Browse Articles

Projected-interacting full configuration interaction plus regularized perturbation theory: DFT-inspired wavefunction theory for huge active spaces

The computational design of molecular quantum devices requires methods that capture “the quantum and the chemistry,” approaching chemical accuracy for large numbers of entangled and/or strongly correlated electrons. Projected-interacting full configuration interaction (PiFCI) is a candidate for such simulations, providing a formally exact and systematically improvable approximation for correlation in large active spaces. PiFCI extends Kohn–Sham density functional theory by introducing multiple reference systems, each experiencing an electron–electron interaction projected onto one or more one-electron states. Compact CI expansions yield near-exact reference system wavefunctions, and projected exchange–correlation (XC) density functionals enable formally exact combinations of reference system correlation energies. This work presents a general treatment of the projected interactions in PiFCI and introduces regularized second-order many-body perturbation theory (MP2) as an approximate projected XC functional. Numerical results show that PiFCI plus regularized MP2 can accurately treat dynamical and nondynamical correlation in relatively large active spaces, including stacks of entangled singlet-coupled tetrathiafulvalene and phenalenyl organic radicals modeling molecular quantum devices.

Methylation-controlled photophysical tuning in isolated acridine cations revealed by cryogenic fluorescence spectroscopy and TD-DFT

Acridine derivatives, such as proflavine, acriflavine, and acridine orange, have been used extensively in biology and biomedicine as fluorescent probes by forming DNA-intercalating complexes. This approach benefits from a comprehensive understanding of their photophysical properties. In this context, we studied the fluorescence properties of proflavine, a reference compound, and its methylated derivatives under cryogenic, isolated conditions. Fluorescence excitation and dispersed emission spectra were measured, and spectral interpretation was supported by time-dependent density functional theory (TD-DFT) calculations at the ωB97XD/aug-cc-pVDZ level of theory. The excitation and emission spectra exhibit progressively red-shifted maxima with increasing methylation, reaching shifts up to 0.270 eV in emission, while the vibronic structure evolves from sharp to broad depending on the methylation site. Molecular geometry optimization, in both ground and excited states, predicts that the methylation of the amino side groups maintains the planar geometry observed in proflavine. In contrast, methylation of the nitrogen heterocycle disrupts symmetry, leading to an out-of-plane bend. These geometric differences lead to distinct active vibronic modes in Franck–Condon simulations, providing an explanation for the observed spectral differences. Additionally, TD-DFT calculations reproduce the red-shift trend experimentally observed, although they systematically overestimate excitation energies. Overall, the findings establish methylation as an effective strategy for tuning the photophysics of diaminoacridines, demonstrating that side substitution enables controlled spectral shifts without compromising emission efficiency or spectral resolution. These insights provide a rational framework for designing functional dyes with tailored optical properties for biological applications.

Field‐Free Spin‐Polarized Charge Transport in Chiral Co ₃ O ₄ Boosts Supercapacitor Kinetics

ABSTRACT Supercapacitors offer ultrahigh power density but remain fundamentally constrained by limited interfacial charge‐transfer kinetics at high rates. Although magnetic‐field‐assisted spin control has recently emerged as a promising strategy to regulate electrochemical kinetics, its reliance on external fields and magnetic components limits practical device integration. Here we establish chirality as an intrinsic, field‐free handle to regulate electron spin transport in supercapacitors by leveraging the chiral‐induced spin selectivity (CISS) effect. Enantiopure threonine is employed to template cobalt hydroxide nanoflakes, and subsequent calcination removes all organic species while imprinting robust chirality into purely inorganic Co 3 O 4 films. Magnetic conductive‐probe AFM reveals pronounced spin‐selective transport with spin polarization up to ∼48% at room temperature. Compared with racemic and non‐templated controls, chiral Co 3 O 4 electrodes exhibit markedly enhanced specific capacitance, superior rate capability, and improved cycling stability under zero magnetic field. Electrochemical impedance spectroscopy and distribution of relaxation times analysis reveal a 6.4‐fold reduction in charge‐transfer resistance and accelerated pseudocapacitive kinetics, consistent with CISS‐induced spin‐polarized currents that suppress spin‐flip scattering and facilitate interfacial electron transfer. This work establishes chirality as a new design dimension for electrochemical energy storage and opens a general pathway toward spin‐aware engineering of high‐performance supercapacitors without external magnetic fields.

