The construction of circularly polarized luminescence (CPL) materials with high porosity and high rigidity is still challenging. Herein, we propose a chiral reticular chemistry strategy to prepare the homochiral porous metal–organic frameworks (MOFs) as CPL-active materials. Two pairs of enantiomeric MOFs are synthesized through the self-assembly of chiral D/L-cam (DL-camphorates) and achiral fluorescent ligand TPB (1,2,4,5-tetra­(pyridin-4-yl)­benzene). The g lum values of Cd-CMOF-D and Cd-CMOF-L were up to 0.010 and 0.009; the high g lum values could be compared to those of the partially pure multicomponent self-assembly systems obtained by the complicated process. We further trace the generation and transfer of the hierarchical chirality from chiral molecule to 3D framework, demonstrating that the CPL was dominated by the original molecular chirality rather than the global chirality of the hierarchical structure. Moreover, the single-phase white-light materials with nearly ideal CIE coordinates (0.33, 0.33) were constructed through the introduction of dye emitters into Zn-CMOF (Zn-based chiral MOF). This work provided not only an insightful view of the chirality transfer and disappearance mechanism but also an efficient method for the preparation of the highly porous CPL materials.

Two Cd-based supramolecular coordination polymers, [Cd 3 (CzIP) 3 (DMF) 2 ] (1) and [Cd 2 (CzIP) 2 (DMF) 4 ] (2), were synthesized by using 5-(carbazol-9-yl) isophthalate (CzIP) as ligands. These two compounds exhibit multiple luminescence emissions; apart from fluorescence, time-and temperaturedependent ultralong phosphorescence (RTP) were also achieved under room conditions. Significantly, compound 1 has a long-lived afterglow of 0.93 s at 545 nm under ambient conditions. Compound 2 shows nearly pure white-light emission with CIE coordinates of (0.33, 0.33) via the dual emission of fluorescence and phosphorescence. It has come to our attention that it is the first example of a luminescent coordination polymer with singlephase white-light emission and color-evolution RTP. In addition, the long-lived RTP materials can be used in time-dependent anticounterfeiting and white-light-emitting diodes. Experimental and singlet and triplet state calculations indicate that both C−H•••π interaction and inter-and intramolecular charge transfer interactions could be beneficial to the emission of ultralong RTP.

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