Zero-Overlap Fluorophores for Fluorescent Studies at Any Concentration

Article abstract of DOI:10.1021/jacs.0c02450

Fluorophores are powerful tools for the study of chemistry, biology, and physics. However, fluorescence is severely impaired when concentrations climb above 5 μM as a result of effects like self-absorption and chromatic shifts in the emitted light. Herein, we report the creation of a charge-transfer (CT) fluorophore and the discovery that its emission color seen at low concentrations is unchanged even at 5 mM, some 3 orders of magnitude beyond typical limits. The fluorophore is composed of a triphenylamine-substituted cyanostar macrocycle, and it exhibits a remarkable Stokes shift of 15 ?000 cm-1 to generate emission at 633 nm. Crucial to the performance of this fluorophore is the observation that its emission spectrum shows near-zero overlap with the absorption band at 325 nm. We propose that reducing the spectral overlap to zero is a key to achieving full fluorescence across all concentrations. The triphenylamine donor and five cyanostilbene acceptor units of the macrocycle generate an emissive CT state. Unlike closely related donor-acceptor control compounds showing dual emission, the cyanostar framework inhibited emission from the second state to create a zero-overlap fluorophore. We demonstrated the use of emission spectroscopy for characterization of host-guest complexation at millimolar concentrations, which are typically the exclusive domain of NMR spectroscopy. The binding of the PF6- anion generates a 2:1 sandwich complex with blue-shifted emission. Distinct from twisted intramolecular charge-transfer (TICT) states, experiment-supported density functional theory shows a 67° twist inside an acceptor unit in the CT state instead of displaying a twist between the donor and acceptor; it is TICT-like. Inspired by the findings, we uncovered similar concentration-independent behavior from a control compound, strongly suggesting this behavior may be latent to other large Stokes-shift fluorophores. We discuss strategies capable of generating zero-overlap fluorophores to enable accurate fluorescence characterization of processes across all practical concentrations.

Full text of DOI:10.1021/jacs.0c02450

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Article
Zero-overlap Fluorophores for Fluorescent Studies at Any Concentration
Ayan Dhara, Tumpa Sadhukhan, Edward G. Sheetz, Andrew
H Olsson, Krishnan Raghavachari, and Amar H Flood
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c02450 • Publication Date (Web): 15 Jun 2020
Downloaded from pubs.acs.org on June 15, 2020
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 42
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ACS Paragon Plus Environment

Page 9 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 12 of 42
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ACS Paragon Plus Environment

Page 13 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 14 of 42
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ACS Paragon Plus Environment

Page 15 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 16 of 42
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ACS Paragon Plus Environment

Page 17 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 18 of 42
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 20 of 42
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ACS Paragon Plus Environment

Page 21 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 22 of 42
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ACS Paragon Plus Environment

Page 23 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 24 of 42
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ACS Paragon Plus Environment

Page 25 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 26 of 42
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ACS Paragon Plus Environment

Page 27 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 28 of 42
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Page 29 of 42
Journal of the American Chemical Society
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ACS Paragon Plus Environment