Through-space Interactions Research Articles

Luminescent Radical Polymers.

Organic radicals are gaining significant interest in luminescent materials due to their unique properties, which present unprecedented opportunities for innovation across various fields, from display technology to biomedical applications. However, addressing challenges related to stability and low fluorescence efficiency is crucial to unlocking their full potential for practical applications. Polymerization has emerged as an effective strategy to enhance intra- and interchain through-space interactions, enabling the creation of stable luminescent radicals with excellent processing and multifunctional properties. This concept emphasizes the strategic use of polymerization in designing and synthesizing stable main-chain and side-chain radical polymers. This approach not only broadens the scope of stable radicals but also improves their luminescence properties as photofunctional materials.

σ Interference: Through-Space and Through-Bond Dichotomy.

Dividing orbital interactions into through-space (TS) and through-bond (TB) modes is valuable for understanding various molecular properties. In this paper, we elucidate how the quantum interference phenomenon known as σ interference in electron transport through σ systems arises from TS and TB interactions. We performed electron transport calculations using a combination of density functional theory and nonequilibrium Green's function methods, focusing on ethylenediamine, a classical molecule that effectively highlights the contrast between TS and TB interactions. Our results confirm that destructive σ interference occurs in the syn and gauche conformers of this molecule. To further investigate both TS and TB interactions, we employed two analytical methods: the fragment molecular orbital (FMO) method, which captures the effects of both TS and TB interactions, and the chemical graph theory method, which specializes in TB interactions. The FMO analysis demonstrated that TB interactions lead to the characteristic distribution and energy level alignment of the frontier orbitals. Additionally, it was clarified that a change in TS interaction, due to a variation in the dihedral angle of the molecule, alters the energy gap between these orbitals, resulting in the manifestation of σ interference in the syn and gauche conformers, but not in the trans conformer. The chemical graph theory analysis based on the ladder C model, aimed at exploring the topological origin of σ interference from the network of TB interactions, revealed that σ interference is caused by the cancellation between the walk associated with geminal interactions (σ-conjugation) and the one related to vicinal interaction (σ-hyperconjugation). Notably, it was found that the vicinal interaction, which changes sign with the dihedral angle, has a decisive influence on whether this cancellation occurs. These findings clarify that σ interference arises from the interplay between TS and TB interactions. This insight will be valuable for designing molecular systems that utilize σ interference.

Anomalous Pressure-Induced Blue-Shifted Emission of Ionic Copper-Iodine Clusters: The Competitive Effect between Cuprophilic Interactions and Through-Space Interactions.

Developing ionic copper-iodine clusters with multiple emitting is crucial for enriching lighting and display materials with various colors. However, the luminescent properties of traditional ionic copper-iodine clusters are often closely associated with low-energy cluster-centered triplet emission, which will redshift further as the Cu⋅⋅⋅Cu bond length decreases. This article utilizes a pressure-treated strategy to achieve an anomalous pressure-induced blue-shifted luminescence phenomenon in ionic Cu4I6(4-dimethylamino-1-ethylpyridinium)2 crystals for the first time, which is based on dominant through-space charge-transfer (TSCT). Herein, we reveal that the more advantageous through-space interactions in the competition between cuprophilic interactions and through-space interactions can lead to a blue-shifted luminescence. High-pressure angle-dispersive X-ray diffraction and high-pressure infrared experiments show that the enhanced through-space interactions mainly originate from forming new intermolecular C-H⋅⋅⋅I hydrogen bonds and the enhancement of van der Waals interactions between organic cations and anionic clusters. Theoretical calculations and experimental studies of excited-state dynamics confirm that the blue-shifted emission is due to the increased energy gap between the excited triplet and ground states caused by the electron delocalization under stronger through-space interactions. This work deepens previous understanding and provides a new avenue to design and synthetic ionic copper-iodine clusters with high-energy TSCT emission.

Emergence of a distinct mechanism of C-N bond formation in photoenzymes.

