Assembly of a homochiral, body-centered cubic network composed of vertex-shared Mg12 cages:: Use of electrospray ionization mass spectrometry to monitor metal carboxylate nucleation

Reaction of Mg(NO3)(2)center dot 6H(2)O with (+)-camphoric acid (H(2)cam) in acetonitrile results in the immediate formation of soluble, dimetallic [Mg-2(Hcam)(3)](+) cations. The formation of these stable cations in solution was determined by electrospray ionization mass spectrometry (ESI-MS). These dimers are 3-fold paddle-wheels, which associate together through the neutral acid units to build the metal-organic framework [Mg-2(Hcam)(3)center dot 3H(2)O]center dot NO3 center dot MeCN, 1. The network consists of a series of fused Mg-12 cages that have 12 water molecules at their centers, creating isolated 0D cavities within the structure. Overall, the extended structure of 1 is a body-centered cubic (bcu) lattice, with the Mg-12 cages being utilized as eight-connected nodes. The framework of 1 is chiral and adopts the very unusual space group /23. Use of 1,3-propanediol as an additive results in the formation of the simple 1D polymer [Mg(cam){HO(CH2)(3)OH}(2)], 2. In 2, each carboxylate-bridged metal center is chelated by two diols. ESI-MS studies confirm the formation of new ions in these solutions. The identities of 1 and 2 were confirmed by a combination of single-crystal X-ray diffraction, elemental analyses, IR, NMR, themogravimetric analyses, and ESI-MS data. ESI-MS has proven to be a valuable technique in the identification of stable SBUs in solution prior to network formation.