Singlet–singlet and triplet-triplet energy-transfer processes between anthracenes and porphyrins have received considerable attention in materials chemistry. Herein, we report the first examples of 3,5-bis(10-phenylanthracen-9-yl)benzene-appended porphyrins (BPABPs) designed to study intramolecular energy transfer between two chromophores. The Curtius rearrangement of 3,5-bis(10-phenylanthracen-9-yl)benzoyl azide in the presence of the platinum(II) complex of 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-hydroxyphenyl)porphyrin or its free base in toluene afforded the corresponding BPABP. Spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the anthracene and porphyrin $\pi$-electron systems of the BPABPs are not conjugated and consequently do not affect each other’s absorption properties. In contrast, the BPABPs exhibited considerably different luminescence properties to those of phenyl 3,5-bis(10-phenylanthracen-9-yl)carbamate and 5,10,15-tris(3,5-di-tert-butylphenyl)-20-(3-methoxyphenyl)porphyrins; the anthracene units of the BPABPs show considerably quenched fluorescence compared to that of the reference anthracene, indicative of efficient intramolecular singlet–singlet energy transfer from the anthracene to the porphyrin unit. The phosphorescence quantum yield of the Pt complex of BPABP is comparable to that of the reference Pt-porphyrin, which suggests that intramolecular triplet-triplet energy transfer from the Pt-porphyrin to the anthracene unit is inefficient. The present findings improve our understanding of how structural factors and excited-state energy levels affect energy transfer and triplet-triplet annihilation upconversion processes of covalently linked bisanthracene-appended porphyrins.

蒽和卟啉之间的单线态-单线态和三线态-三线态能量转移过程在材料化学中受到了相当多的关注。在此，我们报道了 3,5-双（10-苯基蒽-9-基）苯附加卟啉（BPABP）的第一个例子，旨在研究两个发色团之间的分子内能量转移。在 5,10,15-三(3,5-二叔丁基苯基)-铂(II)配合物存在下，3,5-双(10-苯基蒽-9-基)苯甲酰叠氮化物的 Curtius重排20-(3-羟基苯基)卟啉或其游离碱在甲苯中得到相应的BPABP。光谱学、循环伏安法和密度泛函理论计算表明，蒽和卟啉$\pi$- BPABP 的电子系统不共轭，因此不会影响彼此的吸收特性。相比之下，BPABP 表现出与 3,5-双（10-苯基蒽-9-基）氨基甲酸苯酯和 5,10,15-三（3,5-二叔）苯酯显着不同的发光特性。-丁基苯基)-20-(3-甲氧基苯基)卟啉；与参考蒽相比，BPABP 的蒽单元显示出相当大的猝灭荧光，表明从蒽到卟啉单元的有效分子内单线态-单线态能量转移。BPABP 的 Pt 配合物的磷光量子产率与参考 Pt-卟啉的磷光量子产率相当，这表明从 Pt-卟啉到蒽单元的分子内三重态-三重态能量转移是低效的。目前的发现提高了我们对结构因素和激发态能级如何影响共价连接的双蒽附加卟啉的能量转移和三重态-三重态湮灭上转换过程的理解。