C-N bond formation is integral to modern chemical synthesis due to the ubiquity of nitrogen heterocycles in small-molecule pharmaceuticals and agrochemicals. Alkene hydroamination with unactivated alkenes is an atom economical strategy for constructing these bonds. However, these reactions are challenging to render asymmetric when preparing fully substituted carbon stereocenters. Here, we report a photoenzymatic alkene hydroamination to prepare 2,2-disubstituted pyrrolidines by a Baeyer-Villiger Monooxygenase. Five rounds of protein engineering afforded a mutant, providing excellent product yield and stereoselectivity. Unlike related photochemical hydroaminations, which rely on the oxidation of the amine or alkene for C-N bond formation, this work exploits a through-space interaction of a reductively generated benzylic radical and the nitrogen lone pair. This antibonding interaction lowers the oxidation potential of the radical, enabling electron transfer to the flavin cofactor. Experiments indicate that the enzyme microenvironment is essential in enabling a novel C-N bond formation mechanism with no parallel in small molecule catalysis. Molecular dynamics simulations were performed to investigate the substrate in the enzyme active site which further support this hypothesis. This work is a rare example of an emerging mechanism in non-natural biocatalysis, where an enzyme has access to a mechanism that its individual components do not. Our study showcases the potential of enhancing emergent mechanisms using protein engineering to provide unique mechanistic solutions to unanswered challenges in chemical synthesis.

Endo-Encapsulated Multi-Resonance Dendrimers with Through-Space Interactions for Efficient Narrowband Blue-Emitting Solution-Processed OLEDs.

Different from conventional luminescent dendrimers with fluorophore tethered outside to dendron, here we first developed endo-encapsulated luminescent dendrimers with multi-resonance (MR) fluorophore embedded inside of carbazole dendrons by growing dendrons through 1,8-positions of central carbazole moiety to create a cavity for accommodating the fluorophore. This endo-encapsulated structure not only shields the fluorophore to fully resist aggregation-caused spectral broadening, but also induce through-space interactions between dendron and fluorophore via intramolecular π-stacking, giving lowered singlet state energy and reduced singlet-triplet energy splitting to accelerate reverse intersystem crossing (RISC) from triplet to singlet states. The resultant dendrimer containing 1,8-linked second-generation carbazole dendrons and boron, sulfur-doped polycyclic MR fluorophore exhibits narrowband blue emission at 471 nm with FWHM kept at 34 nm even in neat film, together with ~4 times enhancement of RISC rate constant compared to its exo-tethered counterpart. Solution-processed OLEDs based on the endo-encapsulated dendrimer reveal efficient narrowband blue emissions with maximum external quantum efficiency of 22.6%, representing the best device efficiency for blue-emitting multi-resonance dendrimers so far.

Stable Persistent Room-Temperature Phosphorescent Hydrogels Based on Ionically Crosslinked Nonaromatic Carboxylate Polymers.

Developing pure organic room-temperature phosphorescent (RTP) hydrogels is important for expanding the practical applications of phosphorescent materials. However, most of the reported RTP hydrogels containing aromatic phosphors suffer from short phosphorescent lifetimes, unstable underwater RTP emissions, and complex preparation processes. Herein, novel nonaromatic RTP hydrogels are prepared by using two types of non-traditional luminescent polymers, sodium alginate and a polymeric carboxylate, which are not RTP emissive or very weakly emissive in aqueous environments. The prepared hydrogels exhibit the following features: I) color-tunable RTP emissions with ultra-long lifetimes up to 451.1ms, II) excellent anti-swelling properties and stable persistent RTP emission even after being immersed in deionized water for months, III) efficient and large-scale preparation of hydrogel fibers by wet spinning technique. Experiment results and theoretical calculations show that the stable and long-lifetime RTP emissions of the hydrogels originate from the introduction of more nonconventional chromophores which are strongly crosslinked with ionic bonding between carboxylate groups and calcium ions and enhanced through-space interactions between them. This work provides a reliable strategy for designing nonaromatic hydrogels with stable and persistent RTP.

