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Supramolecular copolymers formed by the noncovalent synthesis of multiple components expand the complexity of functional molecular systems. However, varying the composition and microstructure of copolymers through tuning the interactions between building blocks remains a challenge. Here, we report a remarkable discovery of the temperature-dependent supramolecular copolymerization of the two chiral monomers 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tribenzamide (S-T) and 4,4′,4″-(benzene-1,3,5-triyl)tribenzamide (S-B). We first demonstrate in the homopolymerization of the two individual monomers that a subtle change from the central triazine to benzene in the chemical structure of the monomers significantly affects the properties of the resulting homopolymers in solution. Homopolymers formed by S-T exhibit enhanced stability in comparison to S-B. More importantly, through a combination of spectroscopic analysis and theoretical simulation, we reveal the complex process of copolymerization: S-T aggregates into homopolymers at elevated temperature, and upon slow cooling S-B gradually intercalates into the copolymers, to finally give copolymers with almost 80% alternating bonds at 10 °C. The formation of the predominantly alternating copolymers is plausibly contributed by preferred heterointeractions between triazine and benzene cores in S-T and S-B, respectively, at lower temperatures. Overall, this work unravels the complexity of a supramolecular copolymerization process where an intermediate heterointeraction (higher than one homointeraction and lower than the other homointeraction) presents and proposes a general method to elucidate the microstructures of copolymers responsive to temperature changes.

Supramolecular systems are intrinsically dynamic and sensitive to changes in molecular structure and external conditions. Because of these unique properties, strategies to control polymer length, composition, comonomer sequence, and morphology have to be developed for sufficient control over supramolecular copolymerizations. We designed photoresponsive, mono acyl hydrazone functionalized benzene-1,3,5-tricarboxamide (m-BTA) monomers that play a dual role in the coassembly with achiral alkyl BTAs (a-BTA). In the E isomer form, the chiral m-BTA monomers intercalate into stacks of a-BTA and dictate the chirality of the helices. Photoisomerization to the Z isomer transforms the intercalator into a chain capper, allowing dynamic shortening of chain length in the supramolecular aggregates. We combine optical spectroscopy and light-scattering experiments with theoretical modeling to show the reversible decrease in length when switching from the E to Z isomer of m-BTA in the copolymer with inert a-BTA. With a mass-balance thermodynamic model, we gain additional insights into the composition of copolymers and length distributions of the species over a broad range of concentrations and mixing ratios of a-BTA/m-BTA. Moreover, the model was used to predict the impact of an additive (chain capper and intercalator) on the chain length over a range of concentrations, showing a remarkable amplification of efficiency at high concentrations. By employing a stimuli-responsive comonomer in a mostly inert polymer, we can cooperatively amplify the effect of the switching and obtain photocontrol of polymer length. Moreover, this dynamic decrease in chain length causes a macroscopic gel-to-sol phase transformation of the copolymer gel, although 99.4% of the organogel is inert to the light stimulus.

In past studies, spin selective transport was observed in polymers and supramolecular structures that are based on homochiral building blocks possessing stereocenters. Here we address the question to what extent chiral building blocks are required for observing the chiral induced spin selectivity (CISS) effect. We demonstrate the CISS effect in supramolecular polymers exclusively containing achiral monomers, where the supramolecular chirality was induced by chiral solvents that were removed from the fibers before measuring. Spin-selective transport was observed for electrons transmitted perpendicular to the fibers’ long axis. The spin polarization correlates with the intensity of the CD spectra of the polymers, indicating that the effect is nonlocal. It is found that the spin polarization increases with the samples’ thickness and the thickness dependence is the result of at least two mechanisms: the first is the CISS effect, and the second reduces the spin polarization due to scattering. Temperature dependence studies provide the first support for theoretical work that suggested that phonons may contribute to the spin polarization.

Colloidal quantum dots (QDs) made from In-based III-V semiconductors are emerging as a printable infrared material. However, the formulation of infrared inks and the formation of electrically conductive QD coatings is hampered by a limited understanding of the surface chemistry of In-based QDs. In this work, we present a case study on the surface termination of IR active III-V QDs absorbing at 1220 nm that were synthesized by reducing a mixture of indium halides and an aminoarsine by an aminophosphine in oleylamine. We find that this recently established synthesis method yields In(As,P) QDs with minor phosphorus admixing and a surface terminated by a mixture of oleylamine and chloride. Exposing these QDs to protic surface-active compounds RXH, such as fatty acids or alkanethiols, initiates a ligand exchange reaction involving the binding of the conjugate base RX- and the desorption of 1 equiv of alkylammonium chloride. Using density functional theory simulations, we confirm that the formation of the alkylammonium chloride salt can provide the energy needed to drive such acid/base mediated ligand exchange reactions, even for weak organic acids such as alkanethiols. We conclude that the unique surface termination of In(As,P) QDs, consisting of a mixture of L-type and X-type ligands and acid/base mediated ligand exchange, can form a general model for In-based III-V QDs synthesized using indium halides and aminopnictogens.

