Hollow porphyrin prisms: modular formation of permanent, torsionally rigid nanostructures via templated olefin metathesis

Abstract

Hollow, hexa-porphyrin prisms of two sizes were template-assembled and covalently locked, via cross-olefin metathesis, into permanent, torsionally rigid structures whose active sites (metal sites) can be both accessed and altered in a facile manner.

Ring-Closing Metathesis Synthesis of Medium and Large Rings: Challenges and Implications for Sustainable Synthesis

“…In the absence of template, the cyclodimer was obtained as the major product (56%), in preference to the cyclotrimer (0%). Similar behavior was reported by Nguyen and coworkers in a synthesis of hollow porphyrin prisms [130]. Use of tris((4-pyridyl)ethynyl)benzene as template afforded the desired trimer in over 70% yield; in its absence, solely dimers were obtained.…”

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

“…The use of templated ring-clousure metathesis (tRCM) to permenently “set” the structure resulted in the formation of both metallated and metal-free torsionally rigid, irreversible porphyrin prisms. 436 A 3:2 molar ratio reaction of a Zn-diporphyrin conjugated through a butadiyne linker and 2,4,6-tris(4-pyridyl)-1,3,5-triazine ( 285 ) or triethynylpyridylbenzene ( 291 ) panels preorganizes these panels into assemblies that are ready for ring-clousure metathesis. The tRCM using a first generation Grubb’s catalyst afforded the trigonal prisms in high yield.…”

Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

“…301 Stang, Chi and coworkers also used photoluminescence as the basis for the detection of nitroaromatics using trigonal prismatic cages constructed from Ru-based precursors. 141i Mukherjee and coworkers have reported both MOF 302 and SCC sensors for nitroaromatic-containing explosives, as well. 7j The former consisted of micron sized particles of a Zn carboxylate MOF dispersed in ethanol which could be recycled after use by centrifugation and subsequent washing.…”