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Title: Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution

Abstract

Nine new molecular complexes of the proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) with substituted benzoic acid co-formers have been engineered with varying component stoichiometries (1:1, 1:2 or 1:3). These complexes are all ionic in nature, following proton transfer between the acid co-former and DMAN; the extracted proton is held by DMAN in all instances in an intramolecular [N-H…N]+ hydrogen bond. A number of structural features are common to all complexes and are found to be tunable in a predictable way using systematic acid co-former substitution. These features include charge-assisted hydrogen bonds formed between acid co-formers in hydrogen bonding motifs consistent with complex stoichiometry, and weak hydrogen bonds which facilitate the crystal packing of DMAN and acid co-former components into a regular motif. Possible crystal structure tuning by co-former substitution can aid the rational design of such materials, offering the potential to target solid-state properties that may be influenced by these interactions.Varying the electronic character of the acid co-former substituent group predictably alters weak and strong intermolecular interactions.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [2]; ORCiD logo [4]; ORCiD logo [5];  [2]
  1. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, UK
  2. Department of Chemistry, University of Bath, Bath, UK
  3. Department of Chemistry, University of Bath, Bath, UK, School of Physical Sciences
  4. Advanced Light Source, Lawrence Berkeley National Lab, Berkeley, USA
  5. Department of Chemistry, University of Bath, Bath, UK, Research Complex at Harwell
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1437501
Alternate Identifier(s):
OSTI ID: 1465424
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Name: CrystEngComm Journal Volume: 20 Journal Issue: 22; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Saunders, Lucy K., Nowell, Harriott, Spencer, Helen C. E., Hatcher, Lauren E., Shepherd, Helena J., Thomas, Lynne H., Jones, Charlotte L., Teat, Simon J., Raithby, Paul R., and Wilson, Chick C. Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution. United Kingdom: N. p., 2018. Web. doi:10.1039/C8CE00443A.
Saunders, Lucy K., Nowell, Harriott, Spencer, Helen C. E., Hatcher, Lauren E., Shepherd, Helena J., Thomas, Lynne H., Jones, Charlotte L., Teat, Simon J., Raithby, Paul R., & Wilson, Chick C. Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution. United Kingdom. doi:10.1039/C8CE00443A.
Saunders, Lucy K., Nowell, Harriott, Spencer, Helen C. E., Hatcher, Lauren E., Shepherd, Helena J., Thomas, Lynne H., Jones, Charlotte L., Teat, Simon J., Raithby, Paul R., and Wilson, Chick C. Mon . "Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution". United Kingdom. doi:10.1039/C8CE00443A.
@article{osti_1437501,
title = {Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution},
author = {Saunders, Lucy K. and Nowell, Harriott and Spencer, Helen C. E. and Hatcher, Lauren E. and Shepherd, Helena J. and Thomas, Lynne H. and Jones, Charlotte L. and Teat, Simon J. and Raithby, Paul R. and Wilson, Chick C.},
abstractNote = {Nine new molecular complexes of the proton sponge 1,8-bis(dimethylamino)naphthalene (DMAN) with substituted benzoic acid co-formers have been engineered with varying component stoichiometries (1:1, 1:2 or 1:3). These complexes are all ionic in nature, following proton transfer between the acid co-former and DMAN; the extracted proton is held by DMAN in all instances in an intramolecular [N-H…N]+ hydrogen bond. A number of structural features are common to all complexes and are found to be tunable in a predictable way using systematic acid co-former substitution. These features include charge-assisted hydrogen bonds formed between acid co-formers in hydrogen bonding motifs consistent with complex stoichiometry, and weak hydrogen bonds which facilitate the crystal packing of DMAN and acid co-former components into a regular motif. Possible crystal structure tuning by co-former substitution can aid the rational design of such materials, offering the potential to target solid-state properties that may be influenced by these interactions.Varying the electronic character of the acid co-former substituent group predictably alters weak and strong intermolecular interactions.},
doi = {10.1039/C8CE00443A},
journal = {CrystEngComm},
number = 22,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8CE00443A

Citation Metrics:
Cited by: 1 work
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Figures / Tables:

Scheme 1 Scheme 1: The crystal packing of the DMANH+ cation and ACID- anion via weak hydrogen bonding interactions; the hydrogen bonded acid (ACID-) unit is oriented towards the DMAN cation methyl groups.

