Synthesis of a Metalla[2]catenane, Metallarectangles and Polynuclear Assemblies from Di(N-Heterocyclic Carbene) Ligands.

The 2,7-fluorenone-linked bis(6-imidazo[1,5-a]pyridinium) salt H2-1(PF6)2 reacts with Ag2O in CH3CN to yield the [2]catenane [Ag4(1)4](PF6)4. The [2]catenane rearranges in DMF to yield two metallamacrocycles [Ag2(1)2](PF6)2. 2,7-Fluorenone-bridged bis-(imidazolium) salt H2-L(PF6)2 (L = 2a, 2b) react with Ag2O in CH3CN to yield metallamacrocycles [Ag2(L)2](PF6)2 with interplanar distances between the fluorenone rings too small for [2]catenane formation. Intra- and intermolecular p···p interactions between the fluorenone groups were observed by X-ray crystallography. The strongly kinked 2,7-fluorenone bridged bis(5-imidazo[1,5-a]pyridinium) salt H2-4(PF6)2 reacts with Ag2O to yield [Ag2(4)(CN)](PF6) while the tetranuclear assembly [Ag4(4)2(CO3)](PF6)2 was obtained in the presence of K2CO3.

N-Heterocyclic carbenes and their precursors in functionalised porous materials.

Though N-heterocyclic carbenes (NHCs) have emerged as diverse and powerful discrete functional molecules in pharmaceutics, nanotechnology, and catalysis over decades, the heterogenization of NHCs and their precursors for broader applications in porous materials, like metal-organic frameworks (MOFs), porous coordination polymers (PCPs), covalent-organic frameworks (COFs), porous organic polymers (POPs), and porous organometallic cages (POMCs) was not extensively studied until the last ten years. By de novo or post-synthetic modification (PSM) methods, myriads of NHCs and their precursors containing building blocks were designed and integrated into MOFs, PCPs, COFs, POPs and POMCs to form various structures and porosities. Functionalisation with NHCs and their precursors significantly expands the scope of the potential applications of porous materials by tuning the pore surface chemical/physical properties, providing active sites for binding guest molecules and substrates and realizing recyclability. In this review, we summarise and discuss the recent progress on the synthetic methods, structural features, and promising applications of NHCs and their precursors in functionalised porous materials. At the end, a brief perspective on the encouraging future prospects and challenges in this contemporary field is presented. This review will serve as a guide for researchers to design and synthesize more novel porous materials functionalised with NHCs and their precursors.

A metal-carbene template approach enables efficient synthesis of a functionalized cage-annulated crown ether.

A facile synthetic method to form cage-annulated crown ether with anchored imidazolium units was developed. The present work verified the potential application of the metal-carbene template approach (MCTA) in the preparation of novel flexible polyimidazolium cages by photochemical [2+2] cycloaddition reactions and may provide a new method for the preparation of flexible pure organic cages with incorporation of a variety of functional sites.