Robust Sandwich-Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12-Dihydroindolo[2,3-a]carbazole as Bridge.

Constructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V-shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich-structured molecules, and a series of novel and robust TADF materials with regular U-shaped sandwich conformations are constructed by using 11,12-dihydroindolo[2,3-a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9-phenylcarbazole and indolo[3,2,1-JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556-563 oC), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86%-97%). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through-space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited-state energy. The organic light-emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6%, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12-dihydroindolo[2,3-a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.

Design of Cr-Based Molecular Electrocatalyst Systems for the CO2 Reduction Reaction.

ConspectusHuman influence on the climate system was recently summarized by the sixth Intergovernmental Panel on Climate Change (IPCC) Assessment Report, which noted that global surface temperatures have increased more rapidly in the last 50 years than in any other 50-year period in the last 2000 years. Elevated global surface temperatures have had detrimental impacts, including more frequent and intense extreme weather patterns like flooding, wildfires, and droughts. In order to limit greenhouse gas emissions, various climate change policies, like emissions trading schemes and carbon taxes, have been implemented in many countries. The most prevalent anthropogenic greenhouse gas emitted is carbon dioxide (CO2), which accounted for 80% of all U.S. greenhouse gas emissions in 2022. The reduction of CO2 through the use of homogeneous electrocatalysts generally follows a two-electron/two-proton pathway to produce either carbon monoxide (CO) with water (H2O) as a coproduct or formic acid (HCOOH). These reduced carbon species are relevant to industrial applications: the Fischer-Tropsch process uses CO and H2 to produce fuels and commodity chemicals, while HCOOH is an energy dense carrier for fuel cells and useful synthetic reagent. Electrochemically reducing CO2 to value-added products is a potential way to address its steadily increasing atmospheric concentrations while supplanting the use of nonrenewable petrochemical reserves through the generation of new carbon-based resources. The selective electrochemical reduction of CO2 (CO2RR) by homogeneous catalyst systems was initially achieved with late (and sometimes costly) transition metal active sites, leading the field to conclude that transition metal complexes based on metals earlier in the periodic table, like chromium (Cr), were nonprivileged for the CO2RR. However, metals early in the table have sufficient reducing power to mediate the CO2RR and therefore could be selective in the correct coordination environment. This Account describes our efforts to develop and optimize novel Cr-based CO2RR catalyst systems through redox-active ligand modification strategies and the use of redox mediators (RMs). RMs are redox-active molecules which can participate cocatalytically during an electrochemical reaction, transferring electrons─often accompanied by protons─to a catalytic active site. Through mechanistic and computational work, we have found that ligand-based redox activity is key to controlling the intrinsic selectivity of these Cr compounds for CO2 activation. Ligand-based redox activity is also essential for developing cocatalytic systems, since it enables through-space interactions with reduced RMs containing redox-active planar aromatic groups, allowing charge transfer to occur within the catalyst assembly. Following a summary of our work, we offer a perspective on the possibilities for future development of catalytic and cocatalytic systems with early transition metals for small molecule activation.

Activating Electronic Delocalization: Through-Space Lone-Pair Interactions versus Hydrogen Bonding

Activating Electronic Delocalization: Through-Space Lone-Pair Interactions versus Hydrogen Bonding

Photochromic luminescence of organic crystals arising from subtle molecular rearrangement

Photoluminescence (PL) colour-changing materials in response to photostimulus play an increasingly significant role in intelligent applications for their programmability. Nevertheless, current research mainly focuses on photochemical processes, with less attention to PL transformation through uniform aggregation mode adjustment. Here we show photochromic luminescence in organic crystals (e.g. dimethyl terephthalate) with PL varying from dark blue to purple, then to bright orange-red, and finally to red. This change is attributed to the emergence of clusters with red emission, which is barely achieved in single-benzene-based structures, thanks to the subtle molecular rearrangements prompted by light. Crucial to this process are the through-space electron interactions among molecules and moderate short contacts between ester groups. The irradiated crystals exhibit reversible PL transformation upon sufficient relaxation, showing promising applications in information storage and smart optoelectronic devices. This research contributes to the development of smart photochromic luminescent materials with significant PL colour transformations through molecular rearrangement.

