Heterometal expansion of oxozirconium carboxylate clusters

Abstract

Although representing a 'thermodynamic sink', the octahedral oxozirconium {Zr(6)O(4)(OH)(4)} cluster structure can be magnetically functionalized by up to six 3d metal cations with a combination of flexible aminoalkoxide and carboxylate ligands.

Mixed Metal Multinuclear Cr(III) Cage Compounds and Coordination Polymers Based on Unsubstituted Phenolate: Design, Synthesis, Mechanism, and Properties

“…22,23,37,40 This straightforward access to mixed metal aryl-and alkoxides inspired us to use this approach, replacing alkaline earth metal halides by chromium dihalides as starting compounds due to their better solubility and in spite of the sensitivity of such compounds to humidity. 45 Very similar to a compound described by us, [Ca(OPh) 8 Li 6 -(THF) 6 ], 42 the literature reports on a Cr(II) compound, namely, [Cr(OPh) 5 Li 3 (THF) 3 ] 2 , A (Figure 1), described by Edema et al 46 We were intrigued by this structure, expecting it to be easily oxidized yielding new Cr(III) species which are otherwise not available by direct synthesis from Cr(III) salts and reactions with phenolates. Indeed, the known species of Cr(III) clusters and aryloxide ligands are based on substituted phenolates, 46,48−53 while unsubstituted Cr(III) phenolates are unknown to the best of our knowledge.…”

“…(THF) 6 Li 5 Cr 2 (OPh) 8 (OH)Cl 2 units, which are connected via chloride atoms (Cl1 and Cl2#2) by the bridging lithium ions Li5 and its symmetry equivalent ( Figure 4). The coordination sphere of Li5 is completed by two THF molecules.…”

“…The detection of H 2 and HD in the second experiment can be due to the sample preparation of LiOPh-d5. Indeed, LiOPh-d 5 was prepared in nondeuterated THF, isolated by drying and subsequent redissolving in THF-d 8 . The NMR spectrum of the LiOPh-d 5 in THF-d 8 did not show any proton signals, but given the sensitivity of the method, the presence of hydrogen cannot be excluded.…”

“…Mixed metal alkoxide compounds of, e.g., d-block elements with alkali, 1 alkaline earth, 2 lanthanide, 3 and actinide 4 metal ions, are an attractive field of research due to their large panel of applications. Indeed, as a function of the metal ions and ligands, mixed metal compounds can be used in catalysis, 5,6 magnetism, 7,8 optoelectronics, 9,10 luminescence, 11−15 energy storage (battery), 1,16−18 or fuel cells. 19−21 The properties of such polymetallic compounds depend on (a) the types and proportions of metallic species, and (b) the use of ligands allowing the tuning of the properties.…”

Mixed metal multinuclear Cr(III) cage compounds and coordination polymers based on unsubstituted phenolate: design, synthesis, mechanism, and properties

“…The last hypothesis is thus a cumulative participation of THF, phenoxide, and water by scrambling of H/D atoms. We prepared two samples of A with LiOPh-d 5 in solution in THF-d 8 and added to the first sample water and to the second one deuterated water. For both samples, the mass analysis of the formed gas showed the presence of H 2 , HD, and D 2 .…”