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Works referenced in this record:

Systematic experimental charge density analysis of anion receptor complexes
journal, January 2014

  • Kirby, Isabelle L.; Brightwell, Mark; Pitak, Mateusz B.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 22
  • DOI: 10.1039/C3CP54858A

Proton-Transfer-Dependent Reversible Phase Changes in the 4,4′-Bipyridinium Salt of Squaric Acid
journal, February 1994

  • Reetz, Manfred T.; Höger, Sigurd; Harms, Klaus
  • Angewandte Chemie International Edition in English, Vol. 33, Issue 2
  • DOI: 10.1002/anie.199401811

Neutron diffraction of a complex of 1,8-bis(dimethylamino)naphthalene with 1,2-dichloromaleic acid
journal, August 1996

  • Wozniak, K.; Wilson, C. C.; Knight, K. S.
  • Acta Crystallographica Section B Structural Science, Vol. 52, Issue 4
  • DOI: 10.1107/S0108768196003023

Structure and energetics of a ferroelectric organic crystal of phenazine and chloranilic acid
journal, September 2012


Supramolecular hydrogen-bonding patterns of co-crystals containing the active pharmaceutical ingredient (API) phloroglucinol and N -heterocycles
journal, May 2016

  • Cvetkovski, Aleksandar; Bertolasi, Valerio; Ferretti, Valeria
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 3
  • DOI: 10.1107/S2052520616004406

Engineering Short, Strong, Charge-Assisted Hydrogen Bonds in Benzoic Acid Dimers through Cocrystallization with Proton Sponge
journal, March 2016

  • Thomas, Lynne H.; Jones, Andrew O. F.; Kallay, Andras A.
  • Crystal Growth & Design, Vol. 16, Issue 4
  • DOI: 10.1021/acs.cgd.5b01787

Role of Crystal Packing and Weak Intermolecular Interactions in the Solid State Fluorescence of N -Methylpyrazoline Derivatives
journal, June 2015


The Effect of Local Crystalline Environment on Hydrogen Atom Behavior in Molecular Complexes of a Proton Sponge
journal, March 2016

  • Jones, Andrew O. F.; Kallay, Andras A.; Lloyd, Hayleigh
  • Crystal Growth & Design, Vol. 16, Issue 4
  • DOI: 10.1021/acs.cgd.5b01788

Novel arylated chloro- and methoxy-1,3-dibutadienes: Influence of substituents on molecular conformation and crystal packing
journal, June 2014


Investigation of Steric Influences on Hydrogen-Bonding Motifs in Cyclic Ureas by Using X-Ray, Neutron, and Computational Methods
journal, August 2013

  • McCormick, Laura J.; McDonnell-Worth, Ciaran; Platts, James A.
  • Chemistry - An Asian Journal, Vol. 8, Issue 11
  • DOI: 10.1002/asia.201300530

The specificity of the [NHN]+ hydrogen bonds in protonated naphthalene proton sponges
journal, May 2010


Temperature effect on the structure of the complex 1,8-bis(dimethylamino)naphthalene–chloranilic acid (2/1) dihydrate
journal, October 1991

  • Kanters, J. A.; Schouten, A.; Duisenberg, A. J. M.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 47, Issue 10
  • DOI: 10.1107/S0108270191003426

Proton transfer in the intramolecular NHN+ bonds in proton sponges with different hydrogen bridge flexibility
journal, January 2009

  • Majerz, Irena; Olovsson, Ivar
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 9
  • DOI: 10.1039/b814798a

Role of C?H���O hydrogen bonds in the ionic complexes of 1,8-bis(dimethylamino)naphthalene
journal, January 2003

  • Wozniak, Krzysztof; Mallinson, Paul R.; Smith, Garry T.
  • Journal of Physical Organic Chemistry, Vol. 16, Issue 10
  • DOI: 10.1002/poc.683

Tuning Proton Disorder in 3,5-Dinitrobenzoic Acid Dimers: the Effect of Local Environment
journal, January 2013

  • Jones, Andrew O. F.; Blagden, Nicholas; McIntyre, Garry J.
  • Crystal Growth & Design, Vol. 13, Issue 2
  • DOI: 10.1021/cg300906j

From Weak Interactions to Covalent Bonds:  A Continuum in the Complexes of 1,8-Bis(dimethylamino)naphthalene
journal, April 2003

  • Mallinson, Paul R.; Smith, Garry T.; Wilson, Chick C.
  • Journal of the American Chemical Society, Vol. 125, Issue 14
  • DOI: 10.1021/ja029389b

Organic ferroelectrics
journal, May 2008

  • Horiuchi, Sachio; Tokura, Yoshinori
  • Nature Materials, Vol. 7, Issue 5, p. 357-366
  • DOI: 10.1038/nmat2137

Ab Initio Studies of Proton Sponges: 1,8-Bis(dimethylamino)naphthalene
journal, August 1994

  • Platts, J. A.; Howard, S. T.; Wozniak, K.
  • The Journal of Organic Chemistry, Vol. 59, Issue 16
  • DOI: 10.1021/jo00095a046

