Molecular luminescent materials with optical waveguide have wide application prospects in light-emitting diodes, sensors, and logic gates. However, the majority of traditional optical waveguide systems are based on brittle molecular crystals, which limited the fabrication, transportation, storage, and adaptation of flexible devices under diverse application situations. To date, the design and synthesis of photofunctional materials with high flexibility, novel optical waveguide, and multi-port color-tunable emission in the same solid-state system remain an open challenge. Here, we have constructed new types of zero-dimensional organic metal halides (Au-4-dimethylaminopyridine [DMAP] and In-DMAP) with a rarely high elasticity and rather low loss coefficients for optical waveguide. Theoretical calculations on the intermolecular interactions showed that the high elasticity of 2 molecular crystalline materials was original from their herringbone structure and slip plane. Based on one-dimensional flexible microrods of 2 crystals and the 2-dimensional microplate of the Mn-DMAP, heterojunctions with multi-color and space-resolved optical waveguides have been fabricated. The formation mechanism of heterojunctions is based on the surface selective growth on account of the low lattice mismatch ratio between contacting crystal planes. Therefore, this work describes the first attempt to the design of metal-halide-based crystal heterojunctions with high flexibility and optical waveguide, expanding the prospects of traditional luminescent materials for smart optical devices, such as logic gates and multiplexers.
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