Shijun Li

Chiral imine cages featuring an aromatic cavity are developed employing naphthalene diimide and porphyrin subunits via imine condensation reaction. The structures are characterized by NMR, MALDI‐TOF mass spectrometry, UV–vis and, circular dichroism (CD) spectroscopy. Furthermore, the configuration of one type of the imine cage was confirmed by single‐crystal x‐ray diffraction. Self‐sorting studies were further performed. When different‐sized porphyrin monomers of equal molar amounts and naphthalene diimide ligands are mixed and subjected to self‐assembly reactions, two distinct types of porphyrin imine cages can be obtained. Aromatic guest coronene can be efficiently encapsulated within the imine cages, where coronene engages in supramolecular π–π interactions with the two porphyrin planes. This work constructs complex NDI‐based chiral covalent porphyrin cages using relatively simple precursor units, which are anticipated to find applications in fields like host–guest recognition and catalysis.

Bulky indoline donors, optimized linker length and pre-adsorption were employed to improve the photovoltaic performance of doubly concerted companion dyes.

Antiaromatic compounds exhibit intriguing structures, reactivity, and physicochemical properties. To address the challenge in developing stable antiaromatic porphyrinoids, a vinylene bridge and an α,β′‐linked pyrrole unit were used to synthesize a 28π Möbius aromatic N‐confused oxohexaphyrin(2.1.1.1.1.1) ( 1 ). Subsequent oxidative C _β –C _β fusion afforded a stable Hückel antiaromatic formally triply N‐confused oxohexaphyrin(1.1.1.1.1.0) ( 2 ) as a hybrid of 24 and 28π systems with two peripheral NH moieties, enabling further C–N fusion with the adjacent C ₆ F ₅ moiety under basic conditions to yield the corresponding N‐confused dioxohexaphyrin(1.1.1.1.1.0) ( 3 ), which shows Hückel antiaromaticity with a modulated circuit. Coordination of various metals within the distinct coordination cavities afforded two mono‐rhenium complexes 3‐Re‐1 (NNη ² ‐coordinated) and 3‐Re‐2 (NNO‐coordinated) along with a mono‐Pd complex 3‐Pd‐1 (CNNO‐coordinated) with modulated antiaromaticity. On this basis, the heterobimetallic complex 3‐O‐Pd‐Re was synthesized with the conjugation and antiaromaticity disrupted by further oxygenation. Notably, these compounds display distinctive near‐infrared (NIR) absorption, enabling pronounced photothermal conversion under 1064 nm laser irradiation with efficiencies up to 61.4%. This work composes an effective post‐fusion approach for developing multiply N‐confused porphyrinoids with tunable antiaromaticity and distinctive coordination properties to achieve efficient NIR photothermal conversion behavior.

Antiaromatic compounds exhibit intriguing structures, reactivity, and physicochemical properties. To address the challenge in developing stable antiaromatic porphyrinoids, a vinylene bridge and an α,β′‐linked pyrrole unit were used to synthesize a 28π Möbius aromatic N‐confused oxohexaphyrin(2.1.1.1.1.1) ( 1 ). Subsequent oxidative C _β –C _β fusion afforded a stable Hückel antiaromatic formally triply N‐confused oxohexaphyrin(1.1.1.1.1.0) ( 2 ) as a hybrid of 24 and 28π systems with two peripheral NH moieties, enabling further C–N fusion with the adjacent C ₆ F ₅ moiety under basic conditions to yield the corresponding N‐confused dioxohexaphyrin(1.1.1.1.1.0) ( 3 ), which shows Hückel antiaromaticity with a modulated circuit. Coordination of various metals within the distinct coordination cavities afforded two mono‐rhenium complexes 3‐Re‐1 (NNη ² ‐coordinated) and 3‐Re‐2 (NNO‐coordinated) along with a mono‐Pd complex 3‐Pd‐1 (CNNO‐coordinated) with modulated antiaromaticity. On this basis, the heterobimetallic complex 3‐O‐Pd‐Re was synthesized with the conjugation and antiaromaticity disrupted by further oxygenation. Notably, these compounds display distinctive near‐infrared (NIR) absorption, enabling pronounced photothermal conversion under 1064 nm laser irradiation with efficiencies up to 61.4%. This work composes an effective post‐fusion approach for developing multiply N‐confused porphyrinoids with tunable antiaromaticity and distinctive coordination properties to achieve efficient NIR photothermal conversion behavior.

Chiral 3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxides (DHBDs) are core structural units in numerous biologically active molecules and chiral drug molecules. However, current catalytic synthetic methods for chiral DHBDs exhibit limitations, including limited substrate versatility and relatively unsatisfactory stereocontrol efficiency. This study has successfully developed a novel crown ether-derived chiral phosphoric acid catalyst, which can effectively catalyze the asymmetric tandem acetalization reaction between 2-aminobenzenesulfonamides and aldehydes, affording 36 chiral DHBDs under optimized conditions in 63-91% yield and 82-99% ee. Notably, this catalytic system exhibits broad substrate applicability, demonstrating high catalytic activity and excellent enantioselectivity toward both aromatic and aliphatic aldehydes, featuring simple operation and enabling gram-scale preparation. It is evidenced that the electron-rich, flexible structural features of crown ethers allow them to adaptively accommodate substrates through noncovalent interactions and therefore effectively promote the reactions in high reactivity and stereoselectivity.

