CAJ | 학술논문

利用简单的手性有机配体L-酒石酸成功地合成出了一系列类似DNA螺旋构型的左、右旋的一维链状聚合物:{A[Mo()2O4LnⅢ(H2O)6(C4H2O6)2]·4H2O}n(Ln=Sm,Eu,Gd,Ho,Yb,Y;C4H2O6=L-或D-酒石酸;A=NH4或H3O).通过水热法,巧妙地把传统的钼氧单核{ MoO4}、双核{Mo2O7}以及{Mo8O26}等结构单元,通过有机配体配位的过渡金属单元交错地连接成零、一、二、三维的一系列结构新颖的化合物,这类化合物大多数具有可以容纳客体小分子的隧道或空穴,如[Cu(4,4'-bpy)]2MoO4·2H2O,[Cu(4,4'-bpy)]2Mo2O7,[Cu(4,4'-bpy)(Hnic)(H2O)]2Mo8O26等.首次利用水热法合成出了含稀土的杂多酸类化合物,[Gd(H2O)3]3[GdMo12O42]·3H2O.该化合物是由Silverton型的[GdMo12O42]9-阴离子和配位的Gd3+阳离子组成的.在[GdMo12O42]9-离子中首次把顺磁性的钆(Ⅲ)离子引入到该构型的中心,并且通过九配位的钆(Ⅲ)离子把它们连接成具有介孔结构的三维网状化合物.该化合物的获得为今后合成类似化合物提供了一个很好的范例.在水热法合成出的化合物[Cu2(C8H6N2)2(C7H6N2)]2[Mo8O26]中,首次捕捉到喹喔啉的氧化产物苯并咪唑,证明了在水热条件下含氮的芳香杂环类的有机配体可以被二价铜氧化,其氧化产物进而作为配体直接与铜原子配位,最终形成新颖的上述化合物.
이용간단적수성유궤배체L-주석산성공지합성출료일계렬유사DNA라선구형적좌、우선적일유련상취합물:{A[Mo()2O4LnⅢ(H2O)6(C4H2O6)2]·4H2O}n(Ln=Sm,Eu,Gd,Ho,Yb,Y;C4H2O6=L-혹D-주석산;A=NH4혹H3O).통과수열법,교묘지파전통적목양단핵{ MoO4}、쌍핵{Mo2O7}이급{Mo8O26}등결구단원,통과유궤배체배위적과도금속단원교착지련접성령、일、이、삼유적일계렬결구신영적화합물,저류화합물대다수구유가이용납객체소분자적수도혹공혈,여[Cu(4,4'-bpy)]2MoO4·2H2O,[Cu(4,4'-bpy)]2Mo2O7,[Cu(4,4'-bpy)(Hnic)(H2O)]2Mo8O26등.수차이용수열법합성출료함희토적잡다산류화합물,[Gd(H2O)3]3[GdMo12O42]·3H2O.해화합물시유Silverton형적[GdMo12O42]9-음리자화배위적Gd3+양리자조성적.재[GdMo12O42]9-리자중수차파순자성적구(Ⅲ)리자인입도해구형적중심,병차통과구배위적구(Ⅲ)리자파타문련접성구유개공결구적삼유망상화합물.해화합물적획득위금후합성유사화합물제공료일개흔호적범례.재수열법합성출적화합물[Cu2(C8H6N2)2(C7H6N2)]2[Mo8O26]중,수차포착도규악람적양화산물분병미서,증명료재수열조건하함담적방향잡배류적유궤배체가이피이개동양화,기양화산물진이작위배체직접여동원자배위,최종형성신영적상술화합물.
A series of novel double helicates, {A[Mo2ⅥO4LnⅢ (H2O)6(C4H2O6)2]·4H2O}n(Ln =Sm, Eu, Gd, Ho, Yb, Y; C4H2O6 = L-tartaric acid; A = NH4 or H3O), have been synthesized from the reactions of chiral ligands L-tartaric acid with molybdates as well as lanthanide cations. The architectures of these compounds are one dimensional enantiopure novel right- or left-handed double helical one-dimensional chains, which are somehow like DNA in general configurations. By the hydrothermal reaction method, some molybdenum oxide units such as { MoO4 }, { Mo2 O7 } , { Mo8 O26 } are linked up by transition metal/organic ligand fragments to novel zero-, one-, two- or three-dimensional structures. Most of these compounds have voids, which are occupied by some suitable crystallization herterometallate chemistry containing lanthanide cations that is synthesized by the hydrothermal reaction.The compound is built up by Silverton-type [GdMo12O42 ]9- anions linking up nine coordinated Gd3+cations. It is the first example for introducing a paramagnetic lanthanide cation into the Silverton-type anionic center, which provides a very interesting example for the further synthesis of such a kind of compound/polymer. One-dimensional polymer, [ Cu2 ( C8 H6 N2 )2 ( C7 H6 N2 ) ] 2 [ Mo8 O26 ], which consists of β-[ Mo8 O26 ]4- anions linked by quinoxaline and its oxidized product benzimidazole ligands coordinating binuclear copper(Ⅰ) fragments, provides the first example that the isolated copper(Ⅰ) complex under hydrothermal conditions "captures" the reduction product of original starting organonitrogen ligand to form a copper( Ⅰ )-β-octamolybdate complex.