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(ClO4)3·nH2O 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.