Atypical Condensation Domains Guide Discovery and Illuminate Biosynthesis of Myxoglucamides Featuring Vinyl‐Substituted, α‐Oxidized γ‐Amino Acids

ABSTRACT Condensation (C) domains in nonribosomal peptide synthetase (NRPS) pathways exhibit versatile functions that drive biosynthetic and chemical novelty. Through genome mining for atypical C domains, we identified a hybrid NRPS/polyketide synthase (PKS) biosynthetic gene cluster ( mxg ) from Cystobacterineae sp. MCy9003 and discovered myxoglucamides, a family of glycolipopeptides featuring an unprecedented vinyl‐substituted γ‐amino acid bearing an α‐hydroxy/α‐ketoamide functionality. Heterologous expression of the promoter‐refactored pathway revealed new O ‐acylated myxoglucamides, and subsequent studies unveiled the C domain‐like enzyme MxgH as a promiscuous O ‐acyltransferase decorating the glucose moiety with short‐chain acyl groups. Biosynthetic investigations demonstrated that the unusual γ‐amino acid originates from l ‐glutamate. Completion of the cryptic β‐hydroxylation of peptidyl carrier protein‐tethered glutamate by the α‐ketoglutarate‐dependent dioxygenase Ox MxgA occurs only concomitantly with upstream chain extension, revealing a bidirectional checkpoint for substrate fidelity. Unexpectedly, the C‐domain‐like interface domain I MxgB is dispensable for this coupled transformation. Mutational analysis of the FMN‐dependent monooxygenase encoded by mxgE , together with characterization of a shunt metabolite, supported its role in α‐oxidation for α‐hydroxy/α‐ketoamide formation during γ‐amino acid assembly. Together, these findings uncover an unrecognized biosynthetic logic for generating vinyl‐substituted, α‐oxidized γ‐amino acids and substantially expand the functional repertoire of NRPS/PKS assembly lines.

Hierarchical Chirality Memory Governs Dual Chiroptical Inversion in Mesoscopic Helical Covalent Organic Frameworks

ABSTRACT Constructing crystalline chiral covalent organic frameworks (CCOFs) with programmable chiroptical properties from a single chiral source remains highly challenging. Herein, we report a dynamic covalent evolution strategy that transforms supramolecular‐induced helical covalent organic polymers into mesoscopic helical CCOFs through thermodynamic self‐crystallization as well as single‐step and stepwise monomer exchange. Remarkably, two distinct chiroptical inversion modes are preserved during framework evolution: a conventional inversion accompanied by opposite helical sense and a second inversion displaying opposite chiroptical activity despite identical mesoscopic helicity, originating from different sub‐nanometer chiral packing arrangements. Time‐dependent experiments and theoretical calculations reveal persistent chirality‐ and packing‐memory effects throughout dynamic reconstruction. Using a single chiral template system, this strategy affords 24 mesoscopic helical CCOFs with diverse linkage chemistries and programmable chiroptical responses. Furthermore, pore‐confined incorporation of aggregation‐induced emissive guests extends both inversion modes into flexible circularly polarized luminescence films.

Molecularly Templated Buried Interfaces for Inverted Perovskite Solar Cells

ABSTRACT The buried interface between self‐assembled monolayers (SAMs) and perovskite absorbers critically governs charge extraction and stability in inverted perovskite solar cells, yet remains structurally mismatched and poorly controlled. Here, we report a buried‐interface engineering strategy inspired by non‑covalent molecular templating, enabled by complementary triphenylamine‐based molecular building blocks. A triphenylamine‐based ammonium salt, 2‐(4‐(diphenylamino)phenyl)ethanammonium iodide (TPANI), is introduced into the perovskite precursor, while a structurally matched triphenylamine‐based bisphosphonic acid SAM deposited on ITO serves as the hole‐selective layer. Non‐covalent interactions at the buried interface induce molecular templating and interfacial organization of TPANI, strengthening SAM/perovskite adhesion and reducing intergranular groove depth at the buried side of the perovskite film. The resulting monolithically integrated interface suppresses buried interfacial defects, improves energy‐level alignment, and facilitates hole extraction. Consequently, inverted devices achieve a power conversion efficiency of 26.58% with an exceptionally high fill factor of 86.72%, together with markedly enhanced operational stability. These results demonstrate that non‑covalent molecular templating provides an effective and general strategy for engineering buried interfaces in perovskite photovoltaics.

