Chirality and Spin Crossover in Iron(II)–Octacyanidorhenate(V) Coordination Polymers Induced by the Pyridine-Based Ligand’s Positional Isomer
نویسندگان
چکیده
We present two novel coordination polymers based on octacyanidorhenate(V) metalloligands and Fe(II) complexes with different positional isomers of a benzylpyridine ligand, namely 3-benzylpyridine (3-benzpy) that leads to two-dimensional {[FeII(3-benzpy)4]3[ReV(CN)8]2}·2H2O (1) network 4-benzylpyridine (4-benzpy) giving three-dimensional {[FeII(4-benzpy)4]5[ReV(CN)8]3}(ClO4)·2(4-benzpy)·6H2O·MeOH (2) framework. 1 is layered polymer honeycomb topology, crystallizing in the centrosymmetric space group, which exhibits only residual thermal spin-crossover (SCO) effect at low temperatures. The lack significant SCO probably caused by strong supramolecular interactions do not allow framework undergo structural change required spin transition. On other hand, 2 crystallizes as chiral, cationic pillared cyanido-bridged framework, consisting layers deformed square grid further bonded together additional complexes. structure completed noncoordinated 4-benzpy, water, methanol molecules, well perchlorate counterions. chiral character was confirmed single-crystal X-ray diffractions studies second-harmonic generation (SHG) detected room temperature. pronounced two-step, incomplete embedded intricate course transition related presence five crystallographically distinguishable centers environments. first noticeable step realized undergoing between 250 150 K, while second one type remaining Therefore, rare example material showing also nontrivial These properties were achieved subtle modification pyridine-based ligand indicating advantage iron(II)–octacyanidorhenate(V) systems formation functional materials.
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Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan. b Present address:Department of Human Intelligence Systems, Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Kitakyushu, Japan. c Synchrotron X-ray Station at SPring-8, National Institute for Materials Science, Sayo-gun, Hyogo, Japan....
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ژورنال
عنوان ژورنال: Crystal Growth & Design
سال: 2023
ISSN: ['1528-7483', '1528-7505']
DOI: https://doi.org/10.1021/acs.cgd.2c01462