Structural Variation in Mellitate Complexes of First-Row Transition Metals: What Chance for Design?

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• 作者：William Clegg ; James M. Holcroft
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：December 3, 2014
• 年：2014
• 卷：14
• 期：12
• 页码：6282-6293
• 全文大小：877K
• ISSN：1528-7505

文摘

Eight compounds of Co, Ni, and Cu with mellitate ligands display a wide variety of structures with metal鈥搈ellitate coordination polymer dimensionality 0鈥?. Usually mellitate is fully deprotonated (mel^{6鈥?/sup>), but there is one example of Hmel5鈥?/sup> and one of H₂mel4鈥?/sup>. [M₃(mel)(OH₂)₁₂]路6H₂O (M = Co or Ni) are chain polymers with octahedral M, while [Cu₇(OH₂)₁₉(OH)₂(mel)₂]路9H₂O has a 2D polymer sheet structure with square-based pyramidal Cu. Addition of KOH produces different compounds. Two incorporate K+ in the structures: K+₂(OH₂)₅[{Ni(OH₂)₅}₂(mel)]2鈥?/sup>路2H₂O contains discrete nickel鈥搈ellitate anionic units, and K+₂(OH₂)₆[{Cu(OH₂)₃}₂(mel)]2鈥?/sup>路H₂O has a copper鈥搈ellitate two-dimensional (2D) polymeric anion. For Co the product is [Co(OH₂)₆]2+[{Co(OH₂)₄}₅(mel)₂]2鈥?/sup>路4H₂O, with a 2D polymeric anion and discrete cations. A gel-supported synthesis leads to [Cu₃(OH₂)₁₀(Hmel)][Cu₂(OH₂)₆(Hmel)]路7H₂O, with two different copper鈥搈ellitate polymeric sheets arranged alternately in a stack. [{Cu(OH₂)(EtOH)(4,4鈥?bipy)}₂(H₂mel)] contains a three-dimensional copper鈥搈ellitate network with hexagonal channels, occupied by 4,4鈥?bipyridyl molecules coordinated to Cu at one end and hydrogen bonded to H₂mel4鈥?/sup> at the other. While some of these features are familiar from other structures, some are new, raising the question of how far design principles can be applied to the synthesis of mellitate complexes.}