Inside Front Cover: Deep Learning Enables Identification of Antimicrobial Peptides Through Mechanochromic Fingerprints

Pd‐Catalyzed Enantioselective Construction of Isoindolo[2,1‐ <i>a</i> ]indoles

ABSTRACT Isoindolo[2,1‐ a ]indoles are a class of important functionalized indole‐based heterocycles with significant utility in natural products, pharmaceuticals, and functional materials. Larock isoindolo[2,1‐ a ]indole synthesis is one of the most straightforward and efficient methods for the synthesis of isoindolo[2,1‐ a ]indole utilizing internal alkynes and imines derived from o ‐iodoanilines and aldehydes based on Larock indole synthesis. However, developing an asymmetric version for the construction of chiral isoindolo[2,1‐ a ]indoles has posed considerable challenges since its initial report in 1999. Herein, we report a first example of asymmetric Larock isoindolo[2,1‐ a ]indole synthesis by employing a chiral sulfinamide phosphine (Sadphos) ligand (Ming‐Phos) with modification. It allows rapid transformation of a wide range of substrates in good to excellent enantioselectivities, and provides a facile and straightforward access to chiral isoindolo[2,1‐ a ]indole fused heterocycles. Notably, these chiral isoindolo[2,1‐ a ]indole fused heterocycles exhibit bright fluorescence. The optical properties, including circular dichroism and quantum yield, are examined. The transformation offers a chiral highly conjugated system, which could have great potential applications in chiral optoelectronic materials.

Palladium‐Catalyzed Asymmetric Synthesis of Methylidene Cyclobutanes via Enantioselective Intramolecular Heck‐Type Reactions

ABSTRACT Cyclobutanes as well as 2‐substituted alkylidene cyclobutanes (ADCBs) are important skeletons in pharmaceuticals and versatile precursors in organic synthesis. However, enantioselective synthesis of ADCBs remains an underexplored area of research due to the high ring strain and competing side reactions. Herein, we report a Pd‐catalyzed asymmetric intramolecular Heck‐type reaction that provides a series of 1‐methylidene‐2‐arylcyclobutanes in moderate to good yields with excellent enantioselectivity and chemoselectivity. This method features broad substrate scope and demonstrates potential utility for constructing the core skeletons of bioactive molecules. Mechanistic studies indicate that the rate‐determining step of this reaction depends on the electron density of the aryl bromide moiety. Dmdba plays an important role in improving the chemoselectivity.

A Bimetallic Covalent Organic Framework Photonic Synaptic Electrocatalysts

ABSTRACT Photonic synaptic electrocatalysts encode catalytic activity as a writable, retainable state under optical stimulation, enabling history‐dependent performance modulation with potential relevance to scenarios such as intermittent solar illumination and artificial metabolic learning systems. However, most photo‐assisted electrocatalysts are stateless, showing only transient activity enhancement under illumination that vanishes once the light is removed. Here, we establish a photonic synaptic electrocatalyst based on a bimetallic covalent organic framework (Co–Ni─COF), in which optical stimulation writes synaptic information into the catalytic state, and oxygen evolution serves as a stringent functional readout. During electrochemical reactions, Co─Ni─COF shows strong photonic synaptic behavior, featuring excitatory postsynaptic current responses, tunable synaptic plasticity, transitions from short‐term to long‐term plasticity, learning–forgetting–relearning behavior, and long‐term memory retention. Mechanistic investigations reveal that this light‐written and retained state originates from strengthened electronic coupling between Co and Ni centers, promoted charge delocalization and intermetallic charge transfer, and the accumulation of metastable Co(III) active species together with key oxygenated intermediates (*OOH, *OO). Notably, a substantial fraction of enhanced catalytic activity is preserved for hours in the dark, maintaining ∼127% higher than the initial state after 3 h, highlighting its potential for efficient energy conversion under intermittent solar illumination.

Scalable ω‐Substituted α‐Olefins via Living Chain Transfer Telomerization: A Platform for Next Generation Polyolefins

