Wired up and ready to glowDecember 10, 2010 in Chemistry / Materials Science
Thirty years ago, no one believed that elements other than carbon, nitrogen, and oxygen could form double bonds at room temperature. But the discovery of 'kinetic protection' ligands -- large, bulky molecules that trap heavy atoms into multiply-bonded arrangements -- forced a textbook rewrite. Researchers soon found that unsaturated bonds in newly synthesized substances such as disilenes, which have double siliconsilicon connections, generated chemical reactivity unlike any materials seen before.
Kohei Tamao and colleagues from the RIKEN Advanced Science Institute in Wako and Kyoto University have now discovered a way to make disilenes into thermally stable, light-emitting crystals by combining them with aromatic hydrocarbons. The key to their approach is a protecting ligand known as 'Eind' that is rigid enough to lock carbon and silicon atoms into a wire-like network.
Atoms make double bonds by sharing electrons through banana-shaped regions of space known as pi orbitals. If enough pi orbitals exist in a molecule, they can overlap and create conjugated pathways that allow for easy movement of electronsproperties that make such materials extremely responsive to light.
Incorporating disilenes into organic conjugated systems could produce enhanced photo-activity, but positioning two types of double bonds in one geometric plane for maximum pi orbital overlap is difficult. In 2007, Tamao and his team solved this problem by developing Eind ligands to protect a disilenebenzene compound. Eind groups have a stiff framework of three fused hydrocarbon rings that encapsulate the pi network and force it into a planar geometry by stacking perpendicular to it, which enabled the disilenebenzene product to be isolated as a fluorescent orange solid.
In their latest work, the researchers investigated the effects of extended organic pi conjugation by adding naphthalene and fluorene groupsaromatic molecules nearly twice the size of benzene ringsto an Eind-protected disilene. X-ray analysis revealed that the resulting red crystals also had planar siliconcarbon conjugation, a structure that produced intense fluorescent light emissions after ultraviolet irradiation (Fig. 1). We were excited to see such strong solid-state emissions even at room temperature, says Megumi Kobayashi, a co-author of the study.
Furthermore, these novel compounds showed unprecedented thermal stability, a critical requirement for future optical applications. Usually, compounds having unsaturated silicon bonds are reactive and air-sensitive, says Tsukasa Matsuo, another co-author, but our red disilenes are air-stable for almost one year. The team is currently working on improving the solubility of disilenearomatic molecules to help develop longer and more light-sensitive double bonded materials.
-- Kobayashi, M., et al. Air-stable, room-temperature emissive disilenes with π-extended aromatic groups. Journal of the American Chemical Society 132, 1516215163 (2010). article
-- Fukazawa, A., et al. Coplanar oligo(p-phenylenedisilenylene)s based on the octaethyl-substituted s-hydrindacenyl groups. Journal of the American Chemical Society 129, 1416414165 (2007). article
Provided by RIKEN
"Wired up and ready to glow" December 10, 2010 https://phys.org/news/2010-12-wired-ready.html