Changes in crystal morphology induced by lanthanide doping into diacetylene lamellar crystals

In this study, we show that doping lanthanides into lamellar crystals reorganizes the lamellar structure and dramatically changes the crystal morphology. Azo-DA, a compound with azobenzene derivatives and carboxylic acids at both ends of the diacetylene moiety, formed plate-like lamellar crystals. The doping of holmium (Ho), a lanthanide, into the film obtained by stacking Azo-DA lamellar crystals, promoted a dramatic change in crystal morphology, resulting in the formation of an Azo-DA/Ho film with a radial lamellar crystal structure. A detailed investigation of the crystal growth process revealed that Azo-DA/Ho, which is slightly formed in the solution phase during Ho doping, acts as a pseudonucleating agent and dramatically changes the morphology of the lamellar crystals. Additionally, the morphological changes in the lamellar crystal films significantly changed the surface properties of the films, such as their appearance and water repellency. Similar morphological changes in lamellar crystals were induced when other lanthanide elements were used instead of Ho, and the type of lanthanide dopant can affect the magnetic properties of the films. Doping lanthanides into lamellar crystals of diacetylene derivatives with terminal carboxylic acids reorganized the lamellar structure and dramatically changed the crystal morphology. Detailed investigation of the crystal growth process revealed that the complexes of lanthanide and diacetylene derivatives, which are slightly formed in the solution phase during lanthanide doping, may act as a pseudonuclear agent and change the morphology of the lamellar crystals. Furthermore, the morphology changes of the lamellar crystal films significantly altered surface properties such as film appearance and water repellency.