ABSTRACT Isomerically pure, ω‐substituted α‐olefins of general structure, X‐(CH 2 ) m (CH 2 CH 2 ) n ‐1 CH = CH 2 ( m = 0 or 1; X = alkyl or aryl) ( 3 ), have been produced in practical and scalable quantities as narrow Poisson molar mass distributions of separable n ‐mers (e.g. n = 1 – 10) through a one‐pot, two‐step process involving: living ternary chain transfer telomerization of tris(ω‐substituted alkyl)aluminum, [X‐(CH 2 ) m CH 2 CH 2 ] 3 Al ( 1 ), with ethene and a small amount of diethylzinc as a chain transfer mediator, using an in situ generated ion pair initiator derived from the cyclopentadienyl, amidinate (CPAM) Hf pre‐initiator, (η 5 ‐C 5 Me 5 )[κ 2 ‐( N,N’ )‐N(Et)C(Me)N(Et)]HfMe 2 ( 2 ) and the borate co‐initiator, [PhNHMe 2 ][B(C 6 F 5 ) 4 ] ( B ), followed by catalytic displacement of the trialkylaluminum intermediate using bis(1,5‐cyclooctadiene)Ni(0) as the pre‐catalyst. Results are further presented for production of several families of “next generation” polyolefins that are obtained through CPAM Zr‐ and Hf‐mediated stereoselective (enantioselective) living coordination polymerization of different derivatives of 3 and including copolymerization with a variety of linear and branched α‐olefins and 1,5‐hexadiene.

Solvent‐Driven Modulation of Covalent‐Organic Framework Nano‐Architectures for Photothermal‐Catalytic Biomass Valorization and Hydrogen Peroxide Production

ABSTRACT The modulation of three‐dimensional (3D) covalent‐organic frameworks (COFs) into multifunctional nano‐architectures is highly desirable for their extended applications yet still challenging in both material design and morphology investigation. Here, we have designed a functional 3D COF (DPP‐TAM‐COF) and successfully modulated it into diverse nano‐architectures, including nano‐ring, hollow‐sphere, and nano‐urchin, through a solvent‐driven tuning strategy. The produced nano‐architectures possess bifunctional groups, well‐tuned morphology, high porosity, and photothermal properties that can be applied in efficient photothermal biomass valorization coupled with hydrogen peroxide production. Specifically, they can realize the furfuryl alcohol conversion into furoic acid with an optimal generation efficiency of 39.0 mmol/g coupled with the efficient hydrogen peroxide production, which is superior to the majority of reported materials. Based on various characterizations and theoretical calculations, the functions of nano‐architectures and bifunctional groups have been validated in the coupling reaction. Aiming at extending the application regimes of 3D COFs, this work might give new insights into the structure or morphology study of 3D COFs.

Fluorescent cAMP Analogs: Enzymatic Synthesis, Unexpected Photophysical Behavior and Protein Kinase A Recognition

ABSTRACT Cyclic adenosine monophosphate (cAMP) is a second messenger, regulating critical physiological processes. We report the enzymatic synthesis, unique photophysical features, and biological activity of novel emissive cAMP analogs (c th AMP and c tz AMP), comprised of thiopheno‐ and isothiazolo‐based families of isomorphic ribonucleotides. The unexpectedly high brightness of c th AMP compared to th ATP and th AMP, its precursor and hydrolysis products, respectively, driven by an anti ‐to‐ syn conformational shift upon cyclization, is employed for real‐time monitoring of the adenylyl cyclase (AC) mediated synthesis and phosphodiesterase (PDE) mediated hydrolysis. Importantly, these emissive analogs effectively activate protein kinase A (PKA). This study provides critical insights into the biomolecular recognition and catalytic mechanism of cAMP‐regulating enzymes, establishing these isomorphic analogs as potential tools for investigating cAMP‐dependent protein–ligand interaction through fluorescence spectroscopy.

Synergistic Bulk‐Surface Modulation Stabilizing LiCoO ₂ at 4.65 V via Zr‐Pillaring and In Situ Lattice‐Matching Engineering

ABSTRACT Lithium cobalt oxide (LiCoO 2 , LCO) is a critical cathode material for high‐energy‐density lithium‐ion batteries, yet its application above 4.55 V (vs. Li/Li + ) is severely limited by structural degradation via the O3→H1‐3 phase transition, lattice oxygen loss, and cobalt dissolution. Here, we report a synergistic bulk‐surface modification strategy combining Zr‐pillaring (LZCO) with in situ LiCoPO 4 coating (LZCO@P) to stabilize LCO at 4.65 V. Zr‐pillaring stabilizes the lattice and suppresses phase transition by expanding the O 2p‐Co 3d band gap, as suggested by density functional theory (DFT), to mitigate oxygen redox activity. Lattice‐matched interfacial engineering between LZCO and LiCoPO 4 coating results from interfacial P–O tetrahedral formation, which enhances mechanical adhesion and reduces oxygen surface reactivity of LZCO. Consequently, LZCO@P achieves 80.8% capacity retention after 1000 cycles at 1 C (3.5–4.65 V) and 91.2% after 1000 cycles at 3 C (3.5–4.65 V). A practical Li||LZCO@P pouch cell retains 92.3% capacity after 160 cycles at 1 C (3.0–4.6 V). The synergistic bulk‐surface modification strategy contributes through different mechanisms and comprehensively improves the cycling stability of LZCO@P at 4.65 V.

