Meso-tetrapyrenylporphyrin and its metal (CoII, CuII, NiII and ZnII) complexes were synthesized, characterized and studied for their spectral, electrochemical and energy transfer properties. DFT optimization was carried out to gain an insight into the interactions between the porphyrin π-system and the pyrenyl substituents. The pyrenyl substituents and the porphyrin core remain essentially orthogonal to each other in both the free base and the metallated porphyrins. Redox potentials of the pyrenylporphyrins are marginally shifted as compared to their corresponding phenyl derivatives. Förster resonance energy transfer (FRET) studies were carried out in toluene for free-base pyrenylporphyrin and its Zn(II) complex. Since pyrene is a good donor, an efficient energy transfer from pyrene (D) to the porphyrin core (A) on the order of 80–85% was observed for these two compounds. It was observed that energy transfer occurs mainly via ”through-bond” (TB) interaction rather than ”through-space” (TS) interaction.

中文翻译：

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Meso-Tetrapyrenylporphyrins：合成、结构、光谱、电化学性质和 Förster 能量转移 (FRET) 研究

中观-四芘基卟啉及其金属（Co二, 铜二， 你二和锌二) 合成、表征和研究了它们的光谱、电化学和能量转移特性。进行 DFT 优化以深入了解卟啉之间的相互作用π-系统和芘基取代基。在游离碱和金属化卟啉中，芘基取代基和卟啉核心基本上保持相互正交。与它们相应的苯基衍生物相比，芘基卟啉的氧化还原电位略有偏移。Förster 共振能量转移 (FRET) 研究在甲苯中对游离碱芘基卟啉及其 Zn(II) 配合物进行。由于芘是一个很好的供体，对于这两种化合物，观察到从芘 (D) 到卟啉核心 (A) 的有效能量转移约为 80-85%。观察到能量转移主要发生在通过“通过键”（TB）相互作用而不是“通过空间”（TS）相互作用。