Ultrafast conformation-dependent charge transfer in N, N, N′, N′-tetramethyl-1,3-propanediamine: Effect of flexible carbon skeleton on electron lone pair interactions

Flexible three-carbon skeleton makes N, N, N′, N′-tetramethyl-1,3-propanediamine (TMPDA) an important diamine system to investigate the conformation-dependent electron lone pair interactions and charge delocalization. The charge transfer process linked to structural motions of the three-carbon skeleton has been monitored in real time by the Rydberg electron binding energy (BE) spectra of TMPDA coupled with quantum chemical calculations. Optical excitation to the 3p state with a 200 nm pump pulse initially generated a localized charge on one of the two nitrogen atoms that may partially transfer to the other one. Rapid internal conversion (IC) from the 3p to 3s state occurred within 430 fs, resulting in an initial charge delocalized 3s_h/3s_l population ratio of 23.6 %/76.4 %. A final 3s_h/3s_l (51.9 %/48.1 %) equilibrium proceeded within about 2.64 ps. The 3s_h (TTTT+, GG′TG+ and G′GG′G+) and 3s_l (GG′GG′+ and GG′G′G+) (see text for structure definitions) are identified as the extended and folded conformers, respectively. Two types of electron lone pair interactions, i.e., through-space interaction (TSI) and through-bond interaction (TBI), are found to coexist in TMPDA to drive charge transfer. The GG′GG′+ and GG′G′G+ structures exhibit TSI, while the TTTT+ structure shows TBI. The GG′TG+ and G′GG′G+ structures exhibit both TSI and TBI. Flexible three-carbon skeleton provide more opportunities for the two N-electron lone pairs to overlap in space (i.e., TSI), making TMPDA to be favorable for the most stably folded conformation.

Multiple hydrogen-bonding induced nonconventional red fluorescence emission in hydrogels

The development of unconventional long-wavelength fluorescent polymer hydrogels without using polycyclic aromatic hydrocarbons or extended π-conjugation is a fundamental challenge in luminescent materials owing to a lack of understanding regarding the spatial interactions induced inherent clustering-triggered emission under water-rich conditions. Inspired by the color change of protein astaxanthin as a result of heat-induced denaturation, we propose a thermodynamically driven strategy to develop red fluorescence (~610 nm) by boiling multiple hydrogen-bonded poly(N-acryloylsemicarbazide) hydrogels in a water bath. We reveal that thermodynamically driven conformational changes of polymer chains from isolated hydrogen bonding donor-acceptor structures to through-space interaction structures induce intrinsic fluorescence shifts from blue to red during clustering-triggered emission. The proposed multiple hydrogen-bonding supramolecular hydrogel shows good fluorescence stability, mechanical robustness, and 3D printability for customizable shaping. We provide a viable method to prepare nonconventional long-wavelength fluorescent hydrogels towards soft fluorescent devices without initially introducing any fluorescent components.

Proximity effects: Structural implications and quantum-chemical description. Review

Proximity effects occur between vicinal functional groups or between a group and a specific molecular fragment in close proximity, for example an endocyclic N atom in the ortho position relative to the group. They are a combination of through-bond inductive and resonance effects, and through-space interactions, which can be either attractive or repulsive. In this review, we discuss quantum-chemical tools and examples from the literature that explore the structural and physicochemical implications of proximity effects. We focus on derivatives of small molecules: benzene, small polycyclic aromatic hydrocarbons, simple heterocycles, and lastly, purine derivatives.

Phosphine-Capped Effects Enable Full-Color Clusteroluminescence in Nonconjugated Polyesters.