Oxidation and Cu( ii ) metallation of a mono- meso -free N-confused hexaphyrin afforded a dimer (1)2 and mono-copper complexes (1-Cu, 1O2-Cu, and their methoxy derivatives), modulating the structures and absorption spectra of these compounds.

Template-directed synthesis of macromolecules prevails in natural systems. However, artificial template-directed covalent polymerization that proceeds without sacrificing the delicate non-covalent order needed for precursor alignment remains a formidable challenge. Here we report a supramolecular-templating strategy for photopolymerization of triphenylamine-based diyne assemblies. Cooperative hydrogen- and halogen-bonding align C ₃ -symmetric monomers into ordered stacks that evolve from nanodots into micron-scale nanofibers. Ultraviolet irradiation then triggers axial cross-linking of the diyne moieties, producing continuous one-dimensional conjugated polymers. Selective acid treatment cleaves the I···N halogen bond to remove the template while preserving nanofibrillar integrity, yielding a stable covalent network with red-shifted emission. We demonstrate that this self-assemble-then-cure strategy integrates reversible supramolecular organization with irreversible covalent fixation, providing a general and scalable route to vertically oriented conjugated polymer architectures.

Two conformers of a dipyrrolylbenzothiadiazole (DP-BTD) embedded decaphyrin(1.1.1.0.0.1.1.1.0.0) have been synthesized and separated, exhibiting crescent-shaped and figure-eight conformations, respectively. Incorporation of the hydrogen bonding-reinforced pseudorigid and electron-withdrawing DP-BTD segments not only stabilizes the distinct conformations, but also extends the absorption to ca. 1600 nm due to the good conjugation and ICT effect. Although both conformers are stable at room temperature, reversible interconversion occurs between them upon heating or disrupting intramolecular hydrogen bonds by protonation.

Unlike traditional macromolecules, supramolecular polymers are assemblies composed of individual monomeric units that are connected not by covalent bonds but through reversible, noncovalent interactions. This fundamental distinction from conventional polymers endows them with a wide range of novel and tunable properties, such as intrinsic dynamic reversibility, responsiveness to external stimuli (e.g., temperature, pH, light, and chemical environment), self-healing capability, and the ability to undergo controllable disassembly and reassembly. However, standardized or universally applicable techniques for the comprehensive characterization of supramolecular polymers have not been fully established yet. To address this gap, this review provides a detailed and systematic summary of various methodologies currently employed to characterize supramolecular polymers, including nuclear magnetic resonance spectroscopies (VC-NMR, VT-NMR, COSY, NOESY, ROESY, DOSY NMRs), mass spectrometries (ESI, MALDI, APCI), photo spectroscopies (UV–vis, FL, CD, IR, et al.), light scattering methods (DLS, SLS), X-ray techniques (SC-XRD, SAXS, WAXS, et al.), microscopies (AFM, SEM, TEM, CLSM, et al.) and methods used in traditional polymers (SEC, VPO, TGA, DSC, et al.). Due to the complexity and multifaceted nature of supramolecular systems, no single technique is capable of providing a complete and unambiguous description. Therefore, a combination of complementary techniques is typically required to achieve a thorough insight into their thermodynamics, kinetics, morphology, and responsiveness.

Cooperative self‐assembly based on multiple non‐covalent interactions is ubiquitous in nature, yet the rational design of artificial cooperative systems remains challenging. Here we synthesize two carbazole derivatives, CbzE (with an ester group) and CbzA (with amide groups), to investigate how hydrogen bonding (HB) and halogen bonding (XB) jointly guide self‐assembly into nanotubular supramolecular polymers. Using 1,4‐diiodotetrafluorobenzene (DITFB) as XB donor or diplatinum(II) as linker, two types of [4 + 4] macrocycles are constructed and characterized by high‐resolution mass spectrometry, ultraviolet‐visible, infrared, and atomic force microscopy. CbzA , benefiting from strong HB, cooperatively assembles with DITFB into nanofibers and nanotubes, whereas CbzE , lacking amide groups, forms only disordered aggregates. Pt(II) coordination disrupts HB networks and redirects CbzA toward lateral aggregation, underscoring the sensitivity of assembly pathways to the balance of interactions. Remarkably, nanotubular CbzA + DITFB structures disassemble rapidly under trifluoroacetic acid vapor but are restored by triethylamine, demonstrating a reversible gel–sol–gel transition. This orthogonal acid/base responsiveness highlights the tunable and dynamic features of cooperative HB/XB systems. Overall, these results reveal the critical role of HB and XB cooperativity in directing ordered architectures and provide new design principles for intelligent supramolecular polymers with stimuli‐responsive functions.