skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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, Didcot (United Kingdom)
  2. Univ. of Bath, Bath (United Kingdom)
  3. Univ. of Bath, Bath (United Kingdom); Univ. of Kent, Canterbury (United Kingdom)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Univ. of Bath, Bath (United Kingdom); Harwell Science and Innovation Campus, Didcot (United Kingdom)
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:
Journal Article: Published Article
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 20; Journal Issue: 22; Related Information: © 2018 The Royal Society of Chemistry.; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
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 States: 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 States. 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. Wed . "Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution". United States. 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},
issn = {1466-8033},
number = 22,
volume = 20,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c8ce00443a

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

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.

Save / Share:

Works referenced in this record:

Organic ferroelectrics
journal, May 2008

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

    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