Flexible Zigzag Lanthanide Mesh Frameworks for One‐Dimensional Thiophene Crystallization and Oligomerization

ABSTRACT One‐dimensional (1D) thiophene (Th) crystals are important noncovalent motifs for pre‐organized polymerization of Th to produce conducting polythiophene. However, successful 1D Th alignment is difficult. To date, template‐directed 1D Th alignment has been achieved through strong host–guest interactions, but this results in a parallel‐stacked array that is unsuitable for pre‐organized polymerization. Herein, we report fabrication of a flexible zigzag lanthanide mesh framework (TUS‐Eu‐6) that enabled 1D crystallization of Th liquid through spontaneous self‐interactions within adaptable 1D pores [(Th) m ⊂TUS‐Eu‐6]. The 1D Th crystal structure was directly determined by x‐ray diffraction and revealed a T‐shaped configuration suitable for pre‐organized polymerization and oligomerization. Confined oxidative oligomerization of the inner 1D Th crystals occurred upon immersion of the (Th) m ⊂TUS‐Eu‐6 crystals in a Fe(ClO 4 ) 3 · n H 2 O aqueous solution. TUS‐Eu‐6 changed the pore shape and volume in crystalline‐state through solvent‐ligand exchange and exhibited excellent luminescent performance because of the antenna effects of its β ‐diketonate ligands.