Designing molecular crystals for practical applications requires precise control over intermolecular interactions. We report a click-to-stack strategy to enable facile construction and systematic structural modification of tetraarene-fused cyclooctatetraenes. These saddle-shaped molecules self-assemble into one-dimensional columns with exceptional precision, driven solely by weak van der Waals interactions. Single-crystal X-ray crystallographic and computational studies revealed fully eclipsed π–π stacking, reinforced by the shape complementarity of the negatively curved molecular contour. With alkoxy groups tethered, the antiparallel alignment of coaxial cable-like assemblies produces centimeter-long voidless crystals that exhibit remarkable structural durability under mechanical stress. These glow stick-like elastic crystalline rods display optical waveguiding properties, demonstrating the practical utility of highly anisotropic molecular assemblies with structural uniformity and resilience.

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