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A combination of chalcogen bonds, one type of emerging non-covalent bonding force, and imine bonds, allow the control of the dynamic covalent chemistry with orbital interactions and the reversal of kinetic and thermodynamic selectivity.

A combination of diphenylethene and dynamic covalent chemistry for the modulation of reactivity and luminescence, stimuli-responsive multistate emission, and mechanochemical reactions in the solid state.

Urea groups play an important role in organic, supramolecular, and materials chemistry owing to unique structural and molecular recognition features. Herein a strategy of reversible covalent bond constrained ureas was developed toward multi-addressable switchable luminescent molecules and materials. The combination of ortho urea and aldehyde led to equilibrating cyclic hemiaminals, and the fluorescence response can be tuned through multimodes, including acid, base, anion, temperature, and nucleophiles. Moreover, mechanism studies revealed the critical role of an emissive aromatic acyliminium ion intermediate in acidic media, enabling triple-state ON–OFF–ON switching by changing pH. Through controlling the dynamic system thermally activated fluorescence and tunable dynamic covalent reactions with nucleophiles were further achieved. The unique reactivity of the acyliminium ion intermediate also allowed the creation of proton relay mediated signaling cascades toward the regulation of fluorescence outputs. To demonstrate the utility multi-stimuli luminescence switching and the detection of various vapors were realized in the solid state. The current platform provides a new pathway for manipulating urea bonds and should be appealing to future research of assembly, sensing, and labelling.

The imine bond holds a prominent place in supramolecular chemistry and materials science, and one issue is the stability of imines due to their electrophilic nature. Here we introduced ortho-carboxylate groups into a series of aromatic aldehydes/imines for dictating imine dynamic covalent chemistry (DCC) through n → π* interactions, one class of widespread and yet underused non-covalent interactions. The thermodynamically stabilizing role of carboxylate-aldehyde/imine n → π* interactions in acetonitrile was elucidated by the movement of the imine exchange equilibrium and further supported by crystal analysis. Computational studies provided mechanistic insights for n → π* interactions, the strength of which can surpass that of CH hydrogen bonding and is dependent on the orientation of interacting sites based on natural bond orbital analysis. Moreover, the substituent effect and the combination of recognition sites allowed additional means for modulation. Finally, to show the relevance of our findings ortho-carboxylate containing aldehydes were used to regulate imine formation/exchange in water, and modification of the N-terminus of amino acids and peptides was achieved in a neutral buffer. This work represents the latest example of weak interactions governing DCC and sets the stage for assembly and application studies., A versatile strategy of n → π* interactions was developed for tunable control of dynamic imine chemistry and the regulation of imine formation/exchange in water.

A strategy of dynamic covalent chemistry within constrained biaryls was developed for the modulation of axial chirality. The ring fusion partners of amide and aldehyde allowed the manipulation of ring/chain equilibrium and chirality transfer within cyclic diastereomeric hemiaminal. Dynamic covalent reactions (DCRs) with alcohols, thiols, and secondary amines further enabled the reversal of chirality relay and thereby regulation of axial chirality. Moreover, a combination of NMR, X-ray, and density functional theory results shed light on the structural basis of chirality transfer, exhibiting modest to excellent diastereoselectivity under thermodynamic control. The critical role of the amide unit in the modulation of axial chirality was also corroborated. Finally, the chiroptical signal was controlled through changing solvents, DCRs, and stimuli-responsive switching of DCRs.

Achieving complexity is central to the creation of chemical systems, inspired by natural systems. Herein we introduce a strategy of switchable orthogonal dynamic covalent chemistry (DCC) toward the regulation of complex dynamic networks. The control of dual reactivity of tautomers and resulting pathways allowed reversible covalent bonding of a large scope of primary amines, secondary amines, alcohols, and thiols with high efficiency. The selection of reaction pathways next enabled the realization of orthogonal but switchable dynamic covalent reactions (DCRs) with nucleophile pairs of amine/alcohol, alcohol/thiol, and amine/thiol by varying protonation and oxidation states. Control experiments confirmed the crucial role of dual reactivity on the stability and switchability of DCRs. The specificity toward amines, alcohols, and thiols, as well as interconversion between their corresponding assemblies, was further accomplished in one vessel, thus creating tunable communicating networks with three types of DCRs. Moreover, the switchable orthogonality combined with differential reactivity of multiple sulfonamides and nucleophiles enhanced the complexity within dynamic libraries. The generality and versatility of our approaches should facilitate their incorporation into many aspects of chemistry endeavors.

For producing flexible memory materials with controlled memory characteristics, functional copolynaphthalimides (co-PNIs), with varied composition of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 4,4′-(9-fluorenylidene) dianiline (BAPF) and 4,4′-diaminotriphenylamine (DATPA), were designed and synthesized in this work. Optical and electrochemical measurements on the synthesized co-PNIs, denoted as co-PNI-TPAx (where x = 0, 1, 2, 5, 10 for the molar ratio of the DATPA-containing unit in the co-PNIs), indicate gradually enhanced HOMO and continually degraded band gap with increasing DATPA unit, as further approved by molecular simulation. What is more, electrical characterization on the ITO | thin co-PNI active layer | Al sandwich devices witnesses a wide alteration of the memory behaviors from no electrical bistability (NULL, co-PNI-TPA0 and co-PNI-TPA1), to static random access memory (SRAM, co-PNI-TPA2 and co-PNI-TPA5), and then to the write-once read-many times memory (WORM, co-PNI-TPA10), implying the significance of composition control on determining the memory characteristics. Mechanisms associated with the switching effect and the charge transfer in the co-PNIs were analyzed based on the optical, electrochemical results and the B3LYP/6–31G(d) calculations. The conversion of the memory effect from NULL, to volatile SRAM, and then to nonvolatile WORM is suggested to result from the gradually increased ability of the synthesized co-PNIs to form stable charge transfer complexes with the increased electron-donating DATPA species. The fine memory tuning achieved here reveals the particular availability of the copolymerization strategy in designing functional polyimides with controlled performances for practical memory applications.

In an effort to develop reactivity-based dynamic covalent bonding and to expand the scope and application of the dynamic covalent chemistry, in situ-generated simple generic iminium ions were utilized for the dynamic covalent binding of monoalcohols with high affinity. Hammett analysis was conducted to manipulate the equilibrium and correlate with the reactivity of reactants. The structural features of aldehydes and secondary amines were identified, and both polar and steric effects have significant impact on the binding. In particular, the substrates which can participate in π-π and polar-π interactions are able to afford apparent equilibrium constants in the magnitude of 10(4) M(-2), demonstrating the power of weak supramolecular forces to stabilize the dynamic covalent assembly. The generality of the assembly was validated with a series of mono secondary alcohols. To showcase the practicality of our system, chirality discrimination and ee measurement of chiral secondary alcohols were achieved.