Although photoexcited state lifetimes of transition-metal porphyrin complexes are usually too short to exhibit any appreciable reactivity in intermolecular redox reactions with substrates, there are several cases to show enough lifetimes of the photoexcited states of transition-metal porphyrins and analogues to be involved in intermolecular photoredox reactions. This minireview focuses on such examples of photochemistry and photocatalysis of transition-metal porphyrins and analogues. For example, supramolecular complexes of transition-metal porphyrins with fullerene and its derivatives undergo fast charge separation to produce the charge-separated states upon photoexcitation, the lifetimes of which are longer than those of transition-metal porphyrins themselves. The photoexcited state of [Co${}^{\text{III}}$TPP]${}^{+}$ (TPP = tetraphenylporphyrin dianion) acts as a good electron acceptor to form an exciplex with hexamethylbenzene, leading to the photocatalytic oxygenation of hexamethylbenzene with dioxygen. In contrast to [Co${}^{\text{III}}$TPP]${}^{+}$, the photoexcited state of [Mn${}^{\text{III}}$(TBP₈Cz): TBP₈Cz = octakis(p-tert-butylphenyl)corrolazinato${}^{3-}$] acts as an electron donor to react with O₂ (electron acceptor), producing the superoxo-Mn(IV) complex, by which hexamethylbenzene is oxidized to yield pentamethylbenzyl alcohol. A manganese porphyrin complex that is covalently linked to graphene oxide (GO) sheets is shown to act as a photoredox catalyst for photocatalytic asymmetric epoxidation of trans-stilbene with O₂ and isobutyraldehyde in the presence of imidazole to show high enantioselectivity (ee 100%) under photoirradiation. The photoexcited states of photo-labile Mn-porphyrin chlorates or bromates undergo homolytic cleavage to produce active radical species which are responsible for photocatalysis in the photocatalytic oxidation with substrates.

尽管过渡金属卟啉配合物的光激发态寿命通常太短，无法在与底物的分子间氧化还原反应中表现出任何明显的反应性，但有几种情况表明过渡金属卟啉及其类似物的光激发态寿命足以参与分子间氧化还原反应。光氧化还原反应。本小型评论重点关注过渡金属卟啉及其类似物的光化学和光催化作用的例子。例如，过渡金属卟啉与富勒烯及其衍生物的超分子配合物在光激发时发生快速电荷分离，产生电荷分离态，其寿命比过渡金属卟啉本身更长。[Co的光激发态${}^{\text{三、}}$跨太平洋伙伴关系]${}^{+}$（TPP = 四苯基卟啉二阴离子）作为良好的电子受体与六甲基苯形成激基复合物，导致六甲基苯与分子氧发生光催化氧化反应。与[Co${}^{\text{三、}}$跨太平洋伙伴关系]${}^{+}$，[Mn的光激发态${}^{\text{三、}}$(TBP ₈ Cz): TBP ₈ Cz = 八(对叔丁基苯基)咔嗪酸${}^{3-}$]作为电子供体与O ₂（电子受体）反应，生成超氧-Mn(IV)络合物，六甲苯被氧化生成五甲基苯甲醇。与氧化石墨烯 (GO) 片共价连接的锰卟啉络合物可作为光氧化还原催化剂，在咪唑存在下，用于反式二苯乙烯与 O _{2和异丁醛的光催化不对称环氧化，显示出高对映选择性 (} ee 100%)在光照射下。光不稳定的锰卟啉氯酸盐或溴酸盐的光激发态经历均裂，产生活性自由基物质，其在底物的光催化氧化中负责光催化作用。