Aggregation induced-emission (AIE) and antenna effects are important luminescence behaviors. Thus, investigating their emission mechanisms and revealing their behaviors have become critical but challenging. Here we design and prepare metal–organic frameworks (MOFs) with an AIE ligand (i.e., tetrakis­(4-carboxyphenyl)­pyrazine (L1)) and Ln3+ ions (including Eu3+, Tb3+, and Gd3+). The emission from L1 is gradually enhanced during the formation of the MOFs because coordination restricts the intramolecular rotation. Thus, the emission is called as coordination-induced emission (CIE) with the same restriction of intramolecular rotation mechanism as AIE. Meanwhile, benzene rings twist to adapt to the MOFs’ rigid structure, so the emission blueshifts gradually, as an additional evidence of CIE. Both AIE and CIE are “rotation-restricted emission (RRE)”. Eu3+ ions exhibit the strongest emission with gradually enhanced intensity during the formation of L1-Eu MOF. Combined with emission properties from Tb3+ and Gd3+ ions, the antenna effect is verified. We also validate the conditions for the efficient sensitization of Ln3+ ions experimentally and refresh the threshold value of the energy gap between triplet state of a ligand and excited state of Ln3+ ions to 3000 cm–1. Thus, RRE and antenna effects are revealed and validated simultaneously. Because CIE of L1 and antenna effect emission from Eu3+ ions are enhanced simultaneously as strong dual emissions, ratiometric fluorescence detection is realized with the detection of arginine as a model. Our results incorporate AIE and CIE into RRE, which provides explicit information for the construction and application of emission systems with AIE ligands as building blocks. MOFs are also extended to explore the emission mechanism and the energy transfer between ligands and metal ions.

Conspectus Emissive species are powerful for luminescent detection with high sensitivity and simple procedure and for light-emitting diode (LED) lighting because of their high efficiency, long lifetime, and low energy consumption. Here we propose the concept of multiple luminescence emissions from a single matrix or species under single-wavelength excitation. Multiemission not only realizes the high sensitivity of luminescence sensing but also possesses the capacity of self-reference for environment-free interferences. The color change is also convenient for visible detection. In multiemission species, every emissive center responds to a specific analyte to improve the efficiency for multiple-target detection. Multiemission also extends the applications to anticounterfeiting, colorful LEDs, and information storage. To date, it is still challenging to combine more than one type of emissive center in a single matrix or species. Obtaining multiemission under single-wavelength excitation also needs exquisite design. Metal–organic frameworks (MOFs) are porous hybrid assemblies prepared with metal ions and organic ligands. Metal nodes and ligands with large π-conjugated systems have the potential for the construction of luminescent MOFs. Abundant and diverse precursors provide the possibility to prepare MOFs with multiple luminescence emissions. The pores or channels of MOFs also act as hosts to encapsulate luminescent guest species as additional emissive sites. In this Account, we propose the concept of multiple-luminescence MOFs (ML-MOFs) and summarize the recent research progress on their designs, constructions, and applications reported by our group and others. ML-MOFs are MOFs that possess more than one emissive center under single-wavelength excitation. Six different kinds of construction strategies of ML-MOFs are introduced: (1) multiemission from both metal nodes and ligands in single MOFs; (2) use of mixed-metal nodes as multiemission centers in single MOFs; (3) combination of different emissive MOFs as a whole to achieve multiemission application; (4) host–guest emissions from emissive MOFs after encapsulation of luminescent guest species; (5) organization of different emissive ligands in a single MOF for multiemission; and (6) use of single ligands exhibiting dual emission to prepare ML-MOFs. We also discuss the mechanisms that realize multiple emissions from MOFs under single-wavelength excitation, such as the antenna effect and excited-state intramolecular proton transfer. The applications of ratiometric sensing, LED lighting, anticounterfeiting, and information storage are summarized. With this Account, we hope to spark new ideas and to inspire new endeavors in the design and construction of ML-MOFs, especially with postsynthetic techniques such as postsynthetic modification, postsynthetic exchange, and postsynthetic deprotection, to promote the applications of MOFs in sensing, lighting, information storage, and others.

Carbon dots (Cdots) are an important probe for imaging and sensing applications because of their fluorescence property, good biocompatibility, and low toxicity. However, complex procedures and strong acid treatment are often required and Cdots suffer from low photoluminescence (PL) emission. Herein, a facile and general strategy using carbonization of precursors and then extraction with solvents is proposed for the preparation of nitrogen‐doped Cdots (N‐Cdots) with 3‐(3,4‐dihydroxyphenyl)‐L‐alanine (L‐DOPA), L‐histidine, and L‐arginine as precursor models. After they are heated, the precursors become carbonized. Nitrogen‐doped Cdots are subsequently extracted into N,N′‐dimethylformamide (DMF) from the carbogenic solid. A core–shell structure of Cdots with a carbon core and the oxygen‐containing shell was observed. Nitrogen has different forms in N‐Cdots and oxidized N‐Cdots. The doped nitrogen and low oxidation level in N‐Cdots improve their emission significantly. The N‐Cdots show an emission with a nitrogen‐content‐dependent intensity and Cdot‐size‐dependent emission‐peak wavelength. Imaging of HeLa cells, a human cervical cancer cell line, and HepG2 cells, a human hepatocellular liver carcinoma line, was observed with high resolution using N‐Cdots as a probe and validates their use in imaging applications and their multicolor property in the living cell system.

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