The intercalation reaction of 2,2'-bipyridine with layered compound MnPS3

The intercalation process of 2,2'-bipyridine into layered MnPS3 is studied with powder X-ray powder diffraction (XRD) technology as the monitoring tool. From the XRD results, it is found that the absence or presence of acid greatly influences the existing form and the arranged orientation of the guest. Two series of the reactions are carried out. In Series A, only MnPS3 and 2,2'-bipyridine are present. While in Series B, a variety of acetic acid is added. During the intercalation of Series A, there coexist four phases: the 0 0 l phase (with lattice spacing of 6.47 A) is pristine MnPS3; the 0 0 l' phase (with lattice spacing of 9.81 A), indicating the parallel orientation of the 2,2'-bipyridine molecular ring to the layer; the 0 0 l'' phase (with lattice spacing of 12.20 A), indicating the perpendicular orientation of the 2,2'-bipyridine molecular ring to the layer of the host, which is only an intermediate phase for the formation of the 0 0 l''' phase; the 0 0 l''' phase (with the lattice spacing of 15.33 A), indicating the existence of the complex cation [Mn(bipy)3]2+ coming from the in situ coordination of the inserted guest with intralayered Mn2+ ions between the interlayer space of host. As the intercalation proceeds, the 0 0 l, 0 0 l' and 0 0 l'' phases finally disappear, and 0 0 l''' phase is intensified and a complete intercalate is obtained. In Series B, due to the presence of the acid, the formation of the complex cation [Mn(bipy)3]2+ is inhibited, and the amount of the acid in the intercalation plays a key role in the formation of the guest. With the increase of the acid, the protonated bipyridine becomes the main existing form of the guest, which is arranged in the perpendicular orientation of molecular ring to the layer. From the experimental evidences, the possible intercalation mechanisms are proposed and the novel intercalation phenomenon of in situ coordination of the inserted 2,2'-bipyridine with Mn2+ of the host is elucidated