Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands
A new dinuclear Gd(III) complex was synthesized and named [Gd<sub>2</sub>(L)<sub>4</sub>(Phen)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>(DMF)<sub>2</sub>]·2H<sub>2</sub>O·2Cl (<b>1</b>). Here, L is the 6-ph...
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MDPI AG
2023-11-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/22/7595 |
| _version_ | 1797458254404517888 |
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| author | Li-Hua Wang Xi-Shi Tai |
| author_facet | Li-Hua Wang Xi-Shi Tai |
| author_sort | Li-Hua Wang |
| collection | DOAJ |
| description | A new dinuclear Gd(III) complex was synthesized and named [Gd<sub>2</sub>(L)<sub>4</sub>(Phen)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>(DMF)<sub>2</sub>]·2H<sub>2</sub>O·2Cl (<b>1</b>). Here, L is the 6-phenylpyridine-2-carboxylate anion, Phen represents 1,10-phenanthroline, DMF is called <i>N,N</i>-dimethylformamide, and Cl<sup>−</sup> is the chloride anion, which is characterized by IR and single crystal X-ray diffraction analysis. The structural analysis reveals that complex (<b>1</b>) is a cation–anion complex, and each Gd(III) ion is eight-coordinated with four O atoms (O1, O5, O2a, O4a, or O1a, O2, O4, O5a) of four different bidentate L ligands, two O atoms (O6, or O6a) of DMF molecules, two N atoms (N1, N2, or N1a, N2a) of Phen ligands, and two O atoms (O3 or O3a) of coordinated water molecules. Complex (<b>1</b>) forms the three-dimensional π–π stacking network structure with cavities occupied by chloride anions and uncoordinated water molecules. The Hirschfeld surface of the complex (<b>1</b>) shows that the H···H contacts represented the largest contribution (48.5%) to the Hirschfeld surface, followed by C···H/H···C and O···H/H···O contacts with contributions of 27.2% and 6.0%, respectively. To understand the electronic structure of the complex (<b>1</b>), the DFT calculations have been performed. The photocatalytic CO<sub>2</sub> reduction activity shows complex (<b>1</b>) has excellent catalytic activity with yields of 22.1 μmol/g (CO) and 6.0 μmol/g (CH<sub>4</sub>) after three hours. And the selectivity of CO can achieve 78.5%. |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T16:34:26Z |
| publishDate | 2023-11-01 |
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| spelling | doaj.art-8f9e46f0883d4a328ed4ec01c0946a302023-11-24T14:58:22ZengMDPI AGMolecules1420-30492023-11-012822759510.3390/molecules28227595Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline LigandsLi-Hua Wang0Xi-Shi Tai1College of Biology and Oceanography, Weifang University, Weifang 261061, ChinaCollege of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, ChinaA new dinuclear Gd(III) complex was synthesized and named [Gd<sub>2</sub>(L)<sub>4</sub>(Phen)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>(DMF)<sub>2</sub>]·2H<sub>2</sub>O·2Cl (<b>1</b>). Here, L is the 6-phenylpyridine-2-carboxylate anion, Phen represents 1,10-phenanthroline, DMF is called <i>N,N</i>-dimethylformamide, and Cl<sup>−</sup> is the chloride anion, which is characterized by IR and single crystal X-ray diffraction analysis. The structural analysis reveals that complex (<b>1</b>) is a cation–anion complex, and each Gd(III) ion is eight-coordinated with four O atoms (O1, O5, O2a, O4a, or O1a, O2, O4, O5a) of four different bidentate L ligands, two O atoms (O6, or O6a) of DMF molecules, two N atoms (N1, N2, or N1a, N2a) of Phen ligands, and two O atoms (O3 or O3a) of coordinated water molecules. Complex (<b>1</b>) forms the three-dimensional π–π stacking network structure with cavities occupied by chloride anions and uncoordinated water molecules. The Hirschfeld surface of the complex (<b>1</b>) shows that the H···H contacts represented the largest contribution (48.5%) to the Hirschfeld surface, followed by C···H/H···C and O···H/H···O contacts with contributions of 27.2% and 6.0%, respectively. To understand the electronic structure of the complex (<b>1</b>), the DFT calculations have been performed. The photocatalytic CO<sub>2</sub> reduction activity shows complex (<b>1</b>) has excellent catalytic activity with yields of 22.1 μmol/g (CO) and 6.0 μmol/g (CH<sub>4</sub>) after three hours. And the selectivity of CO can achieve 78.5%.https://www.mdpi.com/1420-3049/28/22/75956-phenylpyridine-2-carboxylic acid1,10-phenanthrolinedinuclear Gd(III) complexsynthesiscrystal structurehirschfeld surface analysis |
| spellingShingle | Li-Hua Wang Xi-Shi Tai Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands Molecules 6-phenylpyridine-2-carboxylic acid 1,10-phenanthroline dinuclear Gd(III) complex synthesis crystal structure hirschfeld surface analysis |
| title | Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands |
| title_full | Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands |
| title_fullStr | Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands |
| title_full_unstemmed | Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands |
| title_short | Synthesis, Structural Characterization, Hirschfeld Surface Analysis and Photocatalytic CO<sub>2</sub> Reduction Activity of a New Dinuclear Gd(III) Complex with 6-Phenylpyridine-2-Carboxylic Acid and 1,10-Phenanthroline Ligands |
| title_sort | synthesis structural characterization hirschfeld surface analysis and photocatalytic co sub 2 sub reduction activity of a new dinuclear gd iii complex with 6 phenylpyridine 2 carboxylic acid and 1 10 phenanthroline ligands |
| topic | 6-phenylpyridine-2-carboxylic acid 1,10-phenanthroline dinuclear Gd(III) complex synthesis crystal structure hirschfeld surface analysis |
| url | https://www.mdpi.com/1420-3049/28/22/7595 |
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