Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence
Abstract
Photoluminescent molecules exploiting the sizable spin-orbit coupling constants of main group metals and metalloids to access long-lived triplet excited states are relatively rare compared to phosphorescent transition metal complexes. Here we report the synthesis of three air- and moisture-stable group 14 compounds E(MePDPPh)2, where E = Si, Ge, or Sn and [MePDPPh]2- is the doubly deprotonated form of 2,6-bis(5- methyl-3-phenyl-1H-pyrrol-2-yl)pyridine. In solution, all three molecules exhibit exceptionally long-lived triplet excited states with lifetimes in the millisecond range and show highly efficient photoluminescence (Φ ≤ 0.49) due to competing prompt fluorescence and thermally activated delayed fluorescence at and around room temperature. Temperature-dependent steady-state emission spectra and photoluminescent lifetime measurements provided conclusive evidence for the two distinct emission pathways. Picosecond transient absorption spectroscopy allowed further analysis of the intersystem crossing (ISC) between singlet and triplet manifolds (τISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.
- Authors:
-
[2];
[3];
[3];
[1]
- West Virginia Univ., Morgantown, WV (United States)
- Princeton Univ., NJ (United States); North Carolina State Univ., Raleigh, NC (United States)
- North Carolina State Univ., Raleigh, NC (United States)
- Publication Date:
- Research Org.:
- North Carolina State University, Raleigh, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1869247
- Grant/Contract Number:
- SC0011979; CHE-1752738
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 61; Journal Issue: 19; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Gowda, Anitha S., Lee, Tia S., Rosko, Michael C., Petersen, Jeffrey L., Castellano, Felix N., and Milsmann, Carsten. Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence. United States: N. p., 2022.
Web. doi:10.1021/acs.inorgchem.2c00182.
Gowda, Anitha S., Lee, Tia S., Rosko, Michael C., Petersen, Jeffrey L., Castellano, Felix N., & Milsmann, Carsten. Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence. United States. https://doi.org/10.1021/acs.inorgchem.2c00182
Gowda, Anitha S., Lee, Tia S., Rosko, Michael C., Petersen, Jeffrey L., Castellano, Felix N., and Milsmann, Carsten. Wed .
"Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence". United States. https://doi.org/10.1021/acs.inorgchem.2c00182. https://www.osti.gov/servlets/purl/1869247.
@article{osti_1869247,
title = {Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence},
author = {Gowda, Anitha S. and Lee, Tia S. and Rosko, Michael C. and Petersen, Jeffrey L. and Castellano, Felix N. and Milsmann, Carsten},
abstractNote = {Photoluminescent molecules exploiting the sizable spin-orbit coupling constants of main group metals and metalloids to access long-lived triplet excited states are relatively rare compared to phosphorescent transition metal complexes. Here we report the synthesis of three air- and moisture-stable group 14 compounds E(MePDPPh)2, where E = Si, Ge, or Sn and [MePDPPh]2- is the doubly deprotonated form of 2,6-bis(5- methyl-3-phenyl-1H-pyrrol-2-yl)pyridine. In solution, all three molecules exhibit exceptionally long-lived triplet excited states with lifetimes in the millisecond range and show highly efficient photoluminescence (Φ ≤ 0.49) due to competing prompt fluorescence and thermally activated delayed fluorescence at and around room temperature. Temperature-dependent steady-state emission spectra and photoluminescent lifetime measurements provided conclusive evidence for the two distinct emission pathways. Picosecond transient absorption spectroscopy allowed further analysis of the intersystem crossing (ISC) between singlet and triplet manifolds (τISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.},
doi = {10.1021/acs.inorgchem.2c00182},
journal = {Inorganic Chemistry},
number = 19,
volume = 61,
place = {United States},
year = {Wed May 04 00:00:00 EDT 2022},
month = {Wed May 04 00:00:00 EDT 2022}
}
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