Herein, we present a template approach that allows for the incorporation of normally labile metal centers, such as copper(I), copper(II), and silver(I), into DNA branch points(Scheme 1 a). Remarkably high structural stability and chir-al... Herein, we present a template approach that allows for the incorporation of normally labile metal centers, such as copper(I), copper(II), and silver(I), into DNA branch points(Scheme 1 a). Remarkably high structural stability and chir-ality transfer to the metal complex are demonstrated. More-over, we have used this approach to generate the first example of a dynamic multimetallic metal–DNA assembly, with three metal complexes as the corners, single-stranded DNA as the sides, and multiple DNA double strands at the periphery (Scheme 1 d). We demonstrate quantitative and reversible structural switching of these metal–DNA nanostructures by adding specific DNA strands, resulting in controlled modu-lation of the metal–metal distances.This contribution thus allows the programmable generation of structurally dynamic multimetallic metal–DNA assemblies, with anticipated appli-cations in nanoelectronics, nanooptics, artificial photosyn-thesis, high-density data storage, and catalysis.
To create stable and electroactive metal–DNA junctions,we examined the attachment of the ligand bis(2,9-diphenyl)-1,10-phenanthroline (dpp) to DNA (Scheme 1 a). This ligand has been used by the groups of Sauvage and others to
generate interwoven structures.[10]It forms complexes such as [Cu(dpp)2]+, whose redox potential falls within the compat-ible window for DNA bases (+ 0.8 to-0.7V vs. saturated calomel electrode, SCE)
在此,我们报告一个模板的方法,允许将通常不稳定的金属ZX,如铜(I),铜(II),和银(I),并入DNA分支点(方案1a)。演示证明将高结构稳定性和空间螺旋特性转移到金属络合物。更重要的是,我们已经用这种方法来产生的diyi个例子中动态的多元金属–DNA组合:有三个金属络合物作为角,单链DNA作为两侧,和多个DNA双链在外围(方案1d)。我们通过添加特定的DNA链,展示这些金属–DNA纳米结构的定量和可逆的结构转换.从而控制调节金属与金属之间的距离。这贡献从而允许新一代可编程的动态结构多元金属-DNA组合,预计应用于纳米电子学,纳米光学,人工光合作用、高密度数据存储、和催化作用。为了建立稳定和电活性金属-DNA连接,我们检查了附属DNA的配体双(2,9二苯基)-1、10-菲罗啉(DDP)(方案1a)。这种配位体已被索维奇等群体用来产生交织结构。[10]它形成络合物如[铜(DPP)2)+,其氧化还原势属于DNA碱基内的兼容范围(+ 0.8 - 0.7 V 相对饱和甘汞电极、SCE).