We present a rationalization of the solid state behaviour of 1,1,4,4-tetraphenyl-1,3-butadiene (TPB), a well-known blue luminescent molecule, which retains its emissive properties in the solid state. The crystal structures of four polymorphs and one solvate form are discussed and their relative thermal stability is assessed. The experimental occurrence of the four polymorphs is rationalized on the basis of thermodynamic and kinetic considerations.
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