Intermolecular Dipole-dipole Interactions Research Articles

Hydrogen-bond enhanced interior charge transport and trapping in all-fiber triboelectric nanogenerators for human motion sensing and communication

Maximizing charge density output within confined tribolayer areas is crucial for advancing triboelectric nanogenerator (TENG) performance. While conventional methods primarily focus on enhancing current density by modifying the surface properties of tribo-surfaces, the impact of dipole-dipole interactions between polymer molecular chains in the fibrous tribomaterials has been underexplored. This study reveals that intermolecular dipole-dipole interactions, mediated by hydrogen bonding between chitosan and nylon66 molecular chains, serve as effective bridging mechanisms that substantially boost TENG current density. Furthermore, we developed a breathable and antibacterial electrode by depositing silver nanowires (AgNWs) on the tribolayer surfaces. To prevent air breakdown resulting from excessively high current density, multiwalled carbon nanotubes (MWCNTs) were integrated to enhance electron transfer and storage. The structure we constructed achieved an optimized performance with a high voltage of 335 V, current density of 194.5 mA m−2 and power density of 65.1 W m−2, which demonstrates outstanding performance compared to previously obtained results. Finally, the prepared SWS-TENG was attached to the fingertips, wrist, and neck to track the physiological signals of the human state during standing, walking, and running. In addition, the integration of Morse code functionality introduces new possibilities for healthcare, particularly for non-verbal patients, enabling non-invasive communication of symptoms and emotions. This technology demonstrates significant potential as a versatile and non-invasive tool for point-of-care (PoC) and biomedical applications when deployed on various parts of the human body.

Terminal Group Effect on Two-Dimensional Self-Assembly of Fluorenone-Based Liquid Crystals at the Solid/Liquid Interface.

Self-assemblies of two fluorenone-based derivatives (FE and FEC) consisting of a central 2,7-diphenyl-9-fluorenone polar moiety but differing in the flexible terminal groups were investigated by scanning tunneling microscopy (STM) at the 1-octanoic acid/HOPG interface under different concentrations and density functional theory calculation (DFT). STM results reveal a concentration-dependent polymorphic self-assembly behavior for FE, but without the presence of co-adsorbed solvents. As the concentration decreases, the dimer, bracket-like, and ribbon-like self-assembled structures were observed. On the contrary, FEC molecules assemble into only a type of oval-shaped morphology by the intermolecular N···H-O hydrogen bonds with the solvent molecules. Combined with DFT calculations, it can be deduced that the intermolecular van der Waals forces, dipole-dipole interactions, and hydrogen bonding are the main driving forces to stabilize the molecular packing of fluorenone-based polycatenars with strong polarity. Our work is of significance at the molecular level to further clarify the intermolecular interactions and conformational effects on the formation of molecular packing structures with liquid crystal property.

Enhancing the single-molecule magnetic performance of β-diketonate Dy(III) complexes by modulating the coordination microenvironment and magnetic interaction: from a mononuclear to a dinuclear structure.

Based on a β-diketonate ligand, a mononuclear Dy(III) complex, [Dy(dmpd)3(bpy)] (1) (dmpd = 4,4-dimethyl-1-phenylpentane-1,3-dione, bpy = 2,2'-dipyridyl), of [DyN2O6] type has been synthesized with a capping nitrogen-containing coligand. Then, a dual capping coligand 2,2'-bipyrimidine (bmp) is introduced to be a bridge to link two β-diketonate-Dy(III) motifs, leading to a new dinuclear Dy(III) complex, [Dy2(dmpd)6(bmp)] (2). Dy(III) centers in both complexes feature an N2O6 octacoordinated environment with an approximate square-antiprism geometry (D4d). Without a dc field, the SMM behaviour is absent in complex 1, but can be clearly observed in dinuclear 2 with a Ueff of 87.29 K. The significantly improved magnetism arising in 2 is mainly due to the modulation of the coordination environment around the Dy(III) ions and the superexchange magnetic interactions inside the dinuclear units, thus allowing for the effective inhibition of the quantum tunneling of magnetization at low temperatures and promotion of the uniaxial magnetic anisotropy. For 1, a diamagnetic Y(III) analogue [Y(dmpd)3(bpy)] (3) and diluted sample 1@Y were constructed to further perform the dilution experiment, coupled with theoretical calculations further supporting that the synergetic contributions of intermolecular dipole-dipole interactions, intramolecular coupling and uniaxial magnetic anisotropy cause the enhancement of dynamic magnetic relaxation.

