Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays
Abstract
High quantum yield NIR fluorophores are rare. Factors that drive low emission quantum yields at long wavelength include the facts that radiative rate constants increase proportional to the cube of the emission energy, while nonradiative rate constants increase in an approximately exponentially with decreasing S0–S1 energy gaps (in accordance with the energy gap law). This work demonstrates how the proquinoidal BTD building blocks can be utilized to minimize the extent of excited-state structural relaxation relative to the ground-state conformation in highly conjugated porphyrin oligomers, and shows that 4-ethynylbenzo[c][1,2,5]thiadiazole (E-BTD) units that terminate meso-to-meso ethyne-bridged (porphinato)zinc (PZnn) arrays, and 4,7-diethynylbenzo[c][1,2,5]thiadiazole (E-BTD-E) spacers that are integrated into the backbone of these compositions, elucidate new classes of impressive NIR fluorophores. We report the syntheses, electronic structural properties, and emissive characteristics of neoteric PZn-(BTD-PZn)n, PZn2-(BTD-PZn2)n, and BTD-PZnn-BTD fluorophores. Absolute fluorescence quantum yield (φf) measurements, acquired using a calibrated integrating-sphere-based measurement system, demonstrate that these supermolecules display extraordinary φf values that range from 10–25% in THF solvent, and between 28–36% in toluene solvent over the 700–900 nm window of the NIR. These studies underscore how the regulation of proquinoidal conjugation motifs can be exploited to drive excited-state dynamical properties important for high quantum yield long-wavelengthmore »
- Authors:
-
[1];
[1];
[1]
- Department of Chemistry, French Family Science Center, Duke University, 124 Science Drive, Durham, North Carolina 27708-0346, USA
- Publication Date:
- Research Org.:
- Duke Univ., Durham, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1645145
- Alternate Identifier(s):
- OSTI ID: 1801487; OSTI ID: 1830760
- Grant/Contract Number:
- SC0001517; ACI-1548562
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 31; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Peterson, Erin J., Qi, Wei, Stanton, Ian N., Zhang, Peng, and Therien, Michael J. Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays. United Kingdom: N. p., 2020.
Web. doi:10.1039/D0SC03446K.
Peterson, Erin J., Qi, Wei, Stanton, Ian N., Zhang, Peng, & Therien, Michael J. Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays. United Kingdom. https://doi.org/10.1039/D0SC03446K
Peterson, Erin J., Qi, Wei, Stanton, Ian N., Zhang, Peng, and Therien, Michael J. Wed .
"Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays". United Kingdom. https://doi.org/10.1039/D0SC03446K.
@article{osti_1645145,
title = {Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays},
author = {Peterson, Erin J. and Qi, Wei and Stanton, Ian N. and Zhang, Peng and Therien, Michael J.},
abstractNote = {High quantum yield NIR fluorophores are rare. Factors that drive low emission quantum yields at long wavelength include the facts that radiative rate constants increase proportional to the cube of the emission energy, while nonradiative rate constants increase in an approximately exponentially with decreasing S0–S1 energy gaps (in accordance with the energy gap law). This work demonstrates how the proquinoidal BTD building blocks can be utilized to minimize the extent of excited-state structural relaxation relative to the ground-state conformation in highly conjugated porphyrin oligomers, and shows that 4-ethynylbenzo[c][1,2,5]thiadiazole (E-BTD) units that terminate meso-to-meso ethyne-bridged (porphinato)zinc (PZnn) arrays, and 4,7-diethynylbenzo[c][1,2,5]thiadiazole (E-BTD-E) spacers that are integrated into the backbone of these compositions, elucidate new classes of impressive NIR fluorophores. We report the syntheses, electronic structural properties, and emissive characteristics of neoteric PZn-(BTD-PZn)n, PZn2-(BTD-PZn2)n, and BTD-PZnn-BTD fluorophores. Absolute fluorescence quantum yield (φf) measurements, acquired using a calibrated integrating-sphere-based measurement system, demonstrate that these supermolecules display extraordinary φf values that range from 10–25% in THF solvent, and between 28–36% in toluene solvent over the 700–900 nm window of the NIR. These studies underscore how the regulation of proquinoidal conjugation motifs can be exploited to drive excited-state dynamical properties important for high quantum yield long-wavelength fluorescence emission.},
doi = {10.1039/D0SC03446K},
journal = {Chemical Science},
number = 31,
volume = 11,
place = {United Kingdom},
year = {Wed Aug 12 00:00:00 EDT 2020},
month = {Wed Aug 12 00:00:00 EDT 2020}
}
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