Full-color luminophores have advanced applications in materials and engineering, but constructing color-tunable clusteroluminescence (CL) from nonconjugated polymers based on through-space interactions remains a huge challenge. Herein, we develop phosphine-capped nonconjugated polyesters exhibiting blue-to-red CL (400-700 nm) based on phosphine-initiated copolymerization of epoxides and cyclic anhydrides, especially P1-0.5TPP, which exhibits red CL (610 nm) with a high quantum yield of 32%. Experiments and theoretical calculations disclose that the phosphine-capped effect in polyesters brings about conformational changes and induces phosphine-ester clusters by through-space (n,π*) interactions. Moreover, CL colors and efficiencies can be easily tailored by types of phosphines, compositions and structures of polyesters, and concentration. Significantly, the role of polymer motions (group, segmental, and chain motions) on CL originating from microregions inside polyesters is revealed. Further, phosphine-capped nonconjugated polyesters are demonstrated to be nonconjugated dyes and fluorescent fibers and are also used for multicolor light-emitting diodes including white light. This work not only provides an engineering strategy based on the end-group effect to prepare full-color clusteroluminogens but also broadens the prospects for material applications.

White-light clusteroluminescence of poly(β-hydroxyvinyl N-substituted carbamate)s via through-space interactions

White-light-emitting polymers have attracted considerable attention in the fields of solid-state lighting and flexible displays. However, achieving white light emission from single-component polymers, particularly in clusteroluminescence (CL) polymers, remains a significant challenge. Herein, we synthesize three non-conjugated luminescent poly(β-hydroxyvinyl N-substituted carbamate)s (PHNCs): PHNCs-C with steric cyclohexyl groups, PHNCs-E with side hydroxyethyl groups, and PHNCs-H with flexible n-hexyl carbon chains. All PHNCs show excitation-independent emission, which transitions to excitation-dependent emission as the excitation wavelengths increase. It is proposed that these emissions originate from the π*→n transition of carbamate in hydroxyurethane and CL of hydroxyurethane, respectively. PHNCs-C exhibits the strongest CL and possesses the highest quantum yield (17.9 %) in solution, a performance that surpasses both PHNCs-E and PHNCs-H. This finding implies that a rigid structure can enhance and stabilize the through-space interactions (TSIs) of hydroxyurethane groups, resulting in a wide cluster-size distribution and white-light emission. Theoretical calculations corroborate these experimental results, further revealing that TSIs occur between the oxygen atoms of hydroxyurethane groups, namely, through-space n-n interactions of oxygen atoms. This work not only provides valuable insights into the nature of CL and TSIs, but also offers a novel approach to preparing single-component white-light-emitting CL polymers.

Through-Space Charge-Transfer Organogold(III) Complexes Enable High-Performance X-ray Scintillation and Imaging.

Organic scintillators have recently attracted growing attention for X-ray detection in industrial and medical applications. However, these materials still face critical obstacles of low attenuation efficiency and/or inefficient triplet exciton utilization. Here we developed a new category of organogold(III) complexes, Tp-Au-1 and Tp-Au-2, through adopting a through-space interaction motif to realize high X-ray attenuation efficiency and efficient harvesting of triplet excitons for emission. Thanks to the efficient through-space charge transfer process, this panel of complexes achieved higher photoluminescence quantum yield and shorter radiative lifetimes compared with the through-bond reference complexes. Inspiringly, these organogold(III) complexes exhibited polarity-dependent emission origins: thermally activated delayed fluorescence and/or phosphorescence. Under X-ray irradiation, Tp-Au-2 manifested intense radioluminescence together with a record-high scintillation light yield of 77,600 photons MeV-1 for organic scintillators. The resulting scintillator screens demonstrated high-quality X-ray imaging with >16.0 line pairs mm-1 spatial resolution, outstripping most organic and inorganic scintillators. This finding provides a feasible strategy for the design of superior organic X-ray scintillators.

A Novel Homoconjugated Propellane Triimide: Synthesis, Structural Analyses, and Gas Separation.

