Kosuke Kitase*, Daisuke Akahoshi and Takafumi Kitazawa,
{"title":"由一维和二维氰桥配位聚合物组成的轮烷类配合物：Fe（4-甲基嘧啶）2[Au(CN)2]2·Fe（4-甲基嘧啶）2(H2O)2[Au(CN)2]·[Au(CN)4]","authors":"Kosuke Kitase*, Daisuke Akahoshi and Takafumi Kitazawa, ","doi":"10.1021/acs.cgd.5c0021610.1021/acs.cgd.5c00216","DOIUrl":null,"url":null,"abstract":"<p >Coordination polymers showing the spin-crossover (SCO) phenomenon have attracted considerable attention because of their tunable properties and potential applications as sensors or switching materials. Although many of these polymers have been reported, examples with mixed-valence metal ions and N-heteroaromatic ligands other than pyridine-, pyrazine-, and bipyridine-type ligands are scarce. In this study, we synthesized a novel cyano-bridged coordination polymer, Fe(4-methylpyrimidine)<sub>2</sub>[Au(CN)<sub>2</sub>]<sub>2</sub>·Fe(4-methylpyrimidine)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[Au(CN)<sub>2</sub>]·[Au(CN)<sub>4</sub>] (complex <b>1</b>), with a rotaxane-like structure. This polymer comprised monovalent Au atoms in a two-dimensional Soma–Iwamoto-type {Fe(4-methylpyrimidine)<sub>2</sub>[Au(CN)<sub>2</sub>]<sub>2</sub>}<sub><i>n</i></sub> layer as well as a one-dimensional {Fe(4-methylpyrimidine)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[Au(CN)<sub>2</sub>]}<sub><i>n</i></sub><sup><i>n</i>+</sup> cationic chain and trivalent Au atoms in the zero-dimensional [Au(CN)<sub>4</sub>]<sup>−</sup> anion. Complex <b>1</b> showed a half SCO phenomenon above 300 K. The Fe K-edge X-ray absorption fine structure (XAFS) spectrum of complex <b>1</b> revealed that some of the Fe sites were in a low-spin state at room temperature, while all of the Fe sites were in a high-spin state at 395 K. The Au L<sub>3</sub>-edge XAFS spectrum of complex <b>1</b> revealed that monovalent and trivalent Au sites were present at room temperature and 398 K.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4106–4111 4106–4111"},"PeriodicalIF":3.2000,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Rotaxane-like Complex Consisting of 1D and 2D Cyano-Bridged Coordination Polymers: Fe(4-methylpyrimidine)2[Au(CN)2]2·Fe(4-methylpyrimidine)2(H2O)2[Au(CN)2]·[Au(CN)4]\",\"authors\":\"Kosuke Kitase*, Daisuke Akahoshi and Takafumi Kitazawa, \",\"doi\":\"10.1021/acs.cgd.5c0021610.1021/acs.cgd.5c00216\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Coordination polymers showing the spin-crossover (SCO) phenomenon have attracted considerable attention because of their tunable properties and potential applications as sensors or switching materials. Although many of these polymers have been reported, examples with mixed-valence metal ions and N-heteroaromatic ligands other than pyridine-, pyrazine-, and bipyridine-type ligands are scarce. In this study, we synthesized a novel cyano-bridged coordination polymer, Fe(4-methylpyrimidine)<sub>2</sub>[Au(CN)<sub>2</sub>]<sub>2</sub>·Fe(4-methylpyrimidine)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[Au(CN)<sub>2</sub>]·[Au(CN)<sub>4</sub>] (complex <b>1</b>), with a rotaxane-like structure. This polymer comprised monovalent Au atoms in a two-dimensional Soma–Iwamoto-type {Fe(4-methylpyrimidine)<sub>2</sub>[Au(CN)<sub>2</sub>]<sub>2</sub>}<sub><i>n</i></sub> layer as well as a one-dimensional {Fe(4-methylpyrimidine)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[Au(CN)<sub>2</sub>]}<sub><i>n</i></sub><sup><i>n</i>+</sup> cationic chain and trivalent Au atoms in the zero-dimensional [Au(CN)<sub>4</sub>]<sup>−</sup> anion. Complex <b>1</b> showed a half SCO phenomenon above 300 K. The Fe K-edge X-ray absorption fine structure (XAFS) spectrum of complex <b>1</b> revealed that some of the Fe sites were in a low-spin state at room temperature, while all of the Fe sites were in a high-spin state at 395 K. 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Rotaxane-like Complex Consisting of 1D and 2D Cyano-Bridged Coordination Polymers: Fe(4-methylpyrimidine)2[Au(CN)2]2·Fe(4-methylpyrimidine)2(H2O)2[Au(CN)2]·[Au(CN)4]
Coordination polymers showing the spin-crossover (SCO) phenomenon have attracted considerable attention because of their tunable properties and potential applications as sensors or switching materials. Although many of these polymers have been reported, examples with mixed-valence metal ions and N-heteroaromatic ligands other than pyridine-, pyrazine-, and bipyridine-type ligands are scarce. In this study, we synthesized a novel cyano-bridged coordination polymer, Fe(4-methylpyrimidine)2[Au(CN)2]2·Fe(4-methylpyrimidine)2(H2O)2[Au(CN)2]·[Au(CN)4] (complex 1), with a rotaxane-like structure. This polymer comprised monovalent Au atoms in a two-dimensional Soma–Iwamoto-type {Fe(4-methylpyrimidine)2[Au(CN)2]2}n layer as well as a one-dimensional {Fe(4-methylpyrimidine)2(H2O)2[Au(CN)2]}nn+ cationic chain and trivalent Au atoms in the zero-dimensional [Au(CN)4]− anion. Complex 1 showed a half SCO phenomenon above 300 K. The Fe K-edge X-ray absorption fine structure (XAFS) spectrum of complex 1 revealed that some of the Fe sites were in a low-spin state at room temperature, while all of the Fe sites were in a high-spin state at 395 K. The Au L3-edge XAFS spectrum of complex 1 revealed that monovalent and trivalent Au sites were present at room temperature and 398 K.
期刊介绍：
The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials.
Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.
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