Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1
Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1
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DOI：
10.1002/ejic.201500478
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发表时间：
2015-08
影响因子：
2.3
通讯作者：
WenHua Zhang;Olesia V. Kozachuk;R. Medishetty;A. Schneemann;R. Wagner;Kira Khaletskaya;Konstantin Epp;R. Fischer
中科院分区：
文献类型：
--
作者：
WenHua Zhang;Olesia V. Kozachuk;R. Medishetty;A. Schneemann;R. Wagner;Kira Khaletskaya;Konstantin Epp;R. Fischer
采用可控二级结构单元法（CSA）合成了一系列通式为[Ru 3（BTC）2Xx]·Gg（BTC = 1，3，5-苯三甲酸根; X =反阴离子; G =客体分子）的钌金属有机骨架（MOFs），它们是[M3（BTC）2]（M = Cu，Zn，Ni，Cr，Mo）的结构类似物.化合物[Ru 2（OOCR）4X]和[Ru 2（OOCCH 3）4]Y作为CSA的Ru源而变化;即利用强配位X（Cl-）和弱配位Y（[BF 4]-或[BPh 4]-）以及羧酸根配体[R = CH 3或C（CH 3）3]上的烷基。获得四种相纯Ru-MOF：[Ru3（BTC）2Cl0.5（OH）]·（AcOH）1.5（1）、[Ru3（BTC）2Cl1.2（OH）0.3]·（H3BTC）0.15（AcOH）2.4（PivOH）0.45（2）、[Ru3（BTC）2F0.5（OH）]·（AcOH）1.0（3）和[Ru3（BTC）2（OH）1.5]·（H3BTC）0.5·（AcOH）1.4（4）{AcOH = CH3COOH，PivOH =（CH3）3CCOOH}。一系列表征数据支持1-4的分析组成和同构性质，即采用粉末X射线衍射（PXRD）、IR和1H-NMR光谱、热重分析（TGA）和N2吸附。用X射线吸收光谱（XAS）研究了Ru位的价态。CSA的所选前体和优化的合成、后处理和活化方案允许改善总体结晶度、纯度（即，残余溶剂分子）和Ru-MOF材料的表面积。
A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl–) and weakly coordinating Y ([BF4]– or [BPh4]–) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) {AcOH = CH3COOH, PivOH = (CH3)3CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1–4, i.e. powder X-ray diffraction (PXRD), IR- and 1H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials.