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Chen P, Marshall AS, Chi SH, et al. Luminescent Quadrupolar Borazine Oligomers: Synthesis, Photophysics, and Two-Photon Absorption Properties. Chemistry. 2015;21(50):18237-47doi: 10.1002/chem.201502268.
Chen, P., Marshall, A. S., Chi, S. H., Yin, X., Perry, J. W., & Jäkle, F. (2015). Luminescent Quadrupolar Borazine Oligomers: Synthesis, Photophysics, and Two-Photon Absorption Properties. Chemistry (Weinheim an der Bergstrasse, Germany), 21(50), 18237-47. https://doi.org/10.1002/chem.201502268
Chen, Pangkuan, et al. "Luminescent Quadrupolar Borazine Oligomers: Synthesis, Photophysics, and Two-Photon Absorption Properties." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,50 (2015): 18237-47. doi: https://doi.org/10.1002/chem.201502268
Chen P, Marshall AS, Chi SH, Yin X, Perry JW, Jäkle F. Luminescent Quadrupolar Borazine Oligomers: Synthesis, Photophysics, and Two-Photon Absorption Properties. Chemistry. 2015 Dec 07;21(50):18237-47. doi: 10.1002/chem.201502268. Epub 2015 Oct 30. PMID: 26514664.
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Chemistry. 2015 Dec 07;21(50):18237-47. doi: 10.1002/chem.201502268. Epub 2015 Oct 30.

Luminescent Quadrupolar Borazine Oligomers: Synthesis, Photophysics, and Two-Photon Absorption Properties.

Chemistry (Weinheim an der Bergstrasse, Germany)

Pangkuan Chen, Ariel S Marshall, San-Hui Chi, Xiaodong Yin, Joseph W Perry, Frieder Jäkle

Affiliations

  1. Department of Chemistry, Rutgers University Newark, Newark, NJ, 07102 (USA).
  2. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA, 30332-0400 (USA).
  3. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA, 30332-0400 (USA). [email protected].
  4. Department of Chemistry, Rutgers University Newark, Newark, NJ, 07102 (USA). [email protected].

PMID: 26514664 DOI: 10.1002/chem.201502268

Abstract

A set of monodisperse bent donor-acceptor-donor-type conjugated borazine oligomers, BnNn+1 (n=1-4), incorporating electron-rich triarylamine donor and electron-deficient triarylborane acceptor units has been prepared through an iterative synthetic approach that takes advantage of highly selective silicon-boron and tin-boron exchange reactions. The effect of chain elongation on the electrochemical, one- and two-photon properties and excited-state photodynamics has been investigated. Strong intramolecular charge transfer (ICT) from the arylamine donors to boryl-centered acceptor sites results in emissions with high quantum yields (Φfl >0.5) in the range of 400-500 nm. Solvatochromic effects lead to solvent shifts as large as ∼70 nm for the shortest member (n=1) and gradually decrease with chain elongation. The oligomers exhibit strong two-photon absorption (2PA) in the visible spectral region with 2PA cross sections as large as 1410 GM (n=4), and broadband excited-state absorption (ESA) attributed to long-lived singlet-singlet and radical cation/anion absorption. The excited-state dynamics also show sensitivity to the solvent environment. Electrochemical observations and DFT calculations (B3LYP/6-31G*) reveal spatially separated HOMO and LUMO levels resulting in highly fluorescent oligomers with strong ICT character. The BnNn+1 oligomers have been used to demonstrate the detection of cyanide anions with association constants of log K>7.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: borane; conjugation; donor-acceptor; fluorescence; two-photon absorption

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