Oxazinoquinolinespirohexadienones – Attempting to Create N,O-bridged Analogs of Quinazolinespirohexadienone Photochromes as Potential

Faculty Mentor(s)

Dr. Jason Gillmore, Hope College
Daniel Stanford, Harper College

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Photoinduced charge transfer (PICT) is a useful means of generating organic ion radicals. Cation radicals generated by PICT have relevance in a variety of applications of materials science interest, including new approaches to volume holographic data storage and 3D microfabrication. However a limitation to the use of PICT-initiated cation radical reactions is the persistence of photooxidant in the material subsequent to completion of the desired reaction. For instance, in data storage, this prohibits the use of the writing laser to read out the data without a “fixing” step that may alter the material. We are therefore attempting to develop a reversible "pro-photooxidant" system to gate sensitivity to PICT, in essence only having a photooxidant present when it is desired.

Organic photochromes have long been used to “gate” optical properties, specifically color (absorbance) – in essence Transitions® lenses “gate” the presence of sunglasses. The increase in conjugation that underlies the change in absorbance upon isomerization of a photochrome also has significant impact on electronic properties. This phenomenon has received much less attention. Our group's emphasis continues to be on controlling and utilizing these electrochemical changes which occur concurrently with the photochromic rearrangement's shift in absorbance to create "photochromic photooxidants", in which one isomer of the photochrome is a good photooxidant, while the other isomer is not.

Building on our recently reported work in which the naphthalene moiety in the perimidinespirohexadienone (PSHD) structure is replaced with a quinoline moiety to give a quinazolinespirohexadienone (QSHD),1 we are now working to substitute an oxygen for one of the bridging nitrogens, to study the corresponding oxazinoquinolinespirohexadienones (OSHD). Synthesis, photochemistry, and experimental as well as computationally predicted2 electrochemical results will be presented on both the QSHD and OSHD photochromes.

References: (1) Moerdyk, J.P.; Speelman, A.L.; Kuper, K.E.; Heiberger, B.R.; Ter Louw, R.P.; Zeller, D.J.; Radler, A.J.; Gillmore, J.G. Synthesis and photochemistry of two quinoline analogs of the perimidine-spirohexadienone family of photochromes. J. Photochem. Photobiol. A 2009, 205, 84-92. (2) Speelman, A.L.; Gillmore, J.G. Efficient Computational Methods for Accurately Predicting Reduction Potentials of Organic Molecules. J. Phys. Chem. A 2008, 112 (25), 5684-5690. This material is based upon work supported by the National Science Foundation under grants CHE-0952768 (CAREER), CHE-0629174 (URC), and DUE-0728574 (S-STEM).

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