over the two porphyrin rings.

Original language	English
Pages (from-to)	8374-8377
Number of pages	4
Journal	Journal of physical chemistry
Volume	96
Issue number	21
DOIs	https://doi.org/10.1021/j100200a031
Publication status	Published - 1992

All Science Journal Classification (ASJC) codes

Engineering(all)
Physical and Theoretical Chemistry

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10.1021/j100200a031

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@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",

doi = "10.1021/j100200a031",

language = "English",

volume = "96",

pages = "8374--8377",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

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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

Y1 - 1992

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.

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