Controlling Molecular Crystal Polymorphism with Self-Assembled Monolayer Templates
- 1 December 2005
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 127 (51) , 18321-18327
- https://doi.org/10.1021/ja0565119
Abstract
The control of crystal polymorphism is a long-standing issue in solid-state chemistry, which has many practical implications for a variety of commercial applications. At least four different crystalline forms of 1,3-bis(m-nitrophenyl) urea (MNPU), a classic molecular crystal system, are known to crystallize from solution in various concomitant combinations. Herein we demonstrate that the introduction of gold-thiol self-assembled monolayers (SAMs) of substituted 4'-X-mercaptobiphenyls (X = H, I, and Br) into the crystallization solution can serve as an effective means to selectively template the nucleation and growth of alpha-, beta-, and gamma-MNPU phases, respectively. Polymorph control in the presence of SAM surfaces persists under a variety of solution conditions and consistently results in crystalline materials with high phase purity. The observed selectivity is rationalized on the basis of long-range two-dimensional geometric lattice matching and local complementary chemical interactions at the SAM/crystal interfaces.Keywords
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