Porphyrins and their derivatives have excellent photophysical and electrochemical properties, which have attracted great interest in the fields of catalysis, biosensing, gas storage, solar cells, biomedicine, etc. However, the inherent limitations, such as self-quenching, weak absorption at biological spectral windows and poor photochemical stability, severely hinder their applications in biomedicine, especially in the field of photodynamic therapy (PDT). In recent years, metal–organic frameworks (MOFs) have received increasing attention as a class of hybrid porous coordination polymers assembled from metal ions/secondary building units (SBUs) and organic linkers. By introducing porphyrins into MOFs via the encapsulation in the pores as well as grafting on the surface to form porphyrin@MOFs or using porphyrins as organic linkers to construct porphyrin-MOFs, not only the unique properties of porphyrins and MOFs are combined, but also the limitations of porphyrins are overcome and their applications are facilitated in the biomedicine field. This article reviews important synthetic strategies of forming porphyrin-based MOFs (including porphyrin@MOFs and porphyrin-MOFs), which focuses on the recent research achievements and progress in PDT and tumor therapy fields. Furthermore, by carefully designing the composition of MOFs (such as the modification of organic linkers), MOFs could respond to the tumor microenvironment for on-demand treatment. In addition, some other strategies, including chemotherapy, photothermal therapy (PTT) and the latest cancer immunotherapy, are also combined in the review. Finally, the challenges and prospects in biomedical applications of this class of emerging materials are discussed.

The novel polytriphenylamines derivatives PTPA1-TPE and PTPA2-TPE with TPE as side groups and bis(tert-butyl)-TPE in the backbones have been successfully synthesized via Yamamoto-type coupling under microwave heating. The incorporation of TPE units in the backbones and side-chains endows the polymers with a distinct AIE effect and high fluorescence quantum yields in the solid state. Meanwhile, nitroaromatic explosive detection based on dispersed, electron-rich PTPA1-TPE and PTPA2-TPE nanoaggregates in THF/water was carried out. Both of them show high sensitivity towards the TNT analyte, with a maximum Stern–Volmer quenching constant K_sv of up to 8.3 × 10⁴ M⁻¹. In addition, the paper strip test demonstrates the promising practical application of the polymers as solid state sensors towards PL-based nitroaromatic explosive detection.

Two dendritic host materials consisting of non-conjugated adamantane cores and four first-/second-generation carbazole dendrons (Ad-4D1 and Ad-4D2) are developed for efficient solution-processed blue thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs). The dendrimers with three-dimensional geometries, which are constructed through facile one-step palladium-catalyzed C–N coupling reactions involving tetra-substituted adamantane and carbazole dendrons, show high thermal stability and excellent solubility in common organic solvents. The dendrimers possess high triplet energies (E_Ts) of 2.83–2.95 eV, making them suitable to host blue TADF emitters. Compared with Ad-4D1 with the first-generation dendrons showing a deep highest occupied molecular orbital (HOMO) level of −5.51 eV, Ad-4D2 with the second-generation ones exhibits an elevated HOMO level of −5.32 eV, favorable for hole injection from anode to the emissive layer. Solution-processed blue TADF OLEDs utilizing Ad-4D2 as a host exhibit promising device performance with a maximum luminous efficiency, power efficiency and external quantum efficiency of 44.2 cd A⁻¹, 34.4 lm W⁻¹ and 18.3%, respectively, among the highest values for solution-processed blue TADF OLEDs. This work sheds light on the development of dendritic host materials, as an alternative to soluble small-molecule hosts and polymer hosts, to realize high-efficiency solution-processed TADF OLEDs.