Ring-opening Photochemistry in Cyclohexadiene Derivatives: Ultrafast Dynamics in Solution and Model Membranes.

Abstract

The ultrafast dynamics of molecules in condensed phases is an area of research that has the possibility to inform the design of molecules for functional nano-devices as well as improve on understanding of biological processes. Presented in this thesis are experiments probing the excited and ground state dynamics of molecules based on the 1,3-cyclohexadiene (CHD) chromophore. The reversible photochemistry of these molecules is applicable to the study of photo-switching systems under consideration for molecular memory devices as well as the photobiological synthesis of Vitamin D3. The full reaction mechanism for a number of CHD derivatives is deduced from ultrafast broadband transient absorption spectroscopy and supporting density functional calculations. Steric groups on the cyclohexadiene backbone can affect both the excited state properties as well as the dynamic approach to equilibrium for the hexatriene photoproducts following excitation of CHD. The photoreaction was characterized in multiple solvent environments with a range of viscosity, polarity, hydrogen-bonding capacity, and packing density. The conformational dynamics of the photoproducts depend on the substitution pattern and solvent. The alpha-phellandrene photoproduct relaxes to a fully trans form much like hexatriene, while alpha-terpinene and 7-dehydrocholesterol photoproducts are limited to certain conformations by steric clashes. The solvent affects the relaxation timescales differently for each photoproduct, but all of the dynamics occur within 5 - 10 ps. The ring opening of DHC that occurs in the biological synthesis of Vitamin D3 is also examined in a liposomal model for the cell membrane. In this anisotropic environment, the excited state dynamics are significantly lengthened to ~ 11 – 50 ps depending on the liposome properties. This suggests significant interaction between DHC and the lipids that affects the ring-opening reaction coordinate. The excited state and photoproduct conformational equilibrium is discussed and compared to that in bulk solution. Development of the experimental protocol for investigating chemical dynamics in this highly scattering medium represents the groundwork for many future impactful experiments. These are the first experiments that characterize the photochemistry of 7-dehydrocholesterol in a system that models the in vivo environment.