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Open Access Publications from the University of California

Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes.

  • Author(s): Fu, Wenxin
  • Alam, Todd M
  • Li, Jiachen
  • Bustamante, Jacqueline
  • Lien, Thanh
  • Adams, Ralph W
  • Teat, Simon J
  • Stokes, Benjamin J
  • Yang, Weitao
  • Liu, Yi
  • Lu, Jennifer Q
  • et al.

We report that an agile eight-membered cycloalkane can be stabilized by fusing a benzene ring on each side, substituted with proper functional groups. The conformational change of dibenzocycloocta-1,5-diene (DBCOD), a rigid-flexible-rigid organic moiety, from its Boat to Chair conformation requires an activation energy of 42 kJ/mol, which is substantially lower than those of existing submolecular shape-changing units. Experimental data corroborated by theoretical calculations demonstrate that intramolecular hydrogen bonding can stabilize Boat, whereas electron repulsive interaction from opposing ester substituents favors Chair. Intramolecular hydrogen bonding formed by 1,10-diamide substitution stabilizes Boat, spiking the temperature at which Boat and Chair can readily interchange from -60 to 60 °C. Concomitantly this intramolecular attraction raises the energy barrier from 42 kJ/mol for unsubstituted DBCOD to 68 kJ/mol for diamide-substituted DBCOD. Remarkably, this value falls within the range of the activation energy of highly efficient enzyme-catalyzed biological reactions. With shape changes once considered only possible with high energy, our work reveals a potential pathway exemplified by a specific submolecular structure to achieve low-energy-driven shape changes for the first time. The intrinsic cycle stability and high-energy output systems that would incur damage under high-energy stimuli could particularly benefit from this new kind of low-energy-driven shape-changing mechanism. This work has laid the basis to construct systems for low-energy-driven stimuli-responsive applications, hitherto a challenge to overcome.

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