Tuning charge-assisted and weak hydrogen bonds in molecular complexes of the proton sponge DMAN by acid co-former substitution. Issue 22 (17th May 2018)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: CrystEngComm. Volume 20:Issue 22(2018)
• Page Start: 3074
• Page End: 3083
• Publication Date: 2018-05-17
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c8ce00443a
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : Varying the electronic character of the acid co-former substituent group predictably alters weak and strong intermolecular interactions. 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.