Colloidal Crystals Engineered with DNA and Perylenediimide Exhibit Symmetry-Breaking Charge Transfer.

Diffraction-quality, ultraflexible protein single crystals engineered with DNA

This work reports a valence-centric strategy that enables DNA-bonded, protein single crystals with unconventional mechanical properties and establishes a programmable framework for biomolecular crystallization and nanomaterials engineering with atomic precision.

Nanoparticle Crystallization Driven by Competitive Toehold-Mediated DNA Strand Exchange Reactions.

DNA-mediated colloidal crystal engineering offers a powerful route for constructing three-dimensional nanoparticle superlattices with programmable structures and properties. However, achieving room-temperature fabrication of DNA-bonded colloidal crystals with long-range order remains challenging because nanoparticle assemblies are often kinetically trapped in metastable states. Here, we present a simplified enthalpy-regulation strategy based on a toehold-exchange mechanism to control interactions between DNA-functionalized gold nanoparticles. By tuning the relative lengths of the forward and reverse toeholds and the concentration of a DNA trigger, nanoparticle aggregation kinetics are precisely regulated, enabling a symmetric binary system to circumvent kinetic trapping and assemble into high-quality BCC superlattices. We further extend this approach to an asymmetric binary system, where selective control of linker valence directs the formation of distinct CsCl and AlB2 superlattices. Owing to its simplicity and adaptability, this strategy provides a versatile platform for integrating diverse DNA circuits with colloidal crystal assembly and engineering programmable phase behaviors.

Chiral Alanine Functionalized Perylene Diimides: Supramolecular Self-Assembly and Optical Properties

Water-soluble alanine-functionalized perylene diimide derivatives (PDI-Ala) were synthesized by introducing alanine units at the imide positions of the PDI framework. Their photoluminescence properties and supramolecular aggregation behavior were investigated in solvents of varying polarity. Chiral L-PDI-Ala displayed distinct solvent-dependent emission colors and intensities, whereas the achiral PDI-Ala showed negligible emission under the same conditions. Poor solvents such as acetone and ethyl acetate promoted relatively efficient emission with hypsochromically shifted bands, while good solvents such as N, N-dimethylformamide and dimethyl sulfoxide induced bathochromically shifted emission with much lower quantum yields. The results indicate that strong face-to-face π-π stacking in the solid-state leads to aggregation-caused quenching (ACQ), whereas ordered aggregates formed by intermolecular forces such as hydrogen bonds or stacking in solution can recover luminescence. On the basis of the spectroscopic and structural results, a solvent-regulated emission mechanism involving excimer/exciplex formation together with H-type and J-type aggregation is proposed. This work provides useful insight into the aggregation-controlled optical behavior of chiral amino-acid-modified PDI materials and offers guidance for the design of chiroptical and self-assembled luminescent systems.

Incorporating π-Conjugated Amino Acids Into Multi-Functional Amorphous Materials.

The controlled fabrication of amorphous materials from small organic molecules and their translation into high-performance functional materials remain long-standing challenges. Here, we introduce a multicomponent assembly strategy to developed amorphous materials from π-conjugated amino acids, offering a versatile platform for high-performance adhesive and optical applications. The incorporation of proline-based building blocks into multicomponent networks bypasses the crystallization-induced self-assembly that otherwise dominates in solution, thereby driving liquid-liquid phase separation-like pathways to yield amorphous aggregates. These aggregates exhibit exceptional thermoreversible adhesion to iron-based substrates, with their densely packed architecture facilitating rarely observed excimer emission of fluorene. Furthermore, enhanced charge-transfer interactions with 1,2,4,5-tetracyanobenzene shift the photoluminescence from indigo to green, increase the quantum yield by orders of magnitude, and transition the emission from short-lived prompt fluorescence to long-lived thermally activated delayed fluorescence. Through supercooling, amorphous glasses with high hardness and optical transparency were successfully fabricated, wherein increasing the number of components enables systematic tuning of surface roughness, wettability, quantum yield, emission wavelength, and excited-state lifetime. This work establishes a novel paradigm for synthesizing amorphous materials within multicomponent high-entropy systems, positioning amino acid and short peptide derivatives as a versatile class of biomolecular building blocks for advanced adhesive and photonic applications.

Imide Substitution Drives the Supramolecular Assembly of Perylene Diimide Into Laterally Modulated Metallic/Semiconducting Molecular Patterns

Perylene dyes are key building blocks in organic optoelectronics and photocatalysis owing to their highly tunable electronic structure. Here, we investigate the impact of imide substitution with bulky 2,6‐isopropylphenyl (iPr) on the structural and electronic properties of perylene diimide (PDI) monolayers on Ag(111). By combining scanning tunneling microscopy, X‐ray absorption and photoemission spectroscopies, we identify two distinct molecular configurations coexisting within an ordered herringbone arrangement. Core level photoemission spectra of monolayer iPr‐PDI reveal two chemically inequivalent oxygen species, which originate from the sterically driven differences in adsorption height. This structural inequivalence translates into markedly different electronic coupling: molecules lying closer to the surface exhibit partial filling of the lowest unoccupied molecular orbitals due to charge transfer from the substrate, whereas those located further away remain electronically decoupled, as evidenced by spectroscopic data and supported by density functional theory calculations. These findings demonstrate that imide substitution can conveniently be exploited for modulating the interfacial electronic character of PDI molecules within a single‐component self‐assembly, since steric effects can modify molecular packing, adsorption height, and molecule–substrate coupling. Our results highlight that substrate‐mediated charge transfer remains a critical design parameter for optimizing charge dynamics in application‐specific organic sensitized heterostructures.

Modular synthesis of chemically programmable superlattices