Chen Hongye, Martín-Gomis Luis, Xu Zhiyun, Fischer Jan C, Howard Ian A, Herrero David, Sobrino-Bastán Víctor, Sastre-Santos Ángela, Haldar Ritesh, Wöll Christof
Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), 76344 Eggenstein-Leopoldshafen, Germany.
Área de Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Avda Universidad S/N, 03202, Elche, Spain.
Phys Chem Chem Phys. 2023 Jul 26;25(29):19626-19632. doi: 10.1039/d3cp01865b.
Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes. The spatial arrangement of the organic linkers can be well-defined in a MOF, and hence optoelectronic functions can be adjusted accordingly. We have used such a strategy to assemble a phthalocyanine chromophore and illustrated that the electronic inter-phthalocyanine coupling can be rationally tuned by introducing bulky side grounds to increase steric hindrance. We have designed new phthalocyanine linkers and using a layer-by-layer liquid-phase epitaxy strategy thin films of phthalocyanine-based MOFs have been fabricated and their photophysical properties explored. It was found that increasing the steric hindrance around the phthalocyanine reduced the effect of J-aggregation in the thin film structures.
有机发色团和半导体，如蒽、并五苯、苝和卟啉，容易发生聚集，并且它们在固态下的堆积方式往往难以预测和控制。由于这些发色团和半导体的凝聚相结构对其光电功能至关重要，因此控制它们的组装并提供新结构基序的策略很重要。一种这样的方法是使用金属有机框架（MOF）；将有机发色团转化为连接体，并通过金属离子或节点连接。有机连接体在MOF中的空间排列可以得到很好的定义，因此光电功能可以相应地进行调整。我们已经使用这样的策略来组装酞菁发色团，并表明通过引入庞大的侧基以增加空间位阻，可以合理调节酞菁之间的电子耦合。我们设计了新的酞菁连接体，并使用逐层液相外延策略制备了基于酞菁的MOF薄膜，并对其光物理性质进行了探索。结果发现，增加酞菁周围的空间位阻会降低薄膜结构中J-聚集的影响。
