Complementary hydrogen bonds and ionic interactions give access to the engineering of organometallic crystals

摘要

A crystal synthesis strategy based on a sequence of redox/acid-base/self-assembly/crystallisation processes has been devised and successfully applied to prepare a number of mixed organic/organometallic and organometallic/organometallic crystalline materials. An adequate choice of the building blocks permits design and construction of mono, two- and three-dimensional superanion framework structures encapsulating organometallic cations. The superanions are generated by partial deprotonation of polyprotic acids from the reaction with the organometallic hydroxides [Cr(#eta#~6-C_6H_6)_2][OH] and [Co(#eta#~5-C_5H_5)_2][OH], produced in situ by direct oxidation of the neutral complexes [Cr(#eta#~6-C_6H_6)_2] and [Co(#eta#~5-C_5H_5)_2]. The anionic super-structures are held together by a combination of neutral and interionic O-H...O hydrogen bonds, while the interaction with the organometallic cations is based on a profusion of C-H...O bonds reinforced via charge assistance.