Assembly of dendrimers with redox-active [{CpFe(μ3-CO)}4] clusters at the periphery and their application to oxo-anion and adenosine-5′-triphosphate sensing
Assembly of dendrimers with redox-active [{CpFe(μ3-CO)}4] clusters at the periphery and their application to oxo-anion and adenosine-5′-triphosphate sensing
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DOI：
10.1002/anie.200502291
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Astruc, D
中科院分区：
文献类型：
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作者：
Aranzaes, JR;Belin, C;Astruc, D
金属树枝状聚合物 [1–8] 是成熟的纳米材料，可用作电子设备、[2] 传感器、[3] 和催化剂。[3, 4] 然而，只有少数例子是在树枝状聚合物外围存在过渡金属簇的。[5]据报道，星形装饰有四个氧化催化活性的多金属氧酸盐基团，[6]，外围树枝状聚合物周围的其他氧化还原活性过渡金属基团包括茂金属[7]和钌聚吡啶络合物。[2a]这些分子组装体显示出作为可通过电极修饰使用的电子器件和传感器的前景。[8]在此，我们报告了1) 已知的四铁团簇[{CpFe (μ3-CO)} 4](1),[9, 10] 的功能化，该团簇是富含氧化还原的有机金属团簇的原型； 2)用其衍生化9-、16-和27-支链树枝状聚合物； 3）这些新型金属树枝状聚合物的氧化还原行为和氧化还原鲁棒性以及修饰电极的形成，随着尺寸的增加，簇状树枝状聚合物在其上的吸附力更强； 4) 它们作为含氧阴离子选择性传感器的应用，包括 5'-三磷酸腺苷 (ATP2À)； 5）树突和结构对阴离子识别的影响，特别是在其他阴离子存在的情况下识别 ATP2À 的选择性，并且首次比 H2PO4 更好地识别 ATP2À。簇 1 及其丰富的氧化还原化学早已为人所知。[9]我们通过酸 [Fe4Cp3 (η5-C5H4CO2H)](2)[9d] 与 (COCl) 2 反应合成了其酰氯衍生物 3，通过 3 与 {ÀS (CH2) 11NH3+ ClÀ} 2 反应合成了二硫化物 4，通过 3 与 N-羟基琥珀酰亚胺反应合成了 N-琥珀酰亚胺酯 5（方案 1）。在 NEt3 存在下，复合物 3 与 9 支链氨基树枝状聚合物 7 反应，得到预期的 9 支链酰胺簇树枝状聚合物 8 [Eq.(1)]。然而，商业 (DSM) 第三代 16 支链氨基树枝状聚合物 9 的情况并非如此，[11] 可能是由于空间原因。在 NEt3 存在下，化合物 9 没有产生预期的树枝状酰胺复合物，但观察到意外形成二乙酰胺簇 6，这可能是由于电子从 NEt3 转移到 3 以生成酰基自由基所致
Metallodendrimers [1–8] are well-established nanomaterials that have applications as electronic devices,[2] sensors,[3] and catalysts.[3, 4] However, only a few examples are known with transition-metal clusters at the dendrimer periphery.[5] A star decorated with four polyoxometallate groups active in oxidation catalysis was reported,[6] and other redox-active transitionmetal groups surrounding dendrimers at the periphery include metallocenes [7] and ruthenium polypyridine complexes.[2a] These molecular assemblies show promise as electronic devices and sensors which can be used by electrode modification.[8] Herein we report 1) functionalization of the long-known tetrairon cluster [{CpFe (μ3-CO)} 4](1),[9, 10] the prototype of redoxrich organometallic clusters; 2) derivatization of 9-, 16-, and 27-branched dendrimers therewith; 3) redox behavior and redox robustness of these new metallodendrimers and formation of modified electrodes on which the cluster dendrimers are more strongly adsorbed with increasing size; 4) their application as selective sensors for oxo anions including adenosine-5’-triphosphate (ATP2À); and 5) dendritic and structural effects on anion recognition, in particular the selectivity of recognition of ATP2À in the presence of other anions and, for the first time, better recognition of ATP2À than H2PO4 À. Cluster 1 and its rich redox chemistry have been known for a long time.[9] We have synthesized its acyl chloride derivative 3 by reaction of the acid [Fe4Cp3 (η5-C5H4CO2H)](2)[9d] with (COCl) 2, the disulfide 4 by reaction of 3 with {ÀS (CH2) 11NH3+ ClÀ} 2, and the N-succinimidyl ester 5 by reaction of 3 with N-hydroxysuccinimide (Scheme 1). Complex 3 reacts with 9-branched amino dendrimer 7 in the presence of NEt3 to give the expected 9-branched amido cluster dendrimer 8 [Eq.(1)]. However, this is not the case for commercial (DSM) third-generation 16-branched amino dendrimer 9,[11] probably for steric reasons. Compound 9 did not give the expected dendritic amide complex in the presence of NEt3, but unexpected formation of the diethylamido cluster 6 was observed, presumably resulting from electron transfer from NEt3 to 3 to generate the acyl radical