Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

Gowda, Anitha S.; Lee, Tia S.; Rosko, Michael C.; Petersen, Jeffrey L.; Castellano, Felix N.; Milsmann, Carsten

doi:10.1021/acs.inorgchem.2c00182

Title: Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

Journal Article · 03 May 2022 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.2c00182 · OSTI ID:1869247

Gowda, Anitha S. ^[1];

^[2];

^[3]; Petersen, Jeffrey L. ^[4];

^[3];

^[4]

West Virginia Univ., Morgantown, WV (United States); NC State University
Princeton Univ., NJ (United States); North Carolina State Univ., Raleigh, NC (United States)
North Carolina State Univ., Raleigh, NC (United States)
West Virginia Univ., Morgantown, WV (United States)

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(^MePDP^Ph)₂, where E = Si, Ge, or Sn and [^MePDP^Ph]^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 (τ_ISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.

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Research Organization:: North Carolina State Univ., Raleigh, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0011979

OSTI ID:: 1869247

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 19 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2142966: Experimental Crystal Structure Determination S., Gowda, Anitha; S., Lee, Tia; C., Rosko, Michael https://doi.org/10.5517/ccdc.csd.cc29xxy3 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2142968: Experimental Crystal Structure Determination S., Gowda, Anitha; S., Lee, Tia; C., Rosko, Michael https://doi.org/10.5517/ccdc.csd.cc29xy06 The current record is supplemented by this dataset	dataset	January 2022
CCDC 2142967: Experimental Crystal Structure Determination S., Gowda, Anitha; S., Lee, Tia; C., Rosko, Michael https://doi.org/10.5517/ccdc.csd.cc29xxz4 The current record is supplemented by this dataset	dataset	January 2022

Title: Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

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