Proton sponges
journal, December 1994


Complexes of the “proton sponge” 1,8-bis(dimethylamino)naphthalene (DMAN)
journal, August 1992


Symmetry of N−H−N Hydrogen Bonds in 1,8-Bis(dimethylamino)naphthalene·H + and 2,7-Dimethoxy-1,8-bis(dimethylamino)naphthalene·H +
journal, July 2001

  • Perrin, Charles L.; Ohta, Brian K.
  • Journal of the American Chemical Society, Vol. 123, Issue 27
  • DOI: 10.1021/ja0036965

Fine-Tuning of Crystal Packing and Charge Transport Properties of BDOPV Derivatives through Fluorine Substitution
journal, December 2015

  • Dou, Jin-Hu; Zheng, Yu-Qing; Yao, Ze-Fan
  • Journal of the American Chemical Society, Vol. 137, Issue 50
  • DOI: 10.1021/jacs.5b11114

Temperature dependent solid-state proton migration in dimethylurea–oxalic acid complexes
journal, January 2012

  • Jones, Andrew O. F.; Lemée-Cailleau, Marie-Hélène; Martins, David M. S.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 38
  • DOI: 10.1039/c2cp41782k

The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002


Charge Density Distribution in the “Proton Sponge” Compound 1,8-Bis(dimethylamino)naphthalene
journal, May 1999

  • Mallinson, Paul R.; Woźniak, Krzysztof; Wilson, Chick C.
  • Journal of the American Chemical Society, Vol. 121, Issue 19
  • DOI: 10.1021/ja983393z

Turning colour on and off using molecular disorder and proton transfer in multi-component molecular complexes
journal, January 2014

  • Jones, Charlotte L.; Wilson, Chick C.; Thomas, Lynne H.
  • CrystEngComm, Vol. 16, Issue 26
  • DOI: 10.1039/C4CE00229F

Hydrogen bond-directed cocrystallization and molecular recognition properties of diarylureas
journal, November 1990

  • Etter, Margaret C.; Urbanczyk-Lipkowska, Zofia; Zia-Ebrahimi, Mohammad
  • Journal of the American Chemical Society, Vol. 112, Issue 23
  • DOI: 10.1021/ja00179a028

    Works referencing / citing this record:

    CCDC 1831638: Experimental Crystal Structure Determination: LIGSUS : 8-(dimethylamino)-N,N-dimethylnaphthalen-1-aminium 4-hydroxybenzoate 4-hydroxybenzoic acid
    dataset, March 2018

    • Saunders, Lucy K.; Nowell, Harriott; Spencer, Helen C. E.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1zgz3j

    CCDC 1831642: Experimental Crystal Structure Determination: LIGTON : 8-(dimethylamino)-N,N-dimethylnaphthalen-1-aminium 3-carboxy-5-nitrobenzoate
    dataset, March 2018


    CCDC 1831643: Experimental Crystal Structure Determination: LIGTUT : 8-(dimethylamino)-N,N-dimethylnaphthalen-1-aminium 3-methoxybenzoate 3-methoxybenzoic acid
    dataset, March 2018

    • Saunders, Lucy K.; Nowell, Harriott; Spencer, Helen C. E.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1zgz8p

    CCDC 1831645: Experimental Crystal Structure Determination
    dataset, April 2018

    • , Lucy K. Saunders; , Harriott Nowell; , Helen C. E. Spencer
    • Cambridge Crystallogrphic Data Centre, vp
    • DOI: 10.5517/ccdc.csd.cc1zgzbr

    Proton-Transfer-Dependent Reversible Phase Changes in the 4,4′-Bipyridinium Salt of Squaric Acid
    journal, February 1994

    • Reetz, Manfred T.; Höger, Sigurd; Harms, Klaus
    • Angewandte Chemie International Edition in English, Vol. 33, Issue 2
    • DOI: 10.1002/anie.199401811

    Investigation of Steric Influences on Hydrogen-Bonding Motifs in Cyclic Ureas by Using X-Ray, Neutron, and Computational Methods
    journal, August 2013

    • McCormick, Laura J.; McDonnell-Worth, Ciaran; Platts, James A.
    • Chemistry - An Asian Journal, Vol. 8, Issue 11
    • DOI: 10.1002/asia.201300530

    Role of C?H���O hydrogen bonds in the ionic complexes of 1,8-bis(dimethylamino)naphthalene
    journal, January 2003

    • Wozniak, Krzysztof; Mallinson, Paul R.; Smith, Garry T.
    • Journal of Physical Organic Chemistry, Vol. 16, Issue 10
    • DOI: 10.1002/poc.683

