Towards custom built double core carbon nanothreads using stilbene and pseudo-stilbene type systems

Abstract

Until recently, saturated carbon nanothreads were the missing tile in the world of low-dimension carbon nanomaterials. These one-dimensional fully saturated polymers possess superior mechanical properties by combining high tensile strength with flexibility and resilience. They can be obtained by compressing aromatic and heteroaromatic crystals above 15 GPa exploiting the anisotropic stress that can be achieved by the diamond anvil cell technique. Recently, double-core nanothreads were synthesized by compressing azobenzene crystals, achieving the remarkable result of preserving the azo group as a linker of the resulting double thread. Herein, we demonstrate the generality of these findings through the synthesis of double carbon nanothreads from trans stilbene and azobenzene-stilbene mixed crystals. Employment of Fourier transform infrared spectroscopy and synchrotron X-ray diffraction enabled a comprehensive characterization of the reactivity identifying threshold conditions, kinetics and structure–reaction relationship. In particular, the reaction is anticipated by a phase transition characterized by a sudden increase of the monoclinic angle and a collapse along the b axis direction. Large bidimensional crystalline areas extending several tens of nanometers are evidenced by transmission electron microscopy also confirming the monoclinic unit cell derived from X-ray diffraction data in which threads possessing the polymer 1 structure, as suggested by density functional theory calculations, are packed. The most exciting result of this study is the demonstration of viable synthesis of double nanothreads where the number and the nature of chromophoric groups linking the threads can be tuned by preparing starting crystals of desired composition, thanks to the isomorphism typical of the pseudo-stilbene molecules. This is extremely important in tailoring nanothreads with tunable optical properties and an adjustable band gap, also exploiting the possibility of introducing substituents in the phenyl groups.