Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex
A novel heteroleptic paddlewheel-type dirhodium (Rh<sub>2</sub>) complex [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub>(PABC)] (<b>1</b>; PABC = <i>para</i>-aminobenzenecarboxylate), which has an amino gro...
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MDPI AG
2020-02-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/10/2/85 |
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| author | Kazuki Arakawa Natsumi Yano Nanako Imasaki Yoshihiro Kohara Daiki Yatsushiro Daiki Atarashi Makoto Handa Yusuke Kataoka |
| author_facet | Kazuki Arakawa Natsumi Yano Nanako Imasaki Yoshihiro Kohara Daiki Yatsushiro Daiki Atarashi Makoto Handa Yusuke Kataoka |
| author_sort | Kazuki Arakawa |
| collection | DOAJ |
| description | A novel heteroleptic paddlewheel-type dirhodium (Rh<sub>2</sub>) complex [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub>(PABC)] (<b>1</b>; PABC = <i>para</i>-aminobenzenecarboxylate), which has an amino group as a potential donor site for coordination with the metal ion, was synthesized and characterized by <sup>1</sup>H NMR, ESI-TOF-MS, infrared spectra, and elemental analysis. The slow evaporation of <i>N,N</i>-dimethylformamide (DMF)-dissolved <b>1</b> produces the purple-colored crystalline polymeric species [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub> (PABC)(DMF)]<sub>n</sub> (<b>1P</b>). Single-crystal and powder X-ray diffraction analyses, as well as thermo-gravimetric analysis, clarified that <b>1P</b> formed a one-dimensional polymeric structure, in which the two axial sites of the Rh<sub>2</sub> ion in <b>1P</b> are coordinated by a DMF molecule and an amino group of the PABC ligand of the neighboring molecule <b>1</b>, by coordination-induced self-assembly (polymerization) with an Rh-amino bond. The reversible structural change (self-assembly and disassembly transformations) between the discrete species [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub>(PABC)(DMF)<sub>2</sub>] (<b>1D</b>; green solution) and the polymeric species <b>1P</b> (purple solid) was accompanied by a color change, which easily occurred by the dissolution and evaporation procedures with DMF. |
| first_indexed | 2024-04-14T02:27:05Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-14T02:27:05Z |
| publishDate | 2020-02-01 |
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| series | Crystals |
| spelling | doaj.art-e919f82de2c34c86af765056dae2d80f2022-12-22T02:17:50ZengMDPI AGCrystals2073-43522020-02-011028510.3390/cryst10020085cryst10020085Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium ComplexKazuki Arakawa0Natsumi Yano1Nanako Imasaki2Yoshihiro Kohara3Daiki Yatsushiro4Daiki Atarashi5Makoto Handa6Yusuke Kataoka7Department of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanSpecial Course of Science and Engineering, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanDepartment of Chemistry, Graduate School of Natural Science and Technology, Shimane University, 1060 Nishikawatsu, Matsue, Shimane 690-8504, JapanA novel heteroleptic paddlewheel-type dirhodium (Rh<sub>2</sub>) complex [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub>(PABC)] (<b>1</b>; PABC = <i>para</i>-aminobenzenecarboxylate), which has an amino group as a potential donor site for coordination with the metal ion, was synthesized and characterized by <sup>1</sup>H NMR, ESI-TOF-MS, infrared spectra, and elemental analysis. The slow evaporation of <i>N,N</i>-dimethylformamide (DMF)-dissolved <b>1</b> produces the purple-colored crystalline polymeric species [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub> (PABC)(DMF)]<sub>n</sub> (<b>1P</b>). Single-crystal and powder X-ray diffraction analyses, as well as thermo-gravimetric analysis, clarified that <b>1P</b> formed a one-dimensional polymeric structure, in which the two axial sites of the Rh<sub>2</sub> ion in <b>1P</b> are coordinated by a DMF molecule and an amino group of the PABC ligand of the neighboring molecule <b>1</b>, by coordination-induced self-assembly (polymerization) with an Rh-amino bond. The reversible structural change (self-assembly and disassembly transformations) between the discrete species [Rh<sub>2</sub>(O<sub>2</sub>CCH<sub>3</sub>)<sub>3</sub>(PABC)(DMF)<sub>2</sub>] (<b>1D</b>; green solution) and the polymeric species <b>1P</b> (purple solid) was accompanied by a color change, which easily occurred by the dissolution and evaporation procedures with DMF.https://www.mdpi.com/2073-4352/10/2/85coordination polymerself-assemblycrystal structurepaddlewheel-type complexdirhodium complex |
| spellingShingle | Kazuki Arakawa Natsumi Yano Nanako Imasaki Yoshihiro Kohara Daiki Yatsushiro Daiki Atarashi Makoto Handa Yusuke Kataoka Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex Crystals coordination polymer self-assembly crystal structure paddlewheel-type complex dirhodium complex |
| title | Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex |
| title_full | Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex |
| title_fullStr | Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex |
| title_full_unstemmed | Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex |
| title_short | Coordination-Induced Self-Assembly of a Heteroleptic Paddlewheel-Type Dirhodium Complex |
| title_sort | coordination induced self assembly of a heteroleptic paddlewheel type dirhodium complex |
| topic | coordination polymer self-assembly crystal structure paddlewheel-type complex dirhodium complex |
| url | https://www.mdpi.com/2073-4352/10/2/85 |
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