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Electronic Spectroscopy of 2-Phenyl-1,3,2-benzodioxaborole and Its Derivatives: Important Building Blocks of Covalent Organic Frameworks

  • Cara Savino
    Cara Savino
    Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
    More by Cara Savino
  • Roberta P. Ryan
    Roberta P. Ryan
    Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
  • Joseph L. Knee
    Joseph L. Knee
    Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
  • Carlos A. Jimenez-Hoyos
    Carlos A. Jimenez-Hoyos
    Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
  • , and 
  • Brian H. Northrop*
    Brian H. Northrop
    Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459, United States
    *E-mail: [email protected]
Cite this: J. Phys. Chem. A 2020, 124, 3, 529–537
Publication Date (Web):December 29, 2019
https://doi.org/10.1021/acs.jpca.9b09476
Copyright © 2019 American Chemical Society

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    Abstract

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    Aryl boronate esters, such as 2-phenyl-1,3,2-benzodioxaborole (1), are important components in the formation of a variety of covalent organic frameworks. The addition of substituents on the aromatic rings of aryl boronate esters has the potential to modify the structure, reactivity, and electronic properties of the resulting materials, and so, it is useful to understand at a more fundamental level the properties of these important compounds. Experimental measurements and computational investigations are presented herein that provide insight regarding the structural and electronic properties of parent aryl boronate ester 1 as well as three substituted derivatives: 2-(o-tolyl)-1,3,2-benzodioxaborole (2), 2-(2,6-dimethylphenyl)-1,3,2-benzodioxaborole (3), and 2-(4-(tert-butyl)phenyl)-1,3,2-benzodioxaborole (4). Electronic spectroscopy combined with excited-state calculations reveal two closely spaced electronic states, S1 and S2, which appear to have excitation primarily localized on the aromatic system of the phenyl substituent or the catecholborane moiety, respectively. Interestingly, the ortho-dimethyl derivative (3) shows a significantly red-shifted electronic origin with an extensive vibronic progression of a low-frequency torsional motion about the C–B bond. Franck–Condon calculations on the ab initio determined ground- and excited-state potentials very accurately reproduce this spectrum, confirming the nonplanar ground state of this compound.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.9b09476.

    • Comparison of 1-Ar1 vs 1-Ar2 complexes, comparison of REMPI spectra of 11B and 10B isotopes of aryl boronate ester 1, ZEKE photoelectron spectroscopy of compound 1, and optimized active space orbitals of ground-state CASSCF(16,15) and two sets of (6,6) calculations (PDF)

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    Cited By

    This article is cited by 1 publications.

    1. Andrew J. Greenlee, Chloe I. Wendell, Morgan M. Cencer, Summer D. Laffoon, Jeffrey S. Moore. Kinetic and Thermodynamic Control in Dynamic Covalent Synthesis. Trends in Chemistry 2020, 2 (12) , 1043-1051. https://doi.org/10.1016/j.trechm.2020.09.005

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