Yu Shupei, Reddy Ojasvita, Abaci Alperen, Ai Yongling, Li Yanmei, Chen Hao, Guvendiren Murat, Belfield Kevin D, Zhang Yuanwei
. . Department of Chemistry and Environmental Science, College of Science and Liberal Arts, New Jersey Institute of Technology, 323 Martin Luther King Jr. Blvd., Newark, New Jersey 07102, United States.
. . Otto H. York Department of Chemical and Materials Engineering, New Jersey Institute of Technology, 161 Warren Street, Newark, New Jersey 07102, United States.
ACS Appl Mater Interfaces. 2023 Sep 27;15(38):45281-45289. doi: 10.1021/acsami.3c09326. Epub 2023 Sep 14.
Photobase generators (PBGs) are compounds that utilize light-sensitive chemical-protecting groups to offer spatiotemporal control of releasing organic bases upon targeted light irradiation. PBGs can be implemented as an external control to initiate anionic polymerizations such as thiol-ene Michael addition reactions. However, there are limitations for common PBGs, including a short absorption wavelength and weak base release that lead to poor efficiency in photopolymerization. Therefore, there is a great need for visible-light-triggered PBGs that are capable of releasing strong bases efficiently. Here, we report two novel BODIPY-based visible-light-sensitive PBGs for light-induced activation of the thiol-ene Michael "click" reaction and polymerization. These PBGs were designed by connecting the BODIPY-based light-sensitive protecting group with tetramethylguanidine (TMG), a strong base. Moreover, we exploited the heavy atom effect to increase the efficiency of releasing TMG and the polymerization rate. These BODIPY-based PBGs exhibit extraordinary activity toward thiol-ene Michael addition-based polymerization, and they can be used in surface coating and polymer network formation of different thiol and vinyl monomers.
光碱发生器（PBGs）是一类化合物，它们利用光敏感化学保护基团在目标光照射下实现有机碱释放的时空控制。PBGs可作为外部控制手段来引发阴离子聚合反应，如硫醇-烯迈克尔加成反应。然而，常见的PBGs存在局限性，包括吸收波长短和碱释放能力弱，导致光聚合效率低下。因此，迫切需要能够高效释放强碱的可见光触发型PBGs。在此，我们报道了两种新型的基于硼二吡咯（BODIPY）的可见光敏感PBGs，用于光诱导激活硫醇-烯迈克尔“点击”反应和聚合反应。这些PBGs是通过将基于BODIPY的光敏感保护基团与强碱四甲基胍（TMG）相连而设计的。此外，我们利用重原子效应提高TMG的释放效率和聚合速率。这些基于BODIPY的PBGs对基于硫醇-烯迈克尔加成的聚合反应表现出非凡的活性，可用于不同硫醇和乙烯基单体的表面涂层和聚合物网络形成。