Nanomaterials with highly ordered, one- or two-dimensional molecular morphologies have promising properties for adaptive materials. Here, we present the synthesis and structural characterization of dinitrohydrazone (hydz) functionalized oligodimethylsiloxanes (oDMSs) of discrete length, which form both 1- and 2D nanostructures by precisely controlling composition and temperature. The morphologies are highly ordered due to the discrete nature of the siloxane oligomers. Columnar, 1D structures are formed from the melt within a few seconds as a result of phase segregation in combination with π-π stacking of the hydrazones. By tuning the length of the siloxane, the synergy between these interactions is observed which results in a highly temperature sensitive material. Macroscopically, this gives a material that switches reversibly and fast between an ordered, solid and a disordered, liquid state at almost equal temperatures. Ordered, 2D lamellar structures are formed under thermodynamic control by cold crystallization of the hydrazones in the amorphous siloxane bulk via a slow process. We elucidate the 1- and 2D morphologies from the nanometer to molecular level by the combined use of solid state NMR and X-ray scattering. The exact packing of the hydrazone rods within the cylinders and lamellae surrounded the liquid-like siloxane matrix is clarified. These results demonstrate that controlling the assembly pathway in the bulk and with that, tuning the nanostructure dimensions and domain spacings, material properties are altered for applications in nanotechnology or thermoresponsive materials.

Supramolecular copolymers, non-covalent analogues of synthetic copolymers, constitute a new and promising class of polymers. In contrast to their covalent counterparts, the details of their mechanism of formation, as well as the factors determining their composition and length, are still poorly understood. Here, the supramolecular copolymerization between two slightly structurally different benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with either oligodimethylsiloxane (oDMSi) or alkyl side chains is unraveled by combining experimental and theoretical approaches. By applying the “sergeant-and-soldiers” approach using circular dichroism (CD) experiments, we are able to obtain detailed insights into the structure and composition of these supramolecular copolymers. Moreover, we observe an unexpected chiral induction upon mixing two independently CD-silent solutions of the achiral (soldier) and chiral (sergeant) monomers. We find that the subtle differences in the chemical structure of the two monomers impact their homopolymerization mechanism: whereas alkyl-BTAs cooperatively self-assemble, oDMSi-BTAs self-assemble in an isodesmic manner. The effect of these mechanistic differences in the supramolecular copolymerization process is investigated as a function of the composition of the two monomers and explicitly rationalized by mathematical modeling. The results show that, at low fractions of oDMSi-BTA sergeants (25 mol%), the isodesmic assembly of the increasing amounts of sergeant becomes more dominant, and different species start to coexist in the copolymerization process. The analysis of the experimental data with a newly developed theoretical model allows us to quantify the thermodynamic parameters, the distribution of different species, and the compositions and stack lengths of the formed supramolecular copolymers existing at various feed ratios of the two monomers. This work was financially supported by The Netherlands Organization for Scientific Research (NWO-TOP PUNT Grant 10018944) and the Dutch Ministry of Education, Culture and Science (Gravity Program 024.001.035).

Constitutional dynamic libraries of hydrazones (a)A(b)B and acylhydrazones (a)A(c)C undergo reorganization and adaptation in response to a chemical effector (metal cations) or a physical stimulus (light). The set of hydrazones [(1)A(1)B, (1)A(2)B, (2)A(1)B, (2)A(2)B] undergoes metalloselection on addition of zinc cations which drive the amplification of Zn((1)A(2)B)2 by selection of the fittest component (1)A(2)B. The set of acylhydrazones [E-(1)A(1)C, (1)A(2)C, (2)A(1)C, (2)A(2)C] undergoes photoselection by irradiation of the system, which causes photoisomerization of E-(1)A(1)C into Z-(1)A(1)C with amplification of the latter. The set of acyl hydrazones [E-(1)A(1)C, (1)A(3)C, (2)A(1)C, (2)A(3)C] undergoes a dual adaptation via component exchange and selection in response to two orthogonal external agents: a chemical effector, metal cations, and a physical stimulus, light irradiation. Metalloselection takes place on addition of zinc cations which drive the amplification of Zn((1)A(3)C)2 by selection of the fittest constituent (1)A(3)C. Photoselection is obtained on irradiation of the acylhydrazones that leads to photoisomerization from E-(1)A(1)C to Z-(1)A(1)C configuration with amplification of the latter. These changes may be represented by square constitutional dynamic networks that display up-regulation of the pairs of agonists ((1)A(2)B, (2)A(1)B), (Z-(1)A(1)C, (2)A(2)C), ((1)A(3)C, (2)A(1)C), (Z-(1)A(1)C, (2)A(3)C) and the simultaneous down-regulation of the pairs of antagonists ((1)A(1)B, (2)A(2)B), ((1)A(2)C, (2)A(1)C), (E-(1)A(1)C, (2)A(3)C), ((1)A(3)C, (2)A(1)C). The orthogonal dual adaptation undergone by the set of acylhydrazones amounts to a network switching process.

Constitutional dynamic libraries (CDLs) of hydrazones, acylhydrazones, and imines undergo reorganization and adaptation in response to chemical effectors (herein metal cations) via component exchange and selection. Such CDLs can be subjected to training by exposition to given effectors and keep memory of the information stored by interaction with a specific metal ion. The long-term storage of the acquired information into the set of constituents of the system allows for fast recognition on subsequent contacts with the same effector(s). Dynamic networks of constituents were designed to adapt orthogonally to different metal cations by up- and down-regulation of specific constituents in the final distribution. The memory may be erased by component exchange between the constituents so as to regenerate the initial (statistical) distribution. The libraries described represent constitutional dynamic systems capable of acting as information storage molecular devices, in which the presence of components linked by reversible covalent bonds in slow exchange and bearing adequate coordination sites allows for the adaptation to different metal ions by constitutional variation. The system thus performs information storage, recall, and erase processes.