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Title: Chiral Redox-Active Isosceles Triangles

Abstract

Designing small-molecule organic redox-active materials, with potential applications in energy storage, has received considerable interest of late. Herein, we report on the synthesis, characterization, and application of two rigid chiral triangles, each of which consist of non-identical pyromellitic diimide (PMDI) and naphthalene diimide (NDI)-based redox-active units. 1H and 13C NMR spectroscopic investigations in solution confirm the lower symmetry (C2 point group) associated with these two isosceles triangles. Single-crystal X-ray diffraction analyses reveal their rigid triangular prism-like geometries. Unlike previously investigated equilateral triangle containing three identical NDI subunits, both isosceles triangles do not choose to form one-dimensional supramolecular nanotubes by dint of [C–H···O] interaction-driven columnar stacking. The rigid isosceles triangle, composed of one NDI and two PMDI subunits, forms—in the presence of N,N-dimethylformamide—two different types of intermolecular NDI–NDI and NDI–PMDI π–π stacked dimers with opposite helicities in the solid state. Cyclic voltammetry reveals that both isosceles triangles can accept reversibly up to six electrons. Continuous-wave electron paramagnetic resonance and electron–nuclear double-resonance spectroscopic investigations, supported by density functional theory calculations, on the single-electron reduced radical anions of the isosceles triangles confirm the selective sharing of unpaired electrons among adjacent redox-active NDI subunit(s) within both molecules. The isosceles triangles have been employed asmore » electrode-active materials in organic rechargeable lithium-ion batteries. The evaluation of the structure–performance relationships of this series of diimide-based triangles reveals that the increase in the number of NDI subunits, replacing PMDI ones, within the molecules improves the electrochemical cell performance of the batteries.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1250198
Alternate Identifier(s):
OSTI ID: 1434638
Grant/Contract Number:  
FG02-99ER14999
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 18; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nalluri, Siva Krishna Mohan, Liu, Zhichang, Wu, Yilei, Hermann, Keith R., Samanta, Avik, Kim, Dong Jun, Krzyaniak, Matthew D., Wasielewski, Michael R., and Stoddart, J. Fraser. Chiral Redox-Active Isosceles Triangles. United States: N. p., 2016. Web. doi:10.1021/jacs.6b02086.
Nalluri, Siva Krishna Mohan, Liu, Zhichang, Wu, Yilei, Hermann, Keith R., Samanta, Avik, Kim, Dong Jun, Krzyaniak, Matthew D., Wasielewski, Michael R., & Stoddart, J. Fraser. Chiral Redox-Active Isosceles Triangles. United States. doi:10.1021/jacs.6b02086.
Nalluri, Siva Krishna Mohan, Liu, Zhichang, Wu, Yilei, Hermann, Keith R., Samanta, Avik, Kim, Dong Jun, Krzyaniak, Matthew D., Wasielewski, Michael R., and Stoddart, J. Fraser. Tue . "Chiral Redox-Active Isosceles Triangles". United States. doi:10.1021/jacs.6b02086.
@article{osti_1250198,
title = {Chiral Redox-Active Isosceles Triangles},
author = {Nalluri, Siva Krishna Mohan and Liu, Zhichang and Wu, Yilei and Hermann, Keith R. and Samanta, Avik and Kim, Dong Jun and Krzyaniak, Matthew D. and Wasielewski, Michael R. and Stoddart, J. Fraser},
abstractNote = {Designing small-molecule organic redox-active materials, with potential applications in energy storage, has received considerable interest of late. Herein, we report on the synthesis, characterization, and application of two rigid chiral triangles, each of which consist of non-identical pyromellitic diimide (PMDI) and naphthalene diimide (NDI)-based redox-active units. 1H and 13C NMR spectroscopic investigations in solution confirm the lower symmetry (C2 point group) associated with these two isosceles triangles. Single-crystal X-ray diffraction analyses reveal their rigid triangular prism-like geometries. Unlike previously investigated equilateral triangle containing three identical NDI subunits, both isosceles triangles do not choose to form one-dimensional supramolecular nanotubes by dint of [C–H···O] interaction-driven columnar stacking. The rigid isosceles triangle, composed of one NDI and two PMDI subunits, forms—in the presence of N,N-dimethylformamide—two different types of intermolecular NDI–NDI and NDI–PMDI π–π stacked dimers with opposite helicities in the solid state. Cyclic voltammetry reveals that both isosceles triangles can accept reversibly up to six electrons. Continuous-wave electron paramagnetic resonance and electron–nuclear double-resonance spectroscopic investigations, supported by density functional theory calculations, on the single-electron reduced radical anions of the isosceles triangles confirm the selective sharing of unpaired electrons among adjacent redox-active NDI subunit(s) within both molecules. The isosceles triangles have been employed as electrode-active materials in organic rechargeable lithium-ion batteries. The evaluation of the structure–performance relationships of this series of diimide-based triangles reveals that the increase in the number of NDI subunits, replacing PMDI ones, within the molecules improves the electrochemical cell performance of the batteries.},
doi = {10.1021/jacs.6b02086},
journal = {Journal of the American Chemical Society},
number = 18,
volume = 138,
place = {United States},
year = {Tue Apr 12 00:00:00 EDT 2016},
month = {Tue Apr 12 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/jacs.6b02086

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Cited by: 10 works
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