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Synthesis, Characterization, and Application of Photocaged R-Alkoxysilanes and Siloxane Polymers

Rashed, Mahmud Ramdan
http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1704720976948335

Abstract Details

2024, Doctor of Philosophy (Ph.D.), Bowling Green State University, Photochemical Sciences.
R-alkoxysilanes are the monomer workhorses of silicon-based sol-gel chemistry and are used as the building blocks for materials from silicas to silicones. However, since their inception, the sol-gel and siloxanes communities have struggled with uncontrolled hydrolysis, premature condensation, and overall polymerization and functionalization control. This dissertation focuses on the development of new silicon sol-gel chemistry methodologies which utilize photocaged R-alkoxysilanes and siloxane polymers to aid in synthetic control towards distinct silicon-based materials. We started our investigation with the synthesis and characterization of 2-nitrobenzyloxy photocage systems from ethyl and phenyl derivatives of Rx-(alkoxy)silanes, with x=0-3 and y=1-4, end group photocaged polydimethylsiloxanes, as well as photocaged polyhedral oligomeric silicon-based cage systems. Furthermore, we have also developed Rx-(alkoxy)silanes, with x=0-3 and y=1-4 that contain the 3-dimethylaminobenzyloxy photocage as a more stable alternative to the 2-nitrobenzyloxy based compounds. We have explored the photochemical responses for photo removal including kinetics, efficiency, stability, and tin catalyzed coupling of products to induce polymerization and surface functionalization. We have found that sufficient removal of the photocage groups was achieved, giving a new avenue to generate silicon-based materials. For this dissertation, Chapter 1 describes the background photochemical and silicon-based chemistries needed to understand these processes and their challenges. Chapter 2 details the extensive work on Rx-(alkoxy)silanes containing 2-nitrobenzyloxy groups and their performance in photochemical processes. Chapter 3 defines the work on 2-nitrobenzyloxy polymeric/oligomeric versions of silicon-based materials. Chapter 4 gives an overview of our preliminary work on 3-dimethylaminobenzyloxy photocaged Rx-(alkoxy)silanes. Finally, Chapter 5 gives conclusions and connections for this research to science and application.
Joseph Furgal, Ph.D. (Committee Chair)
Ellen Gorsevski, Ph.D. (Other)
Jayaraman Sivaguru, Ph.D. (Committee Member)
Alexander Tarnovsky, Ph.D. (Committee Member)
308 p.
Chemistry; Organic Chemistry
Photocage; Alkoxysilane; Siloxane; Silsesquioxane; Photoreaction; Photodecomposition; Photopolymerization; Surface Modification; ONB Group; o-Nitrobenzyl Group; DMAB Group; m-Dimethylaminobenzyl Group; Photoremovable Protecting Group; Quantum Yield; Kinetics; Q8M8; PPG; silicon chemistry;

Recommended Citations

Citations

  • Rashed, M. R. (2024). Synthesis, Characterization, and Application of Photocaged R-Alkoxysilanes and Siloxane Polymers [Doctoral dissertation, Bowling Green State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1704720976948335

    APA Style (7th edition)

  • Rashed, Mahmud. Synthesis, Characterization, and Application of Photocaged R-Alkoxysilanes and Siloxane Polymers. 2024. Bowling Green State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1704720976948335.

    MLA Style (8th edition)

  • Rashed, Mahmud. "Synthesis, Characterization, and Application of Photocaged R-Alkoxysilanes and Siloxane Polymers." Doctoral dissertation, Bowling Green State University, 2024. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1704720976948335

    Chicago Manual of Style (17th edition)

bgsu1704720976948335
© 2024, all rights reserved.
This open access ETD is published by Bowling Green State University and OhioLINK.