Abstract Photonic heterostructures with codable properties have shown great values as versatile information carriers at the micro‐ and nanoscale. These heterostructures are typically prepared by a step‐by‐step growth or post‐functionalization method to achieve varied emission colors with different building blocks. In order to realize high‐throughput and multivariate information loading, we report here a strategy to integrate polarization signals into photonic heterojunctions. A U‐shaped di‐Pt(II) complex has been assembled into highly polarized yellow‐phosphorescent crystalline microrods (Y‐rod) by strong intermolecular Pt⋅⋅⋅Pt interaction. Upon end‐initiated desorption of the incorporated CH 2 Cl 2 solvents, the Y‐rod is transformed in a domino fashion into tri‐block polarized photonic heterojunctions (PPHs) with alternate red‐yellow‐red emissions or red‐phosphorescent microrods (R‐rods). The red emissions of these structures are also highly polarized; however, their polarization directions are just orthogonal to those of the yellow phosphorescence of the Y‐rod. With the aid of a patterned mask, the R‐rod can be further programmed into multi‐block PPHs with precisely controlled block sizes by side‐allowed adsorption of CH 2 Cl 2 vapor. X‐ray diffraction analysis and theoretical calculations suggest that the solvent‐regulated modulation of the crystal packing and excited‐state property is critical for the construction of these PPHs.

Vaporchromic Domino Transformation and Polarized Photonic Heterojunctions of Organoplatinum Microrods