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

机译:第一行过渡金属的熔盐配合物的结构变化:设计的机会是什么?

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Eight compounds of Co, Ni, and Cu with mellitate ligands display a wide variety of structures with metalmellitate coordination polymer dimensionality 0-3. Usually mellitate is fully deprotonated (mel(6-)), but there is one example of Hmel(5-) and one of H(2)mel(4-). [M-3(mel)(OH2)(12)]center dot 6H(2)O (M = Co or Ni) are chain polymers with octahedral M, while [Cu-7(OH2)(19)(OH)(2)(mel)(2)]center dot 9H(2)O 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-)center dot 2H(2)O contains discrete nickel-mellitate anionic units, and K-2(+)(OH2)(6)[{Cu(OH2)(3)}(2)(mel)](2-)center dot H2O has a copper-mellitate two-dimensional (2D) polymeric anion. For Co the product is [Co(OH2)(6)](2+)[{Co(OH2)(4)}(5)(mel)(2)](2-)center dot 4H(2)O, with a 2D polymeric anion and discrete cations. A gel-supported synthesis leads to [Cu-3(OH2)(10)-(Hmel)][Cu-2(OH2)(6)(Hmel)]center dot 7H(2)O, with two different copper-mellitate polymeric sheets arranged alternately in a stack. [{Cu(OH2)(EtOH)(4,4'-bipy)}(2)(H(2)mel)] contains a three-dimensional copper-mellitate network with hexagonal channels, occupied by 4,4'-bipyridyl molecules coordinated to Cu at one end and hydrogen bonded to H(2)mel(4-) 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.
机译:Co,Ni和Cu的8种具有铝酸盐配体的化合物显示出多种结构,金属铝酸盐配位聚合物的尺寸为0-3。通常,熔融金属是完全去质子化的(mel(6-)),但是有一个Hmel(5-)和一个H(2)mel(4-)的例子。 [M-3(mel)(OH2)(12)]中心点6H(2)O(M = Co或Ni)是具有八面体M的链状聚合物,而[Cu-7(OH2)(19)(OH)( 2)(mel)(2)]中心点9H(2)O具有2D聚合物薄片结构,具有正方形的金字塔形Cu。 KOH的添加产生不同的化合物。两个在结构中合并了K +:K-2(+)(OH2)(5)[{Ni(OH2)(5)}(2)(mel)](2-)中心点2H(2)O包含离散的镍-熔融的阴离子单元,而K-2(+)(OH2)(6)[{Cu(OH2)(3)}(2)(mel)](2-)中心点H2O具有二维的熔融铜(2D)聚合阴离子。对于Co,乘积为[Co(OH2)(6)](2 +)[{Co(OH2)(4)}(5)(mel)(2)](2-)中心点4H(2)O,具有2D聚合阴离子和离散阳离子。凝胶支持的合成可生成[Cu-3(OH2)(10)-(Hmel)] [Cu-2(OH2)(6)(Hmel)]中心点7H(2)O,其中有两个不同的熔融铜聚合物片材交替堆叠排列。 [{Cu(OH2)(EtOH)(4,4'-bipy)}(2)(H(2)mel)]包含具有六角形通道的三维铜熔体网络,被4,4'-联吡啶基占据分子在一端与Cu配位,在另一端与氢键合到H(2)mel(4-)上。尽管其中一些功能是其他结构所熟悉的,但有些则是新功能,这就提出了设计原理可以应用于合成多金属配合物的问题。

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