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Architectural Isomerism in the Three-Dimensional Prussian Blue Analogue {[CoII(TPA)]3[FeIII(CN)6][CoIII(CN)6]}: Synthesis, Crystal Structures, and Magnetic Properties
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2022-07-21 , DOI: 10.1021/acs.cgd.2c00647
Jing-Lin Liu 1 , Xue-Yang Ji 1 , Jin-Peng Xue 1 , Jie-Sheng Hu 1 , Zi-Shuo Yao 1 , Jun Tao 1
Affiliation  

Prussian Blue analogues (PBAs) with unusual properties such as spin crossover (SCO) and metal-to-metal electron transfer (MMET) are of great interest. However, the construction of new three-dimensional (3D) PBAs is a formidable challenge. Herein, two mixed-valence 3D PBAs, {[CoII(TPA)]3[FeIII(CN)6][CoIII(CN)6]}3DMF·7H2O (1·S) and {[CoII(TPA)]3[FeIII(CN)6][CoIII(CN)6]}2DMF·1H2O (2·S) (TPA = tris(2-pyridylmethyl)amine, DMF = N,N-dimethylformamide), were synthesized by a solvothermal method. Complexes 1 and 2 are architectural isomers with different crystal structures, electronic absorption spectra, and magnetic properties, one of which (1·S) showed reversible thermochromism accompanied by metal-to-metal electron transfer (MMET). Compound 1·S crystallizes in the monoclinic space group P21/c with a = 17.2227(8), b = 23.1538(10), c = 22.5074(12) Å, β = 90.388(5)°, V = 8975.17(7) Å3, and Z = 4. Compound 2·S crystallizes in the tetragonal space group P4/nnc with a = b = 33.1374(5), c = 31.7381(10) Å, V = 34851.2(15) Å3, and Z = 16. In both isomers, the 3D structures are constructed with heptanuclear heterometallic units, {[CoII(TPA)]6[FeIII(CN)6]}9+, which are interconnected by [Fe(CN)6]3– and [Co(CN)6]3– anions in the trans μ-bridge mode. This work may provide a new perspective for the design of functional PBAs materials.

中文翻译:

三维普鲁士蓝类似物 {[CoII(TPA)]3[FeIII(CN)6][CoIII(CN)6]} 中的结构异构:合成、晶体结构和磁性

具有不寻常特性的普鲁士蓝类似物 (PBA) 如自旋交叉 (SCO) 和金属间电子转移 (MMET) 引起了极大的兴趣。然而,构建新的三维 (3D) PBA 是一项艰巨的挑战。在此,两种混合价 3D PBA,{[Co II (TPA)] 3 [Fe III (CN) 6 ][Co III (CN) 6 ]}3DMF·7H 2 O ( 1 ·S) 和 {[Co II (TPA)] 3 [Fe III (CN) 6 ][Co III (CN) 6 ]}2DMF·1H 2 O ( 2 ·S) (TPA = 三(2-吡啶基甲基)胺, DMF =N , N-二甲基甲酰胺),通过溶剂热法合成。配合物12是具有不同晶体结构、电子吸收光谱和磁性的结构异构体,其中一种( 1 ·S)表现出可逆热致变色并伴随金属间电子转移(MMET)。化合物1 ·S在单斜空间群P 2 1 / c中结晶, a = 17.2227(8), b = 23.1538(10), c = 22.5074(12) Å, β = 90.388(5)°, V = 8975.17( 7) Å 3Z= 4. 化合物2 ·S 在四方空间群P 4/ nnc中结晶,a = b = 33.1374(5), c = 31.7381(10) Å, V = 34851.2(15) Å 3 , Z = 16。两种异构体,3D 结构均由七核异金属单元构成,{[Co II (TPA)] 6 [Fe III (CN) 6 ]} 9+由 [Fe(CN) 6 ] 3–和 [Co (CN) 6 ] 3–反式 μ中的阴离子-桥接模式。这项工作可能为功能性 PBA 材料的设计提供新的视角。
更新日期:2022-07-21
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