Luminescent cyanometallate networks: the influence of weak interactions on structure and function

该建议是利用氰金属络合物阴离子作为两种方式的配位网络的组分的效用，每种方式都利用氰根的成键性质的不同方面。首先，发光氰基金属酸盐阴离子与其他金属阳离子的组合将提供一系列基于M-CN-M'桥的网络。或者，氢键阳离子的使用将导致基于阳离子和阴离子之间的氢键而不是配价配位键的配位网络的形成。这些网络将是感兴趣的各种原因：（i）与多达24个氰化物基团的多核氰酸酯将提供网络与前所未有的高连通性在一个单一的节点;（ii）使用光学分辨组件将导致手性框架，这必须导致二阶非线性光学活性;（iii）它们将显示不寻常的发光性质，例如组分之间的光致能量转移，导致来自镧系元素的敏化近红外发光。其次，氰酸酯形成卤键相互作用的能力M-CN。X-C将被详细研究。通过卤素键对[Ru（bipy）CN）4]2-发光的影响来考察相互作用的强度，并对该氰化物的实用性进行了探讨。作为晶体工程合成子的卤素相互作用将首次通过使用基于简单卤代吡啶阳离子和阳离子卤代吡啶络合物的卤素键供体以及基于贫电子全氟碘苯基组装的中性卤素键供体来评价。这些结构单元与氰基金属酸盐阴离子的组合将提供一系列从结构和发光角度来看都是新颖的材料，我们将研究（非共价）M-CN…X-C卤键可以介导光诱导能量转移和磁交换等相互作用。

This proposal is to exploit the utility of cyanometallate complex anions as components for coordination networks in two ways, each of which takes advantage of a different aspect of the bonding properties of cyanometallates. Firstly, combination of luminescent cyanometallate anions with other metal cations will afford a range of networks based on M-CN-M' bridges. Alternatively, use of hydrogen-bonding cations will result in formation of coordination networks based on hydrogen bonds between cations and anions, rather than dative coordinate bonds. These networks will be of interest for a variety of reasons: (i) polynuclear cyanometallates with up to 24 cyanide groups will provide networks with unprecedentedly high connectivity at a single node; (ii) use of optically resolved components will lead to chiral frameworks which must lead to second-order non-linear optical activity; (iii) they will display unusual luminescence properties such as photoinduced energy-transfer between components, leading to sensitised near-infrared luminescence from lanthanides. Secondly, the ability of cyanometallates to form halogen bonding interactions M-CN...X-C will be investigated in detail. Interaction strengths will be examined through the effect of the halogen bonds on the luminescence of [Ru(bipy)CN)4]2-.The utility of this cyanide...halogen interaction as a crystal engineering synthon will be evaluated for the first time by employing halogen bond donors based upon simple halopyridinium cations and cationic halopyridine complexes as well as neutral halogen bond donors based upon assembly of electron-poor perfluoroiodophenyl groups. Combination of these building blocks with cyanometallate anions will provide a range of materials which are novel from both a structural and a luminescence viewpoint, and we will examine how well the (non-covalent) M-CN...X-C halogen bonds can mediate interactions such as photoinduced energy-transfer and magnetic exchange.