Directional emission from molecules
To get directional emission from a molecular substance, just make it into a LASER. Actually, the predecessor to the LASER, the first MASER, was based on microwave emission from ammonia. A $\ce{CO2}$ LASER is quite efficient and fairly easy to make, and the atmosphere of Mars is a natural, solar-pumped laser. So if you want directional emission from molecules, it's not even necessary to align them -- just provide suitable end-reflectors, or even a linear medium with enough gain.

That said, your question is about aligned materials... and there is a strong correlation between alignment and emission. An interesting example is found in topological insulators, which conduct only in certain directions and locations. It is possible to make a LASER from topological insulators. Some of these are as simple as $\ce{Bi2Se3}$, and others are more complex such as bis(methylene) adamantyl carbocation.