Tran Dat T, Zavalij Peter Y, Oliver Scott R J
State University of New York at Binghamton, Department of Chemistry, Binghamton, New York 13902-6016, USA.
J Am Chem Soc. 2002 Apr 17;124(15):3966-9. doi: 10.1021/ja017333w.
Our research involves the development of new cationic materials for anion-based applications. We report the solvothermal synthesis and characterization of Pb(3)F(5)NO(3), a new layered lead fluoride material that, unlike the majority of layered and open-framework materials, is cationic in charge. The structure consists of polyhedral lead centers connected by doubly and triply bridging fluoride groups. We quantitatively exchanged the interlamellar nitrate groups of Pb(3)F(5)NO(3) for dichromate, under ambient aqueous conditions. Nuclear magnetic resonance and UV-vis spectroscopy show the reaction proceeds to 61.0% completion in several days. The material is also stable to 450 degrees C, which is vastly superior to organic resins that are still the standard for anion-exchange. The presence of extraframework anions also opens up other potentially unique anion-based properties, such as new catalytic reactions, anion intercalation, or growth of anionic clusters within the void spaces of the cationic material.
我们的研究涉及开发用于基于阴离子应用的新型阳离子材料。我们报道了Pb(3)F(5)NO(3)的溶剂热合成及表征，这是一种新型层状氟化铅材料，与大多数层状和开放框架材料不同，其电荷呈阳离子性。该结构由通过双齿和三齿桥连氟基团连接的多面体铅中心组成。我们在环境水条件下，将Pb(3)F(5)NO(3)的层间硝酸根离子定量地交换为重铬酸根离子。核磁共振和紫外可见光谱表明，该反应在数天内进行到61.0%的完成度。该材料在450摄氏度下也很稳定，这大大优于仍是阴离子交换标准的有机树脂。骨架外阴离子的存在还开启了其他潜在的独特的基于阴离子的性质，如新的催化反应、阴离子插层或在阳离子材料的空隙空间内生长阴离子簇。
