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Title: Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly

Abstract

Photoinduced structural changes (PSC) is one of the fundamental excited-state dynamical processes, and yet often very challenging to distinguish from competing electronic excited-state relaxation channels having similar or even comparable timescales. Here, we report a detailed study on the PSC of a pyrazolate bridged platinum(II) binuclear complex, a so called molecular butterfly, using time-correlated single photon counting measurements at different wavelengths and sample temperatures. Analysis of the results obtained using dichloromethane (DCM) and ethylene carbonate (EC) as solvents enabled us to reveal an unexpected, strong solvent effect on the PSC processes. We show that a rapid PSC process with a characteristic timescale of 323 ps is observed in DCM, which leads to excitation equilibrium between the ligand center/metal-to-ligand charge transfer ( 3LC/MLCT) and metal-metal-to-ligand charge transfer (3MMLCT) triplet states. The subsequent relaxation from these electronic states to ground state takes place in several nanoseconds. In contrast, the corresponding PSC process in EC appears slow at all temperatures studied in our experiments and showed no sign of such excitation equilibrium. The observed solvent effect is found to arise from distinct solvent properties including their viscosities and polarities as well as the peculiar electronic excited-states of the butterfly-like molecules having charge transfermore » character.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. Florida A&M Univ. - Florida State Univ. (FAMU-FSU) College of Engineering, Tallahassee, FL (United States). Dept. of Chemical and Biomedical Engineering
  3. Florida A&M Univ. - Florida State Univ. (FAMU-FSU) College of Engineering, Tallahassee, FL (United States). Dept. of Chemical and Biomedical Engineering; Florida State Univ., Tallahassee, FL (United States). Materials Science and Engineering Program; Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
OSTI Identifier:
1414711
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 70; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; binuclear complex; platinum(II); phosphorescence; time-resolved photoluminescence; triplet excited-state

Citation Formats

Ma, Ying-Zhong, Zhou, Chenkun, Doughty, Benjamin, Easley, Davis C., Deterding, Justin, and Ma, Biwu. Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly. United States: N. p., 2017. Web. doi:10.1002/chem.201703259.
Ma, Ying-Zhong, Zhou, Chenkun, Doughty, Benjamin, Easley, Davis C., Deterding, Justin, & Ma, Biwu. Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly. United States. doi:10.1002/chem.201703259.
Ma, Ying-Zhong, Zhou, Chenkun, Doughty, Benjamin, Easley, Davis C., Deterding, Justin, and Ma, Biwu. Wed . "Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly". United States. doi:10.1002/chem.201703259.
@article{osti_1414711,
title = {Solvent Effect on the Photoinduced Structural Change of a Phosphorescent Molecular Butterfly},
author = {Ma, Ying-Zhong and Zhou, Chenkun and Doughty, Benjamin and Easley, Davis C. and Deterding, Justin and Ma, Biwu},
abstractNote = {Photoinduced structural changes (PSC) is one of the fundamental excited-state dynamical processes, and yet often very challenging to distinguish from competing electronic excited-state relaxation channels having similar or even comparable timescales. Here, we report a detailed study on the PSC of a pyrazolate bridged platinum(II) binuclear complex, a so called molecular butterfly, using time-correlated single photon counting measurements at different wavelengths and sample temperatures. Analysis of the results obtained using dichloromethane (DCM) and ethylene carbonate (EC) as solvents enabled us to reveal an unexpected, strong solvent effect on the PSC processes. We show that a rapid PSC process with a characteristic timescale of 323 ps is observed in DCM, which leads to excitation equilibrium between the ligand center/metal-to-ligand charge transfer (3LC/MLCT) and metal-metal-to-ligand charge transfer (3MMLCT) triplet states. The subsequent relaxation from these electronic states to ground state takes place in several nanoseconds. In contrast, the corresponding PSC process in EC appears slow at all temperatures studied in our experiments and showed no sign of such excitation equilibrium. The observed solvent effect is found to arise from distinct solvent properties including their viscosities and polarities as well as the peculiar electronic excited-states of the butterfly-like molecules having charge transfer character.},
doi = {10.1002/chem.201703259},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 70,
volume = 23,
place = {United States},
year = {2017},
month = {10}
}

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