吡啶盐/咪唑盐调控钴萘基二膦酸配位聚合物的结构和性质

通过引入质子化的1,3-二(4-吡啶基)丙烷(1,3-dppH₂²⁺)和双(咪唑-1-甲基)苯(1,4-bixH₂²⁺)作为阳离子模板，采用水热反应，得到3种基于1,4-萘二膦酸(1,4-ndpaH₄)配体的钴萘二膦酸配位聚合物：(1,3-dppH₂)₂[Co₄(1,4-ndpa)(1,4-ndpaH)₂(1,4-ndpaH₂)]·6H₂O (1)、(1,4-bixH₂)_0.5[Co(1,4-ndpaH)](2)和(1,4-bixH₂)_0.5[Co₂(1,4-ndpaH)(1,4-ndpaH₂)(H₂O)₂](3)。对配合物1～3分别进行了元素分析、红外光谱、单晶X射线衍射、...

Pyridinium/imidazolium-triggered modulation of structure and properties of cobalt naphthalene-diphosphates

By the introduction of protonated 1, 3-di(4-pyridyl)propane (1, 3-dppH₂²⁺) and protonated bis(imidazol-1- ylmethyl)benzene (1, 4-bixH₂²⁺) as a cationic template, three new cobalt naphthalene-diphosphate coordination poly- mers based on 1, 4-naphthalenediphosphonic acid (1, 4-ndpaH₄), namely (1, 3-dppH₂)₂[Co₄(1, 4-ndpa)(1, 4-ndpaH)₂(1, 4-ndpaH₂)]·6H₂O (1), (1, 4-bixH₂)_0.5[Co(1, 4-ndpaH)] (2), and (1, 4-bixH₂)_0.5[Co₂(1, 4-ndpaH)(1, 4-ndpaH₂)(H₂O)₂] (3), have been hydrothermally synthesized. complexes 1-3 were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction, powder X-ray diffraction, and thermogravimetric analysis, respectively. In complexes 1 and 2, inorganic chains of corner-sharing {CoO₄} and {PO₃C} tetrahedron are cross-linked by naphthalene ligands into 3D open-framework structures. The protonated di-pyridinium/imidazolium moieties, 1, 3-dppH₂²⁺ for 2 and 1, 4-bixH₂²⁺ for 2, lie inside the skeletal voids of the crystal structure, respectively. Interestingly, complex 3 with similar chemical composition to 2 except for an additional 1, 4-ndpaH₂^2- ligand and two coordinated water molecules shows a 2D undulating layer structure, where the chains of corner-sharing {CoO₅} trigonal bipyramid, {CoO6} octahedron, and {PO₃C} tetrahedron are cross-linked by naphthalene groups. Adjacent layers are packed in AB stacking into the supramolecular structure, in which 1, 4-bixH₂²⁺ ions fill and balance the charge of 3. Magnetic studies reveal that dominant antiferromagnetic interactions between the magnetic centers are propagated in complexes 1 and 2.