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.

Key words: α-zirconium phosphate, γ-zirconium phosphate, TMPyP, intercalation