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Lanthanide metal-organic frameworks (Ln-MOFs) have received much attention owing to their structural tunability and widely photofunctional applications. However, successful examples of Ln-MOFs with well-defined photonic performances at micro-/nanometer size are still quite limited. Herein, self-assemblies of 1,3,5-benzenetricarboxylic acid (BTC) and lanthanide ions afford isostructural crystalline Ln-MOFs. Tb-BTC, Eu@Tb-BTC, and Eu-BTC have 1D microrod morphologies, high photoluminescence (PL) quantum yields, and different emission colors (green, orange, and red). Spatially PL resolved spectra confirm that Ln-MOF microrods exhibit an optical waveguide effect with low waveguide loss coefficient (0.012≈0.033 dB μm ) during propagation. Furthermore, these microrods feature both linear and chiral polarized photoemission with high anisotropy.

Micro/nanoscale multicolor barcodes with unique identifiability and a small footprint play significant roles in applications such as multiplexed labeling and tracking systems. Now, a strategy is reported to design multicolor photonic barcodes based on 1D Ln‐MOF multiblock heterostructures, where the domain‐controlled emissive colors and different block lengths constitute the fingerprint of a corresponding heterostructure. The excellent heteroepitaxial growth characteristics of MOFs enable the effective modulation of the coding structures, thereby remarkably increasing the encoding capacity. The as‐prepared multicolor barcodes enable an efficient authentication and exhibit great potential in fulfilling the functions of anti‐counterfeiting, information security, and so on. The results will pave an avenue to novel hybrid MOFs for optical data recording and security labels.

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