Department of Chemistry and Biochemistry and Materials Science Institute, University of Oregon , Eugene, Oregon 97403, United States.
CAMCOR - Center for Advanced Materials Characterization in Oregon, University of Oregon , Eugene, Oregon 97403, United States.
J Am Chem Soc. 2017 Mar 1;139(8):2936-2939. doi: 10.1021/jacs.7b00359. Epub 2017 Feb 21.
Because of their unique cyclic architectures, tunable electronic properties, and supramolecular chemistries, cycloparaphenylenes (CPPs) have the potential to act as a new class of ligands for coordination cages, metal-organic frameworks, and small-molecule transition-metal complexes. However, currently there is no general strategy to coordinate the cyclic framework to a variety of metal centers. We report here a general and scalable synthetic strategy to embed 2,2'-bipyridine units into the backbone of CPPs. We use this approach to synthesize a 2,2'-bipyridine-embedded [8]CPP, which we show can successfully coordinate to both Pd(II) and Ru(II) metal centers. The resulting coordination complexes, a Pd(II)-nanohoop dimer and a bis(bipyridyl)ruthenium(II)-functionalized nanohoop, show unique solid-state and photophysical properties. This work provides a proof of concept for a general strategy to use nanohoops and their derivatives as a new class of ligands.
由于其独特的环状结构、可调谐的电子性质和超分子化学，环对苯撑（CPPs）有可能成为一类新型配体，用于配位笼、金属-有机框架和小分子过渡金属配合物。然而，目前还没有一种通用的策略可以将环状骨架与各种金属中心配位。我们在此报告了一种将 2,2'-联吡啶单元嵌入 CPP 骨架中的通用且可扩展的合成策略。我们使用这种方法合成了一种 2,2'-联吡啶嵌入的[8]CPP，我们证明它可以成功地与 Pd(II)和 Ru(II)金属中心配位。所得的配位配合物，即 Pd(II)-纳米环二聚体和双（联吡啶）钌（II）功能化纳米环，表现出独特的固态和光物理性质。这项工作为使用纳米环及其衍生物作为一类新型配体的通用策略提供了一个概念证明。