Modulated Structure‐Electronic Coupling at Pt/CeO _x –TiO ₂ Interfaces Boosts Low‐Temperature Preferential CO Oxidation

ABSTRACT Preferential oxidation, PROX, of residual CO in a hydrogen‐rich synthetic gas is the final stage of industrial hydrogen production and purification. However, selectively oxidizing around 1 vol. % of CO without consuming hydrogen is technically challenging. Here, we use Pt single atoms (SAs) stabilized on CeO x –TiO 2 supporting oxides toward PROX of CO. Based on a combined study of density functional theory calculations and in situ spectroscopic analyses, we identified the delicate electronic states of the reaction centers. The bifunctional nature of the spatially separated Pt–O–Ti and Pt–O–Ce sites promoted selective PROX of CO. The preferentially adsorbed hydrogen at the Pt–O–Ti site behaves as an activity regulator, donating electrons to Pt, thus reducing Pt–SAs. The oxygen ion at the Pt–O–Ce interface actively oxidizes the weakly adsorbed CO on reduced Pt–SAs. The unique structural and electronic ensembles at the Pt–CeO x –TiO 2 interfaces suppress hydrogen consumption but, instead, promote the PROX of CO under hydrogen‐rich conditions with high specific mass activity and 100 % selectivity for CO 2 at below 100°C. We present a representative case of using electronic modulation of Pt–SAs under reaction conditions, enabled by the unique structural ensemble of Pt‐oxide interfaces, to activate Pt–SAs dynamically.

Surface Hydroxyl Steered Adsorption Configuration for Efficient Photocatalysis Coupling Hydrogen Evolution and 5‐Hydroxymethylfurfural Selective Oxidation Toward 2,5‐Furandicarboxylic Acid Production

ABSTRACT Photocatalytic coupling water reduction reaction and 5‐hydroxymethylfurfural (HMF) selective oxidation toward 2,5‐furandicarboxylic acid (FDCA) offers a promising route for co‐production of green hydrogen and value‐added bio‐based platform chemicals, but limited by low FDCA selectivity and yield. Herein, an Al‐doped SrTiO 3 (STO) photocatalyst integrated with RhCrO x and Co 3 O 4 cocatalysts is investigated for HMF oxidation reaction (HMFOR) under neutral and alkaline conditions. While alkaline conditions markedly improve the FDCA production, the accelerated HMF self‐degradation and competing Cannizzaro side‐reaction compromise the hole utilization efficiency. Spectral and theoretical investigations reveal that surface‐bonded hydroxyl (─OH) species on Co 3 O 4 under alkaline conditions steer HMF adsorption from vertical to a tilted configuration, which facilitates the rate‐determining step of 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA) to 5‐formyl‐2‐furancarboxylic acid (FFCA) conversion. Building upon this mechanistic insight, Co 3 O 4 is substituted with a ─OH terminated Co(OH) 2 oxidation cocatalyst, which sustains the favorable flat HMF adsorption configuration even under neutral and oxygen‐free conditions. The obtained RhCrO x /STO/Co(OH) 2 achieves a FDCA selectivity of 72.7% and a yield of 49.0% for HMFOR, together with hydrogen evolution rate of 626 µmol g −1  h −1 . This study demonstrates that steering reactant adsorption configuration via surface ─OH species offers an effective strategy for efficient solar‐driven photocatalysis coupling biomass valorization and hydrogen production.

Stereoelectronically Controlled Regioselective Allylation of Aldehyde Under Photoredox/Chromium Catalysis

