Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures
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,...
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MDPI AG
2021-01-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/11/1/77 |
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| author | Nur Shuhaila Haryani Haris Nafisah Mansor Mohd Sukeri Mohd Yusof Christopher J. Sumby Maisara Abdul Kadir |
| author_facet | Nur Shuhaila Haryani Haris Nafisah Mansor Mohd Sukeri Mohd Yusof Christopher J. Sumby Maisara Abdul Kadir |
| author_sort | Nur Shuhaila Haryani Haris |
| collection | DOAJ |
| description | 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[<i>N,N′</i>-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L1), 1,2-bis[<i>N,N′</i>-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L2), 1,2-bis[<i>N,N′</i>-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]propane (L3) and 1,2-bis[<i>N,N′</i>-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, {[Cd<sub>3</sub>(L2)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>](NO<sub>3</sub>)<sub>6</sub>·12H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub> and {[Cd(SO<sub>4</sub>)(L4)(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub>. 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(SO<sub>4</sub>)(L4)(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub> 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 {[Cd<sub>3</sub>(L2)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>](NO<sub>3</sub>)<sub>6</sub>·12H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub>, showing potential for materials made from these ligands to serve as anion receptors. |
| first_indexed | 2024-03-09T04:17:50Z |
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| language | English |
| last_indexed | 2024-03-09T04:17:50Z |
| publishDate | 2021-01-01 |
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| spelling | doaj.art-3ff34ceb9738448d87f86f0eef39eaa12023-12-03T13:51:36ZengMDPI AGCrystals2073-43522021-01-011117710.3390/cryst11010077Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal StructuresNur Shuhaila Haryani Haris0Nafisah Mansor1Mohd Sukeri Mohd Yusof2Christopher J. Sumby3Maisara Abdul Kadir4Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 21030, Terengganu, MalaysiaFaculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 21030, Terengganu, MalaysiaFaculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 21030, Terengganu, MalaysiaSchool of Physical Sciences, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, SA 5005, AustraliaFaculty of Science and Marine Environment, Universiti Malaysia Terengganu, Kuala Nerus 21030, Terengganu, MalaysiaThe 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[<i>N,N′</i>-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L1), 1,2-bis[<i>N,N′</i>-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]ethane (L2), 1,2-bis[<i>N,N′</i>-6-(3-pyridylmethylamido)pyridyl-2-carboxyamido]propane (L3) and 1,2-bis[<i>N,N′</i>-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, {[Cd<sub>3</sub>(L2)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>](NO<sub>3</sub>)<sub>6</sub>·12H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub> and {[Cd(SO<sub>4</sub>)(L4)(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub>. 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(SO<sub>4</sub>)(L4)(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub> 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 {[Cd<sub>3</sub>(L2)<sub>4</sub>(H<sub>2</sub>O)<sub>10</sub>](NO<sub>3</sub>)<sub>6</sub>·12H<sub>2</sub>O·CH<sub>3</sub>OH}<sub>n</sub>, showing potential for materials made from these ligands to serve as anion receptors.https://www.mdpi.com/2073-4352/11/1/77synthesiscrystalcoordination polymertetraamidepre-organized amideframework |
| spellingShingle | Nur Shuhaila Haryani Haris Nafisah Mansor Mohd Sukeri Mohd Yusof Christopher J. Sumby Maisara Abdul Kadir Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures Crystals synthesis crystal coordination polymer tetraamide pre-organized amide framework |
| title | Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures |
| title_full | Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures |
| title_fullStr | Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures |
| title_full_unstemmed | Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures |
| title_short | Investigating the Potential of Flexible and Pre-Organized Tetraamide Ligands to Encapsulate Anions in One-Dimensional Coordination Polymers: Synthesis, Spectroscopic Studies and Crystal Structures |
| title_sort | investigating the potential of flexible and pre organized tetraamide ligands to encapsulate anions in one dimensional coordination polymers synthesis spectroscopic studies and crystal structures |
| topic | synthesis crystal coordination polymer tetraamide pre-organized amide framework |
| url | https://www.mdpi.com/2073-4352/11/1/77 |
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