题目：Unconventional Conjugation in Silsesquioxanes
主讲人：R. M. Laine, Professor of University of Michigan
Richard M. Laine received his Ph.D. under the Supervision of Professor Robert Bau at USC in 1973 and did postdoctoral studies with Richard F. Heck (University of Delaware) and Peter C. Ford (UCSB) followed by 11 years at Stanford Research Institute, last as Associate Director of Inorganic and Organometllic Programs. He moved to the Materials Science and Engineering Department at the University of Washington in 1987 as a full research professor and director of the polymeric materials laboratory in the Washington Technology Center. In 1990, he moved to the Materials Science and Engineering Department at the University of Michigan where he is a full professor and Director of the Macromolecular Science and Engineering Center.
We continue efforts to expand the family of silsesquioxane (SQ)-based oligomers and polymers that exhibit through-cage conjugation in the excited state and to map structure-property relationship for practical applications.1 We recently reported synthesizing a series of double decker (DD) and ladder (LL) SQ derived copolymers prepared via Heck catalytic cross-coupling that exhibit unconventional conjugation as evidenced by exceptional, red-shifted emissions relative to model compounds.2 When copolymerized with biphenyl, terphenyl and stilbene, the SQ polymers typically emit ca. 400 nm with ΦF ≥ 0.6 and DPs of 15-20. Copolymerization with thiophene, bithiophene and thienothiophene provides oligomers (DPs 4-8) with lmax emission ≈ 530 nm but with relatively low quantum yields. We have now also reported the synthesis of DD SQ terpolymers with abiphenyl/terphenyl/stilbene and thiophene based co-monomers linkers.3 In this presentation we will also discuss efforts to extend this work to extreme examples of silsesquioxane co-polymers.
1. Laine, R. M.; Sulaiman, S.; Brick, C.; Roll, M.; Tamaki, R.; Asuncion, M. Z.; Neurock, M.; Filhol, J.-S.; Lee, C.-Y.; Zhang, J.; Goodson, T.; Ronchi, M.; Pizzotti, M.; Rand, S. C.; Li, Y. J. Am. Chem. Soc. 2010, 132 (11), 3708–3722
2. Guan, J.; Tomobe, K.; Madu, I.; Goodson, T.; Makhal, K.; Trinh, M. T.; Rand, S. C.; Yodsin, N.; Jungsuttiwong, S.; Laine, R. M. Macromolecules 2019, 52 (19), 7413–7422
3. Zhang, Z.; Guan, J.; Ansari, R.; Kieffer, J.; Yodsin, N.; Jungsuttiwong, S.; Laine, R. M. Macromolecules 2022, 55, 18, 8106–8116