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Polyoxometalate supported transition metal complexes: Synthesis, crystal structures, and supramolecular chemistry

机译:多金属氧酸盐负载的过渡金属配合物:合成,晶体结构和超分子化学

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A new series of polyoxometalate (POM) supported transition metal complexes (TMCs), namely, [2-ampH]_4[{Zn(H_2O)_5}Mo _7O_(24)]?9H_2O (1), [3-ampH] _4[{Zn(3-ampy)(H_2O)_4}Mo_7O _(24)]?4H_2O (2), [3-ampH]_4[{Co(3-ampy)(H _2O)_4}Mo_7O_(24)]?4H_2O (3), [2,3-diampH]_4[Co(H_2O)_6][Mo _7O_(24)]?6H_2O (4), and [2,3-diampH] _2[{Zn(2,3-diampH)_2(H_2O)_2}Mo _8O_(27)]?2H_2O (5) have been synthesized (where amp = aminopyridine and diamp = diaminopyridine) from the corresponding aqueous sodium molybdate solution, by varying the transition metal salts and aminopyridine derivatives in an acidic medium. In compounds 1-4, the POM cluster is [Mo_7O_(24)]~(6-), whereas in compound 5, it is [Mo_8O_(27)]~(6-). In compound 1, the heptamolybdate moiety is functionalized by the zinc-aqua complex [Zn(H_2O) _5]~(2+) and the residual negative charges have been compensated by the protonated 2-aminopyridine molecules acting as cations. In the crystal structure of compound 1, a dimer of 2-aminopyridine has been identified as a supramolecular synthon. Compounds 2 and 3 are isomorphous, in which the POM cluster anion supports the zinc and cobalt coordination complexes, {Zn(3-ampy)(H_2O)_4}~(2+) and {Co(3-ampy)(H _2O)_4}~(2+), respectively. The overall negative charges of the resulting POM supported transition metal complexes in compounds 2 and 3 have been counter-balanced by the protonated 3-aminopyridine molecules. In compound 4, the anionic cluster unit [Mo_7O_(24)] ~(6-) exists as a discrete moiety, where the species {Co(H _2O)_4}~(2+) and protonated 2,3-diaminopyridine act as mere counter cations. Compound 5 is a two-dimensional (2-D) coordination polymer which is constructed by [Mo_8O_(27)]~(6-) anion and [Zn(2,3-diampH)_2(H_2O)_4]~(4+) cation moieties. In the crystal structure of 5, interestingly, a one-dimensional chain is formed by a condensation reaction among [Mo_8O _(27)]~(6-) anionic cluster units through the formation of Mo-O_b-Mo (O_b is bridging oxygen) bonds, and these chains, in turn, are laterally interlinked by [Mo_8O_(27)] ~(6-) supported coordination complexes [{Zn(2,3-diampH) _2(H_2O)_2}Mo_8O_(27)] ~(2-) (as linker) resulting in the formation of a 2-D porous network having well-defined cavities. All compounds 1-5, that are isolated at an ambient temperature, are characterized by single crystal X-ray crystallography and are additionally characterized by elemental analyses, infrared, thermogravimetric analysis/mass spectral studies. The crystal structures analyses of compounds 2, 3, and 5 show the existence of supramolecular tectons.
机译:一系列新的多金属氧酸盐(POM)支持的过渡金属配合物(TMC),即[2-ampH] _4 [{Zn(H_2O)_5} Mo _7O_(24)]?9H_2O(1),[3-ampH] _4 [{Zn(3-ampy)(H_2O)_4} Mo_7O _(24)]?4H_2O(2),[3-ampH] _4 [{Co(3-ampy)(H _2O)_4} Mo_7O_(24)] α4H_2O(3),[2,3-diampH] _4 [Co(H_2O)_6] [Mo _7O_(24)]α6H_2O(4)和[2,3-diampH] _2 [{Zn(2,3 -diampH)_2(H_2O)_2} Mo _8O_(27)] 2H_2O(5)通过改变过渡金属盐和氨基吡啶衍生物从相应的钼酸钠水溶液合成得到(其中amp =氨基吡啶,diamp =二氨基吡啶)在酸性介质中。在化合物1-4中,POM簇为[Mo_7O_(24)]〜(6-),而在化合物5中,POM簇为[Mo_8O_(27)]〜(6-)。在化合物1中,七钼酸部分被锌-水络合物[Zn(H_2O)_5]〜(2+)官能化,并且残留的负电荷已被质子化的2-氨基吡啶分子作为阳离子所补偿。在化合物1的晶体结构中,已经确认了2-氨基吡啶的二聚体为超分子合成子。化合物2和3是同构的,其中POM簇阴离子支持锌和钴配位络合物{Zn(3-ampy)(H_2O)_4}〜(2+)和{Co(3-ampy)(H _2O) _4}〜(2+)。质子化的3-氨基吡啶分子抵消了化合物2和3中所得POM负载的过渡金属配合物的总负电荷。在化合物4中,阴离子簇单元[Mo_7O_(24)]〜(6-)作为离散部分存在,其中{Co(H _2O)_4}〜(2+)和质子化的2,3-二氨基吡啶仅仅是抗衡阳离子。化合物5是一种二维(2-D)配位聚合物,由[Mo_8O_(27)]〜(6-)阴离子和[Zn(2,3-diampH)_2(H_2O)_4]〜(4+ )阳离子部分。有趣的是,在5的晶体结构中,通过[Mo_8O _(27)]〜(6-)阴离子簇单元之间的缩合反应,通过形成Mo-O_b-Mo来形成一维链(O_b为桥连氧)键,然后这些链通过[Mo_8O_(27)]〜(6-)支持的配位化合物[{Zn(2,3-diampH)_2(H_2O)_2} Mo_8O_(27)]横向互连。 (2-)(作为接头)导致形成具有明确限定的腔的2-D多孔网络。在环境温度下分离的所有化合物1-5均通过单晶X射线晶体学表征,并通过元素分析,红外,热重分析/质谱研究进行表征。化合物2、3和5的晶体结构分析表明存在超分子构造。

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