Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity
A new azo-ligand, 1,3-dimethyl-5-(p-carboxy-phenylazo)-6-aminouracil (H3L) containing 6-aminouracil (a biomolecule) and a carboxylic function (a potential linker) was synthesized. This ligand was then employed for complexation with Ni(II), resulting in the Ni(II)/Na(I) heterometallic {[NiNa2(μ-HL)2(...
| Main Authors: | , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
| Published: |
2020
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| Online Access: | https://hdl.handle.net/10356/139638 |
| _version_ | 1826112680312700928 |
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| author | Purkayastha, Atanu Debnath, Diptanu Majumder, Moumita Ortega-Castro, Joaquín Kirillov, Alexander M. Ganguly, Rakesh Klak, Julia Frontera, Antonio Misra, Tarun Kumar |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Purkayastha, Atanu Debnath, Diptanu Majumder, Moumita Ortega-Castro, Joaquín Kirillov, Alexander M. Ganguly, Rakesh Klak, Julia Frontera, Antonio Misra, Tarun Kumar |
| author_sort | Purkayastha, Atanu |
| collection | NTU |
| description | A new azo-ligand, 1,3-dimethyl-5-(p-carboxy-phenylazo)-6-aminouracil (H3L) containing 6-aminouracil (a biomolecule) and a carboxylic function (a potential linker) was synthesized. This ligand was then employed for complexation with Ni(II), resulting in the Ni(II)/Na(I) heterometallic {[NiNa2(μ-HL)2(μ-H2O)2(H2O)6]·6H2O}n (1) and Ni(II) homometallic {[Ni2(μ-HL)2(H2O)4]·5·.5H2O}n (2) 1D coordination polymers. These were obtained from similar reaction mixtures and conditions, except the type of the base (NaOH for 1 or KOH/Et3N for 2). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, UV-vis, NMR, and IR spectroscopy. Both the coordination polymers 1 and 2 show resembling zigzag chains that are topologically classified as 2-connected underlying nets with the 2C1 topology. In 1, the 1D metal-organic chains are further extended by intermolecular H-bonds, giving rise to a 3D H-bonded net; it is topologically described as a uninodal 6-connected net with the pcu topology. In solution, the 1D polymeric structures of both compounds disaggregate into monomeric Ni(II)-square-planar complex units [Ni(HL)2]2−, as evidenced by NMR and UV-vis spectroscopy studies. The magnetic properties of 2 were also investigated, indicating a dominant zero field splitting parameter D of the Ni(II) center. The type of the base is important for tuning the selective formation of the desired product 1 or 2. Density functional theory (DFT) study justifies the experimental findings for a base-assisted selectivity between the compounds 1 or 2 by optimizing their structures at the PBE-D/DNP level of theory. The existence of agostic interactions between the C–H bonds of the methyl groups of the coordinated HL2− moieties and the Ni centers in both structures is suggested by natural bond orbital (NBO) calculations at the M06-2X/6-31 + G∗ level of theory. The compound 1 proves to be a potential inhibitor of a bacterial virulence factor, pyocyanin. |
| first_indexed | 2024-10-01T03:11:10Z |
| format | Journal Article |
| id | ntu-10356/139638 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T03:11:10Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1396382020-05-20T09:20:07Z Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity Purkayastha, Atanu Debnath, Diptanu Majumder, Moumita Ortega-Castro, Joaquín Kirillov, Alexander M. Ganguly, Rakesh Klak, Julia Frontera, Antonio Misra, Tarun Kumar School of Physical and Mathematical Sciences Science::Chemistry Coordination Polymer Crystal Structure A new azo-ligand, 1,3-dimethyl-5-(p-carboxy-phenylazo)-6-aminouracil (H3L) containing 6-aminouracil (a biomolecule) and a carboxylic function (a potential linker) was synthesized. This ligand was then employed for complexation with Ni(II), resulting in the Ni(II)/Na(I) heterometallic {[NiNa2(μ-HL)2(μ-H2O)2(H2O)6]·6H2O}n (1) and Ni(II) homometallic {[Ni2(μ-HL)2(H2O)4]·5·.5H2O}n (2) 1D coordination polymers. These were obtained from similar reaction mixtures and conditions, except the type of the base (NaOH for 1 or KOH/Et3N for 2). Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, UV-vis, NMR, and IR spectroscopy. Both the coordination polymers 1 and 2 show resembling zigzag chains that are topologically classified as 2-connected underlying nets with the 2C1 topology. In 1, the 1D metal-organic chains are further extended by intermolecular H-bonds, giving rise to a 3D H-bonded net; it is topologically described as a uninodal 6-connected net with the pcu topology. In solution, the 1D polymeric structures of both compounds disaggregate into monomeric Ni(II)-square-planar complex units [Ni(HL)2]2−, as evidenced by NMR and UV-vis spectroscopy studies. The magnetic properties of 2 were also investigated, indicating a dominant zero field splitting parameter D of the Ni(II) center. The type of the base is important for tuning the selective formation of the desired product 1 or 2. Density functional theory (DFT) study justifies the experimental findings for a base-assisted selectivity between the compounds 1 or 2 by optimizing their structures at the PBE-D/DNP level of theory. The existence of agostic interactions between the C–H bonds of the methyl groups of the coordinated HL2− moieties and the Ni centers in both structures is suggested by natural bond orbital (NBO) calculations at the M06-2X/6-31 + G∗ level of theory. The compound 1 proves to be a potential inhibitor of a bacterial virulence factor, pyocyanin. 2020-05-20T09:20:07Z 2020-05-20T09:20:07Z 2018 Journal Article Purkayastha, A., Debnath, D., Majumder, M., Ortega-Castro, J., Kirillov, A. M., Ganguly, R., . . . Misra, T. K. (2018). Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity. Inorganica Chimica Acta, 482, 384-394. doi:10.1016/j.ica.2018.06.037 0020-1693 https://hdl.handle.net/10356/139638 10.1016/j.ica.2018.06.037 2-s2.0-85049306152 482 384 394 en Inorganica Chimica Acta © 2018 Elsevier B.V. All rights reserved. |
| spellingShingle | Science::Chemistry Coordination Polymer Crystal Structure Purkayastha, Atanu Debnath, Diptanu Majumder, Moumita Ortega-Castro, Joaquín Kirillov, Alexander M. Ganguly, Rakesh Klak, Julia Frontera, Antonio Misra, Tarun Kumar Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title | Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title_full | Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title_fullStr | Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title_full_unstemmed | Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title_short | Nickel(II) based homo- vs heterometallic 1D coordination polymers derived from a novel 6-aminouracil building block : structures, topologies, non-covalent interactions, magnetism, and antibacterial activity |
| title_sort | nickel ii based homo vs heterometallic 1d coordination polymers derived from a novel 6 aminouracil building block structures topologies non covalent interactions magnetism and antibacterial activity |
| topic | Science::Chemistry Coordination Polymer Crystal Structure |
| url | https://hdl.handle.net/10356/139638 |
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