Unusual liquid-solid transition effects in a methoxypentamethylflavan

Abstract

The solid phase of the compound 2'-methoxy-2 : 4 : 4 : 7 : 4'- pentamethylflavan differs in many respects from normally crystalline materials, yet is not amorphous. It tends to form spherical masses which exhibit no regular crystal boundaries, even when seen under the microscope. The solid melts over a range of up to 3° C and the actual temperatures at which melting begins and ends vary according to the thermal treatment previously received by the specimen. The temperature at which the melt starts to solidify on cooling is always several degrees below the melting range; this is not due to normal supercooling. Solidification from the melt presents several other interesting features, including some rhythmic effects. Variations in the external conditions during solidification can give rise to three superficially different forms of the solid phase. The solid-liquid and liquid-solid transitions have been followed by measurements of density, rigidity and dielectric constant, all of which give further indications of the diffuse nature of the melting process and the existence of hysteresis between melting and solidifica­tion. These effects recall the behaviour of some crystalline high polymers and examination of solid methoxypentamethylflavan by polarized light, X-rays and electron microscopy has revealed further analogies with such materials. It is tentatively concluded that the solid is composed of submicroscopic crystalline regions which are organized into larger spherulitic aggregates, but no definite explanations of the failure of the compound to form macroscopic crystals or of the similarities between it and polymers seem possible at present.