Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
J Am Chem Soc. 2010 Jan 27;132(3):922-3. doi: 10.1021/ja909629f.
Phosphorescent cyclometalated iridium tris(2-phenylpyridine) derivatives were designed and incorporated into coordination polymers as tricarboxylate bridging ligands. Three different crystalline coordination polymers were synthesized using a solvothermal technique and were characterized using a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, IR spectroscopy, gas adsorption measurements, and luminescence measurements. The coordination polymer built from Ir3-(2-pyridyl)benzoate, 1, was found to be highly porous with a nitrogen BET surface area of 764 m(2)/g, whereas the coordination polymers built from Ir4-(2-pyridyl)benzoate, 2 and 3, were nonporous. The (3)MLCT phosphorescence of each of the three coordination polymers was quenched in the presence of O(2). However, only 1 showed quick and reversible luminescence quenching by oxygen, whereas 2 and 3 exhibited gradual and irreversible luminescence quenching by oxygen. The high permanent porosity of 1 allows for rapid diffusion of oxygen through the open channels, leading to efficient and reversible quenching of the (3)MLCT phosphorescence. This work highlights the opportunity of designing highly porous and luminescent coordination polymers for sensing other important analytes.
设计了具有磷光的金属铱配合物三(2-苯基吡啶)衍生物，并将其作为三羧酸桥联配体引入配位聚合物中。使用溶剂热技术合成了三种不同的结晶配位聚合物，并通过多种方法进行了表征，包括单晶 X 射线衍射、PXRD、TGA、IR 光谱、气体吸附测量和发光测量。由 Ir3-(2-吡啶基)苯甲酸酯，1 构建的配位聚合物具有很高的多孔性，氮气 BET 比表面积为 764 m(2)/g，而由 Ir4-(2-吡啶基)苯甲酸酯，2 和 3 构建的配位聚合物则是无孔的。三种配位聚合物的每个都具有(3)MLCT 磷光，在存在 O(2)的情况下被猝灭。然而，只有 1 表现出对氧气的快速和可逆的发光猝灭，而 2 和 3 则表现出逐渐和不可逆的发光猝灭。1 的高永久孔隙率允许氧气通过开放通道快速扩散，从而有效地和可逆地猝灭(3)MLCT 磷光。这项工作突出了设计具有高孔隙率和发光性的配位聚合物用于传感其他重要分析物的机会。
