A Naphthalene Diimide Based Macrocycle Containing Quaternary Ammonium Groups: An Electron‐Deficient Host for Aromatic Carboxylate Derivatives. Issue 7 (7th July 2020)

• Record Type: Journal Article
• Authors: Türel, Tankut; Valiyaveettil, Suresh
• Is Part Of: ChemPlusChem. Volume 85:Issue 7(2020)
• Page Start: 1430
• Page End: 1437
• Publication Date: 2020-07-07
• Subjects: anion recognition -- host-guest complexation -- macrocycle -- naphthalene diimide -- π-π interactions; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.202000258
• Languages: English
• ISSNs: 2192-6506

Abstract

Abstract: Naphthalene diimide (NDI) compounds are widely used as electron acceptors in various applications. Herein, we combine NDI with quaternary ammonium groups for the synthesis of a highly electron‐deficient linear compound 2 and macrocycle 3 . The complexation studies of the water‐soluble macrocycle 3 with aromatic di‐ and tetra‐ carboxylate anions in water were done using absorption, emission, 1 H NMR and NOESY spectroscopic titrations. The NDI incorporated macrocycle 3 showed high binding affinities towards linear aromatic tetracarboxylate anions owing to the size and charge complementarity of the host‐guest complex. Macrocycle 3 binds tetracarboxylate anion much better than dicarboxylate anions. Furthermore, the macrocycle 3 is solvated differently in acetonitrile and in water or dimethyl sulfoxide, which induces changes in conformation and photophysical properties. Such electron‐deficient optically active macrocycles are useful for developing useful sensor materials. Abstract : Tetracarboxylate anions are welcome : A water‐soluble naphthalene diimide based macrocycle with highly electron‐deficient and linear cavity is synthesized and fully characterised, which includes single‐crystal analysis. The macrocycle forms strong complexes with electron‐rich aromatic carboxylate anions through complementary size‐cavity fit, electrostatic and π‐π interactions. The conformation and optical properties of the macrocycle are different in water and in acetonitrile solvents due to the different degree of solvation.