Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures

Date

2021

Authors

Haris, N.S.H.
Mansor, N.
Mohd Yusof, M.S.
Sumby, C.J.
Abdul Kadir, M.

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Crystals, 2021; 11(1):77-1-77-14

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Nur Shuhaila Haryani Haris, Nafisah Mansor, Mohd Sukeri Mohd Yusof, Christopher J. Sumby and Maisara Abdul Kadir

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Abstract

The synthesis of amide-based molecules, possessing pre-organized structures, has received significant attention due to their potential applications as molecular receptors and as components of nanomaterials. In this study, four extended tetraamide ligands incorporating ethylene and propylene spacers, namely 1,2-bis[N,N′-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L1), 1,2-bis[N,N′-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L2), 1,2-bis[N,N′-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]propane (L3) and 1,2-bis[N,N′-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]propane (L4), were successfully synthesized. Further, reaction of L2 and L4, incorporating pendant 4-pyridyl donors as the metal coordinating sites, with cadmium salts, produced two close-packed one-dimensional coordination polymers, {[Cd3(L2)4(H2O)10](NO3)6·12H2O·CH3OH}n and {[Cd(SO4)(L4)(H2O)2]·4H2O·CH3OH}n. X-ray crystallography reveals that the flexible tetraamide ligands fold upon themselves in the coordination polymer structure. As a consequence, the anion pocket in {[Cd(SO4)(L4)(H2O)2]·4H2O·CH3OH}n incorporating the ligand with the propylene spacer was blocked from encapsulating charge-balancing anions, which were involved in bridging the di-cadmium units. Interestingly, a strong interaction between the 2,6-pyridine dicarboxamide moiety with the nitrate anions was found in {[Cd3(L2)4(H2O)10](NO3)6·12H2O·CH3OH}n, showing potential for materials made from these ligands to serve as anion receptors.

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Published: 19 January 2021

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© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).

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