    Complexes of the “proton sponge” 1,8-bis(dimethylamino)naphthalene (DMAN)
    journal, August 1992


    Proton sponges
    journal, December 1994


    The specificity of the [NHN]+ hydrogen bonds in protonated naphthalene proton sponges
    journal, May 2010


    Novel arylated chloro- and methoxy-1,3-dibutadienes: Influence of substituents on molecular conformation and crystal packing
    journal, June 2014


    Role of Crystal Packing and Weak Intermolecular Interactions in the Solid State Fluorescence of N -Methylpyrazoline Derivatives
    journal, June 2015


    Engineering Short, Strong, Charge-Assisted Hydrogen Bonds in Benzoic Acid Dimers through Cocrystallization with Proton Sponge
    journal, March 2016

    • Thomas, Lynne H.; Jones, Andrew O. F.; Kallay, Andras A.
    • Crystal Growth & Design, Vol. 16, Issue 4
    • DOI: 10.1021/acs.cgd.5b01787

    The Effect of Local Crystalline Environment on Hydrogen Atom Behavior in Molecular Complexes of a Proton Sponge
    journal, March 2016

    • Jones, Andrew O. F.; Kallay, Andras A.; Lloyd, Hayleigh
    • Crystal Growth & Design, Vol. 16, Issue 4
    • DOI: 10.1021/acs.cgd.5b01788

    Tuning Proton Disorder in 3,5-Dinitrobenzoic Acid Dimers: the Effect of Local Environment
    journal, January 2013

    • Jones, Andrew O. F.; Blagden, Nicholas; McIntyre, Garry J.
    • Crystal Growth & Design, Vol. 13, Issue 2
    • DOI: 10.1021/cg300906j

    Hydrogen bond-directed cocrystallization and molecular recognition properties of diarylureas
    journal, November 1990

    • Etter, Margaret C.; Urbanczyk-Lipkowska, Zofia; Zia-Ebrahimi, Mohammad
    • Journal of the American Chemical Society, Vol. 112, Issue 23
    • DOI: 10.1021/ja00179a028

    Symmetry of N−H−N Hydrogen Bonds in 1,8-Bis(dimethylamino)naphthalene·H + and 2,7-Dimethoxy-1,8-bis(dimethylamino)naphthalene·H +
    journal, July 2001

    • Perrin, Charles L.; Ohta, Brian K.
    • Journal of the American Chemical Society, Vol. 123, Issue 27
    • DOI: 10.1021/ja0036965

    From Weak Interactions to Covalent Bonds:  A Continuum in the Complexes of 1,8-Bis(dimethylamino)naphthalene
    journal, April 2003

    • Mallinson, Paul R.; Smith, Garry T.; Wilson, Chick C.
    • Journal of the American Chemical Society, Vol. 125, Issue 14
    • DOI: 10.1021/ja029389b

    Charge Density Distribution in the “Proton Sponge” Compound 1,8-Bis(dimethylamino)naphthalene
    journal, May 1999

    • Mallinson, Paul R.; Woźniak, Krzysztof; Wilson, Chick C.
    • Journal of the American Chemical Society, Vol. 121, Issue 19
    • DOI: 10.1021/ja983393z

    Fine-Tuning of Crystal Packing and Charge Transport Properties of BDOPV Derivatives through Fluorine Substitution
    journal, December 2015

    • Dou, Jin-Hu; Zheng, Yu-Qing; Yao, Ze-Fan
    • Journal of the American Chemical Society, Vol. 137, Issue 50
    • DOI: 10.1021/jacs.5b11114

    Ab Initio Studies of Proton Sponges: 1,8-Bis(dimethylamino)naphthalene
    journal, August 1994

    • Platts, J. A.; Howard, S. T.; Wozniak, K.
    • The Journal of Organic Chemistry, Vol. 59, Issue 16
    • DOI: 10.1021/jo00095a046

    Organic ferroelectrics
    journal, May 2008

    • Horiuchi, Sachio; Tokura, Yoshinori
    • Nature Materials, Vol. 7, Issue 5, p. 357-366
    • DOI: 10.1038/nmat2137

    Proton transfer in the intramolecular NHN+ bonds in proton sponges with different hydrogen bridge flexibility
    journal, January 2009

    • Majerz, Irena; Olovsson, Ivar
    • Physical Chemistry Chemical Physics, Vol. 11, Issue 9
    • DOI: 10.1039/b814798a

    Temperature dependent solid-state proton migration in dimethylurea–oxalic acid complexes
    journal, January 2012

    • Jones, Andrew O. F.; Lemée-Cailleau, Marie-Hélène; Martins, David M. S.
    • Physical Chemistry Chemical Physics, Vol. 14, Issue 38
    • DOI: 10.1039/c2cp41782k