Fort he creation of next-generation organic electronic materials,t he integration of p-systems has recently become ac entral theme.S uch functional materials can be assembled by supramolecular polymerization when aromatic p-systems are used as monomers,a nd the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers.Here,wedemonstrate the construction of as upramolecular polymer consisting of an antiaromatic p-system as the monomer.A na mide-functionalized Ni II norcorrole derivative formed ao ne-dimensional supramolecular polymer through p-p stacking and hydrogenbonding interactions,e nsuring the persistency of the conducting pathway against thermal perturbation, which results in higher charge mobility along the tightly bound linear aggregates than that of the aromatic analogue composed of Zn II porphyrins.

We have investigated the folding and assembly behavior of a cystine‐based dimeric diamide bearing pyrene units and solubilizing alkyl chains. In low‐polarity solvents, it forms a 14‐membered ring through double intramolecular hydrogen bonds between two diamide units. The spectroscopic studies revealed that the folded state is thermodynamically unstable and eventually transforms into more energetically stable helical supramolecular polymers that show an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Importantly, compared to an alanine‐based monomeric diamide, the dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well as an increased thermodynamic stability in the aggregated state. Accordingly, the initiation of supramolecular polymerization can be regulated using a seeding method even under microfluidic mixing conditions. Furthermore, taking advantage of a self‐sorting behavior observed in a mixture of l‐cysteine‐ and d‐cysteine‐based dimeric diamides, a two‐step supramolecular polymerization was achieved by stepwise addition of the corresponding seeds.

We have investigated the folding and assembly behavior of a cystine‐based dimeric diamide bearing pyrene units and solubilizing alkyl chains. In low‐polarity solvents, it forms a 14‐membered ring through double intramolecular hydrogen bonds between two diamide units. The spectroscopic studies revealed that the folded state is thermodynamically unstable and eventually transforms into more energetically stable helical supramolecular polymers that show an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Importantly, compared to an alanine‐based monomeric diamide, the dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well as an increased thermodynamic stability in the aggregated state. Accordingly, the initiation of supramolecular polymerization can be regulated using a seeding method even under microfluidic mixing conditions. Furthermore, taking advantage of a self‐sorting behavior observed in a mixture of l‐cysteine‐ and d‐cysteine‐based dimeric diamides, a two‐step supramolecular polymerization was achieved by stepwise addition of the corresponding seeds.

We have investigated the folding and assembly behavior of an alanine-based monomeric diamide and a cystine-based dimeric diamide bearing pyrene units and solubilizing alkyl chains at their C-termini andN-termini, respectively. In low-polarity solvents, the former molecule forms a folded 7-membered ring conformation with an intramolecular hydrogen bond, while the latter molecule forms a 14-membered ring through double intramolecular hydrogen bonds between two diamide units. Spectroscopic studies revealed that both folded states are thermodynamically unstable and eventually transform into more energetically stable supramolecular polymers. Importantly, compared to the alanine-based diamide, the cystine-based dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well asan increased thermodynamic stability in the aggregated state. Consequently, spontaneous transformation from the folded state into the aggregated state is retarded even under the conditions of rapid molecular diffusion. Accordingly, the initiation of supramolecular polymerization can be regulated via a seeding approach under microfluidic mixing conditions. Furthermore, the supramolecular polymer composed of the cystine-based dimeric diamide has a helical structure with an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Taking advantage of the self-sorting behavior observed in a mixture of l-cysteine- and d-cysteine-based dimeric diamides, a two-step supramolecular polymerization from a racemic mixture was achieved by stepwise addition of the corresponding seeds.

For the creation of next‐generation organic electronic materials, the integration of π‐systems has recently become a central theme. Such functional materials can be assembled by supramolecular polymerization when aromatic π‐systems are used as monomers, and the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers. Here, we demonstrate the construction of a supramolecular polymer consisting of an antiaromatic π‐system as the monomer. An amide‐functionalized NiII norcorrole derivative formed a one‐dimensional supramolecular polymer through π‐π stacking and hydrogen‐bonding interactions, ensuring the persistency of the conducting pathway against thermal perturbation, which results in higher charge mobility along the tightly bound linear aggregates than that of the aromatic analogue composed of ZnII porphyrins.

We have investigated the folding and assembly behavior of an alanine-based monomeric diamide and a cystine-based dimeric diamide bearing pyrene units and solubilizing alkyl chains at their C-termini andN-termini, respectively. In low-polarity solvents, the former molecule forms a folded 7-membered ring conformation with an intramolecular hydrogen bond, while the latter molecule forms a 14-membered ring through double intramolecular hydrogen bonds between two diamide units. Spectroscopic studies revealed that both folded states are thermodynamically unstable and eventually transform into more energetically stable supramolecular polymers. Importantly, compared to the alanine-based diamide, the cystine-based dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well asan increased thermodynamic stability in the aggregated state. Consequently, spontaneous transformation from the folded state into the aggregated state is retarded even under the conditions of rapid molecular diffusion. Accordingly, the initiation of supramolecular polymerization can be regulated via a seeding approach under microfluidic mixing conditions. Furthermore, the supramolecular polymer composed of the cystine-based dimeric diamide has a helical structure with an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Taking advantage of the self-sorting behavior observed in a mixture of l-cysteine- and d-cysteine-based dimeric diamides, a two-step supramolecular polymerization from a racemic mixture was achieved by stepwise addition of the corresponding seeds.