The molecular engineering of chromophores that enables the controlled and reliable formation of hierarchical solid-state architectures is at the forefront of developing hybrid semiconducting materials. While the rules and principles to assemble monomeric porphyrin-derived building blocks are well established, the aggregation of larger π-conjugated cores that feature electronically coupled porphyrin arrays has been vastly underexplored. In the present contribution, we report the synthesis, spectroscopy, assembly, and solid-state properties of a class of butadiyne-bridged (porphinato)zinc(II) dimer chromophores. A spectroscopic investigation unraveled the formation of aggregates in an aqueous medium, leading to the formation of two-dimensional objects that expanded across microscale dimensions. An analysis of the height profile, by atomic force microscopy, indicated that one porphyrin dimer comprises the thickness of the solid-state hierarchical superstructure, which underscores the promise of this approach to engineer solid-state platforms for (opto)electronic devices. Furthermore, the initiation of noncovalent interactions between building blocks by means of a chemical stimulus (pH) revealed that a nucleation–growth process governs the aggregation of the π-conjugated chromophores in an aqueous medium. This work provides tools to modulate the structure–function relationships of supramolecular architectures equipped with enticing optical properties.

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丁二炔桥接（卟啉）锌（II）发色团组装成自由站立的纳米片

发色团的分子工程学能够控制和可靠地形成分层的固态体系结构，这是开发混合半导体材料的前沿。尽管组装单体卟啉衍生构件的规则和原理已得到很好的确立，但以电子耦合卟啉阵列为特征的较大的π共轭核的聚集尚未得到充分研究。在目前的贡献，我们报告的合成，光谱学，组装和固态性质的一类丁二烯桥（卟啉）锌（II）二聚体发色团。光谱研究揭示了在水介质中聚集体的形成，从而导致了二维物体的形成，该物体在微观尺度上扩展。高度剖面分析 原子力显微镜的结果表明，一个卟啉二聚体包含了固态分层上层结构的厚度，这突显了这种方法有望为（光）电子设备设计固态平台的前景。此外，通过化学刺激（pH）引发结构单元之间非共价相互作用的结果表明，成核-生长过程控制着π-共轭发色团在水性介质中的聚集。这项工作提供了工具来调节具有诱人的光学性能的超分子结构的结构-功能关系。此外，通过化学刺激（pH）引发结构单元之间非共价相互作用的结果表明，成核-生长过程控制着π-共轭发色团在水性介质中的聚集。这项工作提供了工具来调节具有诱人的光学性能的超分子结构的结构-功能关系。此外，通过化学刺激（pH）引发结构单元之间非共价相互作用的结果表明，成核-生长过程控制着π-共轭发色团在水性介质中的聚集。这项工作提供了工具来调节具有诱人的光学性能的超分子结构的结构-功能关系。