School of Chemistry and Biochemistry, University of Geneva, Geneva, Switzerland.
Department de Química, Universitat de les Illes Balears, Palma de Mallorca, Spain.
Chemistry. 2020 Nov 6;26(62):14059-14063. doi: 10.1002/chem.202003550. Epub 2020 Oct 1.
Naphthalenediimides (NDIs) are privileged scaffolds par excellence, of use in functional systems from catalysts to ion channels, photosystems, sensors, ordered matter in all forms, tubes, knots, stacks, sheets, vesicles, and colored over the full visible range. Despite this extensively explored chemical space, there is still room to discover core-substituted NDIs with fundamentally new properties: NDIs with cyclic trisulfides (i.e., trisulfanes) in their core absorb at 668 nm, emit at 801 nm, and contract into disulfides (i.e., dithietes) upon irradiation at <475 nm. Intramolecular 1,5-chalcogen bonds account for record redshifts with trisulfides, ring-tension mediated chalcogen-bond-mediated cleavage for blueshifts to 492 nm upon ring contraction. Cyclic oligochalcogenides (COCs) in the NDI core open faster than strained dithiolanes as in asparagusic acid and are much better retained on thiol exchange affinity columns. This makes COC-NDIs attractive not only within the existing multifunctionality, particularly artificial photosystems, but also for thiol-mediated cellular uptake.
萘二酰亚胺（NDIs）是一种特殊的优势骨架，可用于从催化剂到离子通道、光系统、传感器、各种形式的有序物质、管、结、堆、片、囊泡等功能系统中。尽管已经广泛探索了这一化学空间，但仍有空间发现具有根本新性质的核心取代 NDIs：具有环状三硫代物（即三硫烷）的 NDIs 在其核心处吸收波长为 668nm，发射波长为 801nm，并在低于 475nm 的照射下收缩成二硫代物（即二硫杂环戊烷）。分子内 1,5-杂原子键导致三硫代物的记录性红移，而环张力介导的杂原子键介导的断裂则导致环收缩至 492nm 的蓝移。NDIs 核心中的环状寡杂化物（COCs）的开环速度比在天门冬氨酸中的应变二硫杂环戊烷快，并且在巯基交换亲和柱上的保留性更好。这使得 COC-NDI 不仅在现有的多功能性（特别是人工光系统）中具有吸引力，而且在巯基介导的细胞摄取中也具有吸引力。
