Category
Theoretical Proposal
Description
This study investigates the synthesis and monomer/dimer (M/D) characteristics of both meta- and para-nitrosoazobenzenes (NOAB). Previous studies have shown that nitrosobenzenes can interchange between dimer and monomer forms under various conditions. Additionally, various substituted azobenzenes can isomerize from their cis- to trans- configuration via UV light exposure. We hypothesize that dimerization of nitrosoazobenzenes can be achieved and controlled via the use of UV light. Upon isomerization of the azobenzene (AB) group, and reduction of AB conjugation, the NOAB should equilibrate from its dimer to monomer form. We intend to synthesize both m- and p-NOABs and use NMR and IR spectroscopic techniques to characterize the products and equilibria. For each isomer, the synthesis will begin with the corresponding m- or p-nitroaniline which undergoes a Mills condensation at low temperatures and acidic conditions to achieve the azobenzene. Subsequently, the nitrosobenzene moiety will be added by reduction of an existing nitro moiety. The resulting NOABs will be dimerized via environmental manipulation (i.e., temperature, solvent, organic host encapsulation). A library of p- and m- nitrosoazobenzenes will be created to form a data set that shows the characteristic control of the NOAB monomer-dimer equilibrium. UV and visible light exposure to the NOAB dimers subsequently induces a change from a cis- to trans- at the AB group. This should result in the presence of NOAB monomers as the isomerization of the AB structure induces cleavage of the N=N bond to give stable N=O bonds. This research identifies a gap in literature and combines previously utilized techniques to introduce a molecular controller that can be applied to biological life. NOABs with a photoswitch can be incorporated into materials that allow a transition from an “active” state to an “inactive” state. Such an application would provide various uses in the creation of inducible synthetic materials.
Appending Azobenzenes to Nitrosoarenes: Creating Reversible Light Control Over Monomerization
Theoretical Proposal
This study investigates the synthesis and monomer/dimer (M/D) characteristics of both meta- and para-nitrosoazobenzenes (NOAB). Previous studies have shown that nitrosobenzenes can interchange between dimer and monomer forms under various conditions. Additionally, various substituted azobenzenes can isomerize from their cis- to trans- configuration via UV light exposure. We hypothesize that dimerization of nitrosoazobenzenes can be achieved and controlled via the use of UV light. Upon isomerization of the azobenzene (AB) group, and reduction of AB conjugation, the NOAB should equilibrate from its dimer to monomer form. We intend to synthesize both m- and p-NOABs and use NMR and IR spectroscopic techniques to characterize the products and equilibria. For each isomer, the synthesis will begin with the corresponding m- or p-nitroaniline which undergoes a Mills condensation at low temperatures and acidic conditions to achieve the azobenzene. Subsequently, the nitrosobenzene moiety will be added by reduction of an existing nitro moiety. The resulting NOABs will be dimerized via environmental manipulation (i.e., temperature, solvent, organic host encapsulation). A library of p- and m- nitrosoazobenzenes will be created to form a data set that shows the characteristic control of the NOAB monomer-dimer equilibrium. UV and visible light exposure to the NOAB dimers subsequently induces a change from a cis- to trans- at the AB group. This should result in the presence of NOAB monomers as the isomerization of the AB structure induces cleavage of the N=N bond to give stable N=O bonds. This research identifies a gap in literature and combines previously utilized techniques to introduce a molecular controller that can be applied to biological life. NOABs with a photoswitch can be incorporated into materials that allow a transition from an “active” state to an “inactive” state. Such an application would provide various uses in the creation of inducible synthetic materials.
