Metal-Deficient Supramolecule Based on a Fivefold-Symmetric Building Block

Angew Chem Int Ed Engl. 2020 Aug 3;59(32):13647-13650. doi: 10.1002/anie.202004988. Epub 2020 May 26.

Abstract

An unprecedented cationic supramolecule [(Cp''Fe(η5 -P5 ))12 {CuNCMe}8 ]8+ 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF3 )3 }4 ]- for the first time and characterized by X-ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal-deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal-deficient pentaphosphaferrocene-based supramolecules [{CpR Fe(η5 -P5 )}12 (CuX)20-n ]. The 12 vacant metal sites between the cyclo-P5 rings, the largest number attained to date, make this compound a facile precursor for potential inner and outer modifications of the core as well as for functionalization via the substitution of labile acetonitrile ligands.

Keywords: copper; pentaphosphaferrocene; self-assembly; supramolecular chemistry; weakly coordinating anions.