Rigid three-dimensional (3D) polycyclic propellanes have garnered interest due to their unique conformational spaces, which display great potential use in selectivity, separation and as models to study through-space electronic interactions. Herein we report the synthesis of a novel rigid propellane, trinaphtho[3.3.3]propellane triimide, which comprises three imide groups embedded on a trinaphtho[3.3.3]propellane. This propellane triimide exhibits large bathochromic shift, amplified molar absorptivity, enhanced fluorescence, and lower reduction potential when compared to the subunits. Computational and experimental studies reveal that the effective through-space π-orbitals interacting (homoconjugation) occurs between the subunits. Single-crystal XRD analysis reveals that the propellane triimide has a highly quasi-D3h symmetric skeleton and readily crystallizes into different superstructures by changing alkyl chains at the imide positions. In particular, the porous 3D superstructure with S-shaped channels is promising for taking up ethane (C2H6) with very good selectivity over ethylene (C2H4), which can purify C2H4 from C2H6/C2H4 in a single separation step. This work showcases a new class of rare 3D polycyclic propellane with intriguing electronic and supramolecular properties.

Detection and Identification of Nitrile Compounds via Recognition-Enabled Chromatographic 19F NMR.

The surge in applications of nitrile compounds across diverse fields, such as pharmaceuticals, agrochemicals, dyes, and functional materials, necessitates the development of rapid and efficient detection and identification methods. In this study, we introduce a chemosensing strategy employing a novel 19F-labeled probe, facilitating swift and accurate analysis of a broad spectrum of nitrile-containing analytes. This approach leverages the reversible interaction between the 19F-labeled probe and the analytes to produce chromatogram-like outputs, ensuring the precise identification of various pharmaceuticals and pesticides within complex matrices. Additionally, this dynamic system offers a versatile platform to investigate through-space 19F-19F interactions, showcasing its potential for future applications in mechanistic studies.

Direct Through-Space Substituent-π Interactions in Noncovalent Arene-Fullerene Assemblies.

The arene-arene interactions between electron-rich and deficient aromatics have been less understood. Herein, we focus on a [60]fullerene π-surface as an electron-deficient aromatics. Using a 1H signal of H2O@C60 as a magnetic probe, the presence of benzene-fullerene interactions was confirmed. To investigate substituent effects on the noncovalent arene-fullerene interactions, NMR titration experiments were carried out using an open-[60]fullerene and a series of substituted benzenes, i. e., PhX (X=NO2, CN, Cl, OMe, H, CH3, and NH2), demonstrating a 1 : 2 stoichiometry with a positive correlation between stabilization energies upon the first association (ΔG1) and Hammet constants (σm). The destabilization of the self-assembled structure for X=OMe with a σ-withdrawing nature clearly showed direct through-space substituent-π interactions describable by the Wheeler-Houk model while the second association was suggested to be considerably perturbed by the secondary effects.

RNAvigate: efficient exploration of RNA chemical probing datasets.

Chemical probing technologies enable high-throughput examination of diverse structural features of RNA, including local nucleotide flexibility, RNA secondary structure, protein and ligand binding, through-space interaction networks, and multistate structural ensembles. Deep understanding of RNA structure-function relationships typically requires evaluating a system under structure- and function-altering conditions, linking these data with additional information, and visualizing multilayered relationships. Current platforms lack the broad accessibility, flexibility and efficiency needed to iterate on integrative analyses of these diverse, complex data. Here, we share the RNA visualization and graphical analysis toolset RNAvigate, a straightforward and flexible Python library that automatically parses 21 standard file formats (primary sequence annotations, per- and internucleotide data, and secondary and tertiary structures) and outputs 18 plot types. RNAvigate enables efficient exploration of nuanced relationships between multiple layers of RNA structure information and across multiple experimental conditions. Compatibility with Jupyter notebooks enables nonburdensome, reproducible, transparent and organized sharing of multistep analyses and data visualization strategies. RNAvigate simplifies and accelerates discovery and characterization of RNA-centric functions in biology.