A one-pot strategy for the construction of CF2-linked molecules using iododifluoromethyl phenyl sulfone (PhSO2CF2I) as a difluoromethylene diradical synthon is described. With the advantage of the distinct reactivity of the C-I and C-S bonds in PhSO2CF2I, two chemically differentiated CF2-centered radicals are generated sequentially under visible light irradiation. The stepwise generation and trapping of two distinct CF2-centered radicals enables arenes and alkenes to be sequentially installed in one pot, offering a streamlined route to a wide array of CF2-linked molecules. The method proceeds under mild conditions with a broad substrate scope and excellent functional group compatibility and is applicable to the late-stage modification of bioactive molecules.

We pioneered a strategy based on low-frequency vibronic coupling to design narrowband room-temperature phosphorescent (RTP) materials. Here we select coronene derivative (CoDe) system and report that attaching aroyl group to the coronene core disrupts its intrinsic symmetry and introduces abundant low-frequency vibrational modes, thereby affording efficient room-temperature phosphorescence with a full width at half maximum (FWHM) of approximately 25 nm or narrower. In CoDe systems functionalized with additional thioether groups, ultra-narrowband organic phosphorescence materials with exceptionally small FWHM (9.6 nm), high afterglow efficiency (50%), and long phosphorescence lifetimes (1.5 s) are achieved in host matrices under ambient conditions. Mechanistic studies reveal that this spectral narrowing relates to the selective amplification of low-frequency vibronic coupling through a moderate heavy-atom effect provided by the thioether groups. Equally crucial would be the suppression of excited-state relaxation and spectral broadening via relatively strong noncovalent interactions between the thioether groups and the host matrices (sulfur bonding interactions) at room temperature.

For the first time, polyhedral oligomeric silsesquioxane (POSS) has been used to prepare an octatopic component to co-assemble with cucurbit[8]uril (CB[8]) at room temperature to afford a three-dimensional POSS-based supramolecular organic framework pSOF. Dynamic light scattering experiment reveals that the new highly water-soluble SOF has concentration-dependent nano-scaled sizes, while solution- and solid-phase synchrotron radiation small-angle X-ray scattering experiments indicate that the SOF possesses a mesoporosity with an average size of 2.9 nm and a quite large size distribution. Mice model reveals that pSOF adsorbs photofrin and significantly alleviates its post-treatment phototoxicity, the largest limitation of photofrin as clinically used photodynamic therapeutic agent, but does not impose a negative effect on its photodynamic therapeutic efficacy. The maximum tolerated dose of pSOF for mice is determined to be 170 mg/kg, which is conspicuously higher than the highest value (120 mg/kg) reported for diamondoid-styled SOFs and endows it with the highest therapeutic index.

An efficient and regioselective coupling-cyclization reaction between allenyl benzoxazinanones and allenyl ethers or allenyl amides has been developed, enabling the synthesis of challenging eight-membered cycles in decent yields under mild conditions. In contrast to our prior work, the regioselectivity is reversed: the reaction takes place at the non-terminal C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 C bond of allenyl ethers and allenyl amides. A plausible mechanism involving intramolecular nucleophilic addition has been proposed.

pi-Conjugated-polymer-containing nanofibers have been considered as appealing building blocks of high-performance functional materials with broad applications from nanomedicine to microelectronics. Self-seeding of living crystallization-driven self-assembly (CDSA) has emerged as a facile approach toward controlled preparation of pi-conjugated nanofibers. Despite impressive advances in self-seeding of pi-conjugated block copolymers, the reports on the generation of pi-conjugated-polymer-containing nanofibers with a charged corona are scarce. Herein, we report the synthesis of a series of block copolymers containing a pi-conjugated BT-OPE7-BT (BT = benzothiadiazole, OPE = oligo(p-phenylene ethynylene)) segments and either neutral poly(N-(2-(methylthio)ethyl) acrylamide) (PMTEAM) of varying chain lengths or positively charged PMTEAM-derived segments with different contents of sulfonium units. The solvent, PMTEAM chain length, and sulfonium content significantly affected CDSA behavior with a direct heating/cooling protocol. Uniform fiber-like micelles with positively charged shells of varying contents of sulfonium units can be generated by a self-seeding approach. It was disclosed that the resistance of seed micelles to dissolution upon heating increased with the decrease of PMTEAM chain length and increase of contents of sulfonium units. This work not only offers a facile strategy toward controlled preparation of pi-conjugated nanofiber, but also deepens our understanding on self-seeding behavior of pi-conjugated block copolymers with charged corona-forming chains.