ABSTRACT The formation of structurally defined α,γ‐disubstituted allylmetallic intermediate which could undergo regioselective allylation with carbonyl compounds remains a formidable challenge in synthetic chemistry. Although regioselective in situ formation of α,γ‐disubstituted allylchromium intermediate controlled by coordinative directing groups has been achieved, how to achieve high selectivity for reactions involving α,γ‐disubstituted allylic chromium intermediates through electronic control has been elusive. In this study, we report a silyl‐group‐directed strategy that exploits the α‐silicon effect to achieve exceptional regiocontrol (rr &gt; 95:5) in the chromium‐catalyzed radical‐type allylation of aldehydes with α‐silyl‐substituted diene and Hantzsch ester under photoredox catalysis. The method establishes a paradigm of electronic steering mode for chromium catalysis, enabling the highly regioselective and diastereoselective synthesis of a wide variety of valuable alkenylsilane‐containing homoallylic alcohols commencing from readily accessible α‐silyl‐substituted dienes. The three‐component reactions display good substrate generality and broad functional group compatibility, and could be successfully applied in the post‐functionalization of biologically active complex molecules. Moreover, the resulting alkenylsilane‐containing homoallylic alcohols could be easily converted into other value‐added organic molecules, and the preinstalled silyl substituent could be readily manipulated for straightforward access of diverse substituents (e.g., alkyl, aryl, alkenyl, and alkynyl), which are difficult to access by using documented methodologies.

Imide Cyclophane Assemblies Enable Aquaporin‐Like Water Transport

ABSTRACT Artificial water channels (AWCs) that replicate the high efficiency and selectivity of natural aquaporins are of considerable interest for desalination, water purification, and biomedical applications, yet the simultaneous realization of high permeability and perfect selectivity remains challenging. Herein, we report a class of self‐assembled AWCs based on an imide cyclophane. Single‐crystal analysis reveals that macrocycle 1 features an internal cavity of 3.5 Å × 6.3 Å, with a narrow constriction closely matching the dimensions of the selectivity filter of aquaporin 1. The assembled channel ( 1 ) 4 exhibits a single‐channel water transport rate of up to 3.9 × 10 9  H 2 O s −1 , corresponding to approximately 36% of AQP1 and representing one of the best‐performing small‐molecule self‐assembled AWCs reported to date. Notably, it completely excludes NaCl, KCl, and protons. This work demonstrates that both the key structural feature and function of aquaporins can be emulated through a bottom‐up supramolecular approach, providing a platform for the design of high‐performance biomimetic membranes and channel‐based therapeutics.

Tenfold Expansion Submicrometer MALDI Mass Spectrometry Imaging of Tissues and Cultured Cells

ABSTRACT Achieving  submicrometer lateral resolution in matrix‐assisted laser desorption/ionization mass spectrometry imaging (MALDI‐MSI) is essential for molecular characterization at the single‐cell and subcellular levels but is fundamentally limited by optical focusing and matrix crystallization. Here, we present tenfold expansion mass spectrometry imaging (10X ExMSI), an expansion MALDI‐MSI workflow that reaches an effective lateral resolution of ∼500 nm on standard commercial instruments using a 5 µm acquisition step size without pixel oversampling. The SDS‐free digestion protocol minimizes lipid leaching and supports broad detection of major lipid classes, including glycerophospholipids and sphingolipids, although a reduction in primary amine‐containing lipids is observed due to cross‐linking. Using 10X ExMSI, we resolve subcellular structures in mouse brain tissues, such as dendritic arborizations, that are challenging to access with existing MALDI‐MSI implementations. We further demonstrate expansion‐based MSI on cultured A549 cells, achieving subcellular‐level lipid mapping. The method is fully compatible with standard MALDI‐MSI systems, providing an accessible and scalable route to high‐resolution, label‐free molecular imaging. These capabilities open new opportunities for studying cellular architecture and molecular heterogeneity in biological and biomedical research.

Programmable Nanostructural Orientation on Amorphous Phase‐Separating Systems

ABSTRACT Currently, there remains a lack of broadly applicable strategies for programming the nanostructural orientation in a bottom‐up way (e.g., for those widely used amorphous phase‐separating systems). This is because, for the systems lacking mesogenic units, the orientation is primarily governed by interfacial energy, which is difficult to modulate spatiotemporally. Herein, we present a strategy to make the orientation of amorphous phase‐separating systems photo‐programmable. Taking amorphous block copolymers as a clean model system, a persulfurated aromatic modulator that interacts with both domains can be designed, allowing a minimized interfacial energy mismatch between the two domains and the substrate, which favors perpendicular orientation. Upon light irradiation, photoinduced aggregation of the modulator redistributes its partitioning between the domains, amplifying the interfacial energy asymmetry and driving self‐assembly to parallel orientation. This orientation switching is resettable through light removal. Such an orientation control strategy is fit for density multiplication of the nanostructures, and can even serve as a template for other material incorporation (e.g., introducing conductive polymers and creating a 25‐fold conductivity contrast through orientation), enabling effective function expansion in practical nanotechnology.