Molčanov Lidija, Androš Dubraja Lidija, Žilić Dijana, Molčanov Krešimir, Barišić Dario, Pajić Damir, Lončarić Ivor, Šantić Ana, Jurić Marijana
Ruđer Bošković Institute, Bijenička Cesta 54, Zagreb 10000, Croatia.
Department of Physics, Faculty of Science, University of Zagreb, Bijenička Cesta 54, Zagreb 10000, Croatia.
Inorg Chem. 2023 Oct 23;62(42):17219-17227. doi: 10.1021/acs.inorgchem.3c02351. Epub 2023 Oct 12.
A one-dimensional (1D) ladder-like coordination polymer {NH[{Cu(bpy)}(CO)Fe(CO)]·HO} (; bpy = 2,2'-bipyridine) containing [Cu(bpy)(μ-CO)Cu(bpy)] cationic units linked by oxalate groups of [Fe(CO)] building blocks was investigated as a new type of photoactive solid-state system. It exhibits a photocoloration effect when exposed to direct sunlight or UV/vis irradiation. The photochromic properties and mechanism were studied by powder and single-crystal X-ray diffraction, UV/vis diffuse reflectance, IR and electron paramagnetic resonance spectroscopy, magnetization and impedance measurements, and density functional theory calculations. The process of photochromism involves simultaneous intramolecular electron transfers from the oxalate ligand to Fe(III) and to [Cu(bpy)(μ-CO)Cu(bpy)], leading to the reduction of the metal centers to the electronic states Fe(II) and Cu(I), accompanied by the release of gaseous CO.
一种一维（1D）梯状配位聚合物{NH₄[Cu(bpy)(μ-CO)Fe(CO)₄]·H₂O}（；bpy = 2,2'-联吡啶），其包含由[Fe(CO)₄]结构单元的草酸根连接的[Cu(bpy)(μ-CO)Cu(bpy)]阳离子单元，作为一种新型光活性固态体系进行了研究。当暴露于直射阳光或紫外/可见光照下时，它表现出光致变色效应。通过粉末和单晶X射线衍射、紫外/可见漫反射、红外和电子顺磁共振光谱、磁化和阻抗测量以及密度泛函理论计算研究了其光致变色性质和机理。光致变色过程涉及草酸根配体同时向Fe(III)和[Cu(bpy)(μ-CO)Cu(bpy)]进行分子内电子转移，导致金属中心还原为Fe(II)和Cu(I)电子态，同时伴有气态CO的释放。
