Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays

Peterson, Erin J.; Qi, Wei; Stanton, Ian N.; Zhang, Peng; Therien, Michael J.

doi:10.1039/D0SC03446K

Title: Driving high quantum yield NIR emission through proquinoidal linkage motifs in conjugated supermolecular arrays

Journal Article · Wed Aug 12 00:00:00 EDT 2020 · Chemical Science

DOI:https://doi.org/10.1039/D0SC03446K· OSTI ID:1645145

^[1]; Qi, Wei ^[1]; Stanton, Ian N. ^[1];

^[1];

^[1]

Department of Chemistry, French Family Science Center, Duke University, 124 Science Drive, Durham, North Carolina 27708-0346, USA

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 (PZn_n) 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-PZn_n-BTD fluorophores. Absolute fluorescence quantum yield (φ_f) measurements, acquired using a calibrated integrating-sphere-based measurement system, demonstrate that these supermolecules display extraordinary φ_f 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.

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Research Organization:: Duke Univ., Durham, NC (United States)

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

Grant/Contract Number:: SC0001517; ACI-1548562

OSTI ID:: 1645145

Alternate ID(s):: OSTI ID: 1801487; OSTI ID: 1830760

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 11 Journal Issue: 31; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 6 works

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