Efficient artificial light-harvesting systems based on organic small microcrystals in aqueous suspension

Four efficient artificial light-harvesting systems have been developed in the present work. They assemble sodium dodecyl sulphate (SDS) with organic small molecule chromophores to synthesize microcrystals to mimic chlorophyll. In microcrystals, the chromophores are ordered through intermolecular dipole-dipole interactions, which results in efficient energy transfer. In the D-2/A-2 light-harvesting system, the donor concentrates excitation energy from 500 chromophores into a single acceptor with a relative high energy transfer efficiency (86%) and an antenna efficiency (33). The microcrystals exhibit high energy harvesting performance and act as an ideal framework for artificial light-harvesting systems.

Cavity Born-Oppenheimer Hartree-Fock Ansatz: Light-Matter Properties of Strongly Coupled Molecular Ensembles.

Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, the current understanding of the interplay between molecules and confined light modes is incomplete. Accurate theoretical models that take into account intermolecular interactions to describe ensembles are therefore essential to understand the mechanisms governing polaritonic chemistry. We present an ab initio Hartree-Fock ansatz in the framework of the cavity Born-Oppenheimer approximation and study molecules strongly interacting with an optical cavity. This ansatz provides a nonperturbative, self-consistent description of strongly coupled molecular ensembles, taking into account the cavity-mediated dipole self-energy contributions. To demonstrate the capability of the cavity Born-Oppenheimer Hartree-Fock ansatz, we study the collective effects in ensembles of strongly coupled diatomic hydrogen fluoride molecules. Our results highlight the importance of the cavity-mediated intermolecular dipole-dipole interactions, which lead to energetic changes of individual molecules in the coupled ensemble.

Novel Fluorinated Biphenyl Compounds Synthesized via Pd(0)-Catalyzed Reactions: Experimental and Computational Studies.

Five new difluorinated biphenyl compounds, 4'-(tert-butyl)-3,4-difluoro-1,1'-biphenyl (TBDFBP), 1-(3',4'-difluoro-[1,1'-biphenyl]-4-yl)ethanone (DFBPE), 3',4'-difluoro-2,5-dimethoxy-1,1'-biphenyl (DFDMBP), 3,4-difluoro-3'-nitro-1,1'-biphenyl (DFNBP), and (3',4'-difluoro-[1,1'-biphenyl]-3-yl)(methyl)sulfane (DFBPMS), have been successfully synthesized by the well-known Suzuki-Miyaura coupling with excellent yields averaging 78%. UV-visible, Fourier transform infrared ,and 13C NMR and 1H NMR spectroscopies along with single-crystal X-ray diffraction (SC-XRD) analysis (for TBDFBP and DFBPE) were used for the structure elucidation of the synthesized compounds. The SC-XRD results demonstrated the crystal systems of the studied compounds, TBDFBP and DFBPE, to be monoclinic, and their space groups were found to be P21/c. Also, a detailed density functional theory study was performed. The calculated structures for TBDFBP and DFBPE were found to agree quite well with the experimental results. The natural bonding orbital charge analysis suggested that molecules of these compounds should interact quite noticeably with each other in the solid phase and with polar solvent molecules. Molecular electrostatic potential analysis suggests that accumulation of positive and negative potential implies possibility of quite significant dipole-dipole intermolecular interactions in crystals of these compounds, as well as quite strong interactions with polar solvent molecules. The global reactivity parameters analysis suggests all compounds to be quite stable in redox reactions, with the compound DFNBP being relatively more reactive and the compounds TBDFBP and DFDMBP being relatively more stable.

Structural Disorder as the Origin of Optical Properties and Spectral Dynamics in Squaraine Nano-Aggregates.

In contrast to regular J- and H-aggregates, thin film squaraine aggregates usually have broad absorption spectra containing both J-and H-like features, which are favorable for organic photovoltaics. Despite being successfully applied in organic photovoltaics for years, a clear interpretation of these optical properties by relating them to specific excited states and an underlying aggregate structure has not been made. In this work, by static and transient absorption spectroscopy on aggregated n-butyl anilino squaraines, we provide evidence that both the red- and blue-shifted peaks can be explained by assuming an ensemble of aggregates with intermolecular dipole-dipole resonance interactions and structural disorder deriving from the four different nearest neighbor alignments─in sharp contrast to previous association of the peaks with intermolecular charge-transfer interactions. In our model, the next-nearest neighbor dipole-dipole interactions may be negative or positive, which leads to the occurrence of J- and H-like features in the absorption spectrum. Upon femtosecond pulse excitation of the aggregated sample, a transient absorption spectrum deviating from the absorbance spectrum emerges. The deviation finds its origin in the excitation of two-exciton states by the probe pulse. The lifetime of the exciton is confirmed by the band integral dynamics, featuring a single-exponential decay with a lifetime of 205 ps. Our results disclose the aggregated structure and the origin of red- and blue-shifted peaks and explain the absence of photoluminescence in squaraine thin films. Our findings underline the important role of structural disorder of molecular aggregates for photovoltaic applications.

Parent B2 N2 -Perylenes with Different BN Orientations.

Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of BN-PAHs with specific BN positions and orientations. Here, three new parent B2 N2 -perylenes with different BN orientations are synthesized with BN-naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties. The intermolecular dipole-dipole interaction shortens the π-π stacking distance. The crystal structure, (anti)aromaticity, and photophysical properties vary with the change of BN orientation. The revealed BN doping effects may provide a guideline for the synthesis of BN-PAHs with specific stacking structures, and the synthetic strategy employed here can be extended toward the synthesis of larger BN-embedded PAHs with adjustable BN patterns.

Dynamics in the plastic crystalline phase of cyanocyclohexane and isocyanocyclohexane probed by 1H field cycling NMR relaxometry.

Proton Field-Cycling (FC) nuclear magnetic resonance (NMR) relaxometry is applied over a wide frequency and temperature range to get insight into the dynamic processes occurring in the plastically crystalline phase of the two isomers cyanocyclohexane (CNCH) and isocyanocyclohexane. The spin-lattice relaxation rate, R1(ω), is measured in the 0.01-30MHz frequency range and transformed into the susceptibility representation χNMR ″ω=ωR1ω. Three relaxation processes are identified, namely, a main (α-) relaxation, a fast secondary (β-) relaxation, and a slow relaxation; they are very similar for the two isomers. Exploiting frequency-temperature superposition, master curves of χNMR ″ωτ are constructed and analyzed for different processes. The α-relaxation displays a pronounced non-Lorentzian susceptibility with a temperature independent width parameter, and the correlation times display a non-Arrhenius temperature dependence-features indicating cooperative dynamics of the overall reorientation of the molecules. The β-relaxation shows high similarity with secondary relaxations in structural glasses. The extracted correlation times well agree with those reported by other techniques. A direct comparison of FC NMR and dielectric master curves for CNCH yields pronounced difference regarding the non-Lorentzian spectral shape as well as the relative relaxation strength of α- and β-relaxation. The correlation times of the slow relaxation follow an Arrhenius temperature dependence with a comparatively high activation energy. As the α-process involves liquid-like isotropic molecular reorientation, the slow process has to be attributed to vacancy diffusion, which modulates intermolecular dipole-dipole interactions, possibly accompanied by chair-chair interconversion of the cyclohexane ring. However, the low frequency relaxation features characteristic of vacancy diffusion cannot be detected due to experimental limitations.

Unraveling exciton processes in Ir(ppy)3:CBP OLED films upon photoexcitation.

Emissive layers in phosphorescent organic light-emitting diodes commonly make use of guest-host blends such as Ir(ppy)3:CBP to achieve high external quantum efficiencies. However, while the Ir(ppy)3:CBP blend has been studied experimentally, crucial questions remain regarding how exciton diffusion is dependent on the distribution of the guest in the host, which can currently only be addressed at the atomic level via computational modeling. In this work, kinetic Monte Carlo simulations are utilized to gain insight into exciton diffusion in Ir(ppy)3:CBP blend films. The effects of both guest concentration and exciton density on various system properties are analyzed, including the probability of singlet excitons being converted to triplets, and the probability of those triplets decaying radiatively. Significantly, these simulations suggest that triplet diffusion occurs almost exclusively via guest-guest Dexter transfer and that concentration quenching of triplets induced by guest-guest intermolecular dipole-dipole interactions has a negligible effect at high exciton densities due to the prevalence of triplet-triplet annihilation. Furthermore, results for vacuum deposited morphologies derived from molecular dynamics simulations are compared to the results obtained using a simple cubic lattice approximation with randomly distributed guest molecules. We show that while differences in host-based processes such as singlet diffusion are observed, overall, the results on the fate of the excitons are in good agreement for the two morphology types, particularly for guest-based processes at low guest concentrations where guest clustering is limited.

Switching resonance character within merocyanine stacks and its impact on excited-state dynamics

Summary In this study, the optical properties and excited-state dynamics of the unique self-assembled donor-acceptor (DA) merocyanine dye stacks from dimer up to octamer, prepared via dipole-dipole interactions, are reported in terms of coherent exciton dynamics and formation of an excimer-like state. Our findings are based on the steady-state absorption/emission, time-resolved fluorescence, and transient absorption (anisotropy) measurements, including wavepacket analysis and quantum mechanical calculations. Coherent exciton of torsional motions-restricted dye stacks rapidly localizes into the weakly emissive excimer-like state, by shortening the inter-moiety distance and changing the bond-length alternation pattern. The inner merocyanine moiety, having two neighboring units, has a reversed resonance character (non-polar (N) Z) in the ground state. This difference has led to two conclusions: (1) tetramers and octamers exhibit different features of excimer-like state than the dimer, and (2) octamers exhibit slower localization dynamics due to the enhanced homogeneity (six inner-