Solid-State Assembly by Chelating Chalcogen Bonding in Quinodimethane Tetraesters Fused with a Chalcogenadiazole

In contrast to p-quinodimethane tetraesters, which undergo facile polymerization due to their diradical character, newly synthesized 1 and 2 consisting of a chalcogenadiazole fused to a p-naphthoquinodimethane tetraester are thermodynamically stable due to butterfly-shaped deformation. Such a folded molecular structure is also favorable for chalcogen bond (ChB) formation through intermolecular close contacts between a chalcogen atom (E: Se or S) and the oxygen atoms of ester groups in a crystal. The less-explored chelating-ChB through a C=O⋅⋅⋅E⋅⋅⋅O=C contact [Se⋅⋅⋅O: 2.94-3.37 Å] is the key supramolecular synthon for the formation of a one-dimensional rod-like assembly in a crystal, which is commonly observed in selenadiazole-tetraesters (1) with OMe, OEt, and OiPr groups. The formation of inclusion cavities between the rods shows that 1 could serve as solid-state host molecules for clathrate formation, as found in a hexane-solvated crystal. In contrast, thiadiazole-tetraesters (2) are less suitable for the formation of a rod-like assembly since the ChB involving S is less effective, and thus is overwhelmed by weak hydrogen bonds through C-H⋅⋅⋅O contacts.