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Synthesis of Pyridine– and Pyrazine–BF3 Complexes and Their Characterization in Solution and Solid State

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† ‡ ⊥ Joint Center for Energy Storage Research, School of Chemical Sciences, §NMR/EPR Laboratory, School of Chemical Sciences, G.L. Clark X-ray Facility, School of Chemical Sciences, and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
# Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
% Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
*E-mail: [email protected] (J.S.M.).
Cite this: J. Phys. Chem. C 2016, 120, 16, 8461–8471
Publication Date (Web):March 31, 2016
https://doi.org/10.1021/acs.jpcc.6b00858
Copyright © 2016 American Chemical Society

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    Abstract

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    Following the discovery of the redox-active 1,4-bis-BF3-quinoxaline complex, we undertook a structure–activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF3-quinoxaline adduct. Using solution and solid-state NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1D and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF3–heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b00858.

    • Experimental details and characterization of complexes, including 1H, 13C, 11B, 19F, COSY, HSQC, and HMBC solution NMR spectroscopy spectrum, IR spectroscopy, single crystal X-ray diffraction information, additional 11B ssNMR spectroscopy spectra, and computational and experimental cyclic voltammetry results (PDF)

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