Electroactive MOF Networks

在这里，我们的目标是开发具有周期性、互穿电子供体和受体相网络的金属有机框架，这些框架可以最大限度地控制具有特定电子特性的分子构建块的性质、它们的组装顺序、它们相对于彼此的空间取向、它们的壁厚以及它们相对于衬底的总体取向。我们基于MOF结构构建了这种高度定义的模型系统，以增强我们对电子和结构参数与由此产生的光电特性（包括载流子动力学）之间关系的理解。在一条研究路线中，我们希望合成具有不同堆叠（杂）芳电子给体和受体基团的mof，从而形成高度有序（互穿）的网络，用于光诱导电荷分离和光探测。第二项研究是基于MOF-74拓扑结构范例，其中线性构建块通过二价金属离子的配位连接成蜂窝状结构。在这里，我们将改变金属配位球和线性构建块的结构和电子特性。此外，我们引入了一种通过kagome类平铺来分割电子耦合孔系统的策略，以保护载流子免受重组并延长其寿命。通过包合化学将互补的载流子相引入到MOF主体结构中。构建模块包括扩展的杂环发色团与推挽元件，以调整光电性能，以及扭曲系统与潜在的单线/三重态转换控制的mof基发光二极管。此外，我们的目标是开发基于不同沉积策略的薄膜生长技术，用于定向MOF和异质外延MOF-MOF结构，最终集成到模型光伏器件，光电探测器和MOF- led中，并通过广泛的技术和与其他研究小组合作研究其详细的载流子动力学。这项工作将辅以强大的理论建模，解决优化结构和分子构建块的包装，mof的先进电子性质计算，电荷传输计算和电导路径搜索，以确定限制因素和优化策略，以及薄膜生长的形态预测。

Here, we aim to develop metalorganic frameworks with periodic, interpenetrating networks of electron donor- and acceptor-phases that give maximum control over the nature of the molecular building blocks with specific electronic properties, their sequence of assembly, their spatial orientation relative to each other, their wall-thickness, and their overall orientation relative to a substrate. We build such highly defined model systems based on MOF structures, to enhance our understanding of the relationship between the electronic and structural parameters and the resulting optoelectronic properties, including charge-carrier dynamics. In one line of research, we wish to synthesize MOFs with different stacked (hetero)aromatic electron donor- and acceptor moieties, thus forming highly ordered (interpenetrating) networks for light-induced charge separation and photodetection. A second line of research is based on the structural paradigm of the MOF-74 topology, in which linear building blocks are connected into honeycomb-like structures through coordination of divalent metal ions. Here, we will vary both the structural and electronic properties of the metal coordination sphere and of the linear building blocks. Moreover, we introduce a strategy to partition the electronically coupled pore systems through Kagome-like tiling in order to protect charge carriers from recombination and to increase their lifetimes. Complementary charge-carrier phases will be introduced into the MOF host structures through inclusion chemistry. Building blocks include extended heterocyclic chromophores with push-pull elements to tune optoelectronic properties, and twisted systems with potential singlet/triplet conversion control for MOF-based light-emitting diodes. Furthermore, we aim to develop film-growth techniques based on different deposition strategies for oriented MOF- and heteroepitaxial MOF-MOF structures, ultimately to be integrated into model photovoltaic devices, photodetectors and MOF-LEDs, and to study their detailed charge-carrier dynamics with a wide range of techniques and in collaboration with other research groups. The work will be complemented with powerful theoretical modeling, addressing optimized structure and packing of the molecular building blocks, advanced electronic property calculations of the MOFs, charge transport calculations and conductance-path searches to determine limiting factors and optimization strategies, as well as morphology prediction for the growth of thin films.