Photo-active polymers are one of the most important materials because of their potential applications in solar energy conversion and photo-catalytic systems. Many research groups have developed separately efficient photo-catalytic systems or self-healing materials. Although significant developments of photo-active materials have been achieved but there are still remaining problems. Especially organic photoactive polymers are limited in terms of both applications and commercialization due to its low stability and short life time. In our systems, we envisaged regenerative photoactive polymer systems could be successfully achieved through metal-tpy interaction, resulting in biomimetic, sustainable photoactive systems. To develop the stability of photoactive polymer, we synthesized a polymers functionalized with terpyridine (tpy). Tpys can reversibly bind to metal ions (e.g., Fe2+, Zn2+, Co2+, and Mg2+) and those metals are easily removed by addition of stronger ligands such as EDTA and halides. Tpy functionalized polymers can fabricate photoactive thin film with MWNTs hybrid and photoactive gel with metal-ligand interaction that showed photocurrent generation and photocatalytic activity. Assembly was achieved by addition of Mg2+, as confirmed by red-shifted ligand absorptions (~330 nm) due to the planarization of pyridine groups by binding to Mg2+. Disassembly was accomplished by using TBAF due to higher binding affinity of F- to Mg2+ than tpy, returning the tpy ligands to the pristine, free state. The photocatalytic polymer complex was showed promoting visible light induced photo-oxidative coupling of benzylamine to N-benzyl benzaldimine. Additionally, the photocatalytic activity was recovered through re-assembly, and repeated several times without significant decrease of its efficiency. The self-assembly of photocatalytic systems based on metal-ligand interaction will enable self-repairable photoactive materials.

Development of sustainable photoactive polymer systems based on metal-terpyridine ligand dynamics

254th National Meeting (2017)

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