水溶性阳离子型卟啉对层状磷酸锆插层行为的研究

比较了水溶性卟啉meso-四(4-N-甲基吡啶基)卟啉(TMPyP)对具有不同层间距和结构的层状磷酸锆α-磷酸锆(α-ZrP)和γ-磷酸锆(γ-ZrP)]的插层行为. 研究发现: 相比α-磷酸锆, γ-磷酸锆虽然具有相对较大的层间距, 但同α-磷酸锆一样, TMPyP不能直接嵌入其中. 为嵌入TMPyP, 用预撑剂正丁胺(BA)处理磷酸锆. TMPyP可以嵌入α-ZrP?BA和α-ZrP?2BA(分别为单层丁胺和双层丁胺嵌入α-磷酸锆而形成的插层化合物), 其中, TMPyP以较短的时间与单层排列的丁胺交换而嵌入磷酸锆; 而卟啉却不能嵌入具有较大层间距的γ-ZrP?2BA(双层丁胺嵌入γ-磷酸锆而形成的一种很稳定的形式), 表明预撑剂在磷酸锆层板间的流动性是影响卟啉嵌入的一个重要因素. 另外, 结合XRD、红外、可见吸收等实验数据和α-磷酸锆层板高电荷密度的特性, 我们可推算出: TMPyP以自由碱的形式呈单层倾斜方式紧密堆积在α-磷酸锆层板间.

Study on the Different Layered Zirconium Phosphates Hosts for Intercalating Soluble Cationic Porphyrins

The different intercalation behavior of 5,10,15,20-tetrakis(1-methyllpyridinium-4-ylporphine] (TMPyP) into α-zirconium phosphate (α-ZrP) and γ-zirconium phosphate (γ-ZrP) was investigated. Although the interlayer distance of γ-ZrP is more than that of α-ZrP, it can not incorporate TMPyP either. Through pre-intercalating n-butylamine (BA) to expand the interlayer distances of α-ZrP and γ-ZrP, TMPyP was intercalated into α-ZrP?BA and α-ZrP?2BA, where BA forms a flat monolayer or a canted bilayer in α-ZrP. And porphyrins exchange with monolayer BA in a shorter time than bilayer BA. However, porphyrins still can not insert into γ-ZrP?2BA with large interlayer spacing, where BA forms a very stable bilayer in γ-ZrP. So flexibility of spacers is an important intercalation factor that influences the intercalation of porphyrins. In addition, our results revealed that the porphyrin presented as free base was orderly arranged with their planes inclined to the host lamella.