Macromolecular Architectures, Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Engesserstraße 18, 76128, Karlsruhe, Germany.
Institute for Inorganic Chemistry (AOC), Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Chemistry. 2018 Dec 17;24(71):18933-18943. doi: 10.1002/chem.201803966. Epub 2018 Dec 6.
A tetrazole-based photoligation protocol for the spatially-resolved encoding of various defined metallopolymers onto solid surfaces is introduced. By using this approach, fabrication of bi- and trifunctional metallopolymer surfaces with different metal combinations were achieved. Specifically, α-ω-functional copolymers containing bipyridine as well as triphenylphosphine ligands were synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization, and subsequently metal loaded to afford metallopolymers of the widely-used metals gold, palladium, and platinum. Spatially-resolved surface attachment was achieved by means of a nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) based photoligation protocol, exploiting tethered tetrazoles and metallopolymers equipped with a maleimide chain terminus. Metallopolymer coated surfaces with three different metals were prepared and characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and spatially-resolved X-ray photoelectron spectroscopy (XPS) mapping, supporting the preserved chemical composition of the surface-bound metallopolymers. The established photochemical technology platform for arbitrary spatially-resolved metallopolymer surface designs enables the patterning of multiple metallopolymers onto solid substrates. This allows for the assembly of designer metallopolymer substrates.
介绍了一种基于四唑的光连接方案，用于将各种定义明确的金属聚合物在固态表面上进行空间分辨编码。通过这种方法，可以实现具有不同金属组合的双功能和三功能金属聚合物表面的制造。具体而言，通过可逆加成-断裂链转移（RAFT）聚合合成了含有联吡啶和三苯基膦配体的α-ω-官能度共聚物，然后进行金属负载，得到了广泛使用的金、钯和铂等金属的金属聚合物。通过腈亚胺介导的四唑-烯环加成（NITEC）光连接方案实现了空间分辨的表面附着，该方案利用了连接的四唑和带有马来酰亚胺链末端的金属聚合物。制备了三种不同金属的金属聚合物涂层表面，并通过飞行时间二次离子质谱（ToF-SIMS）和空间分辨 X 射线光电子能谱（XPS）映射进行了表征，支持表面结合的金属聚合物的化学组成得以保留。所建立的用于任意空间分辨金属聚合物表面设计的光化学技术平台可将多种金属聚合物图案化到固体基底上。这允许组装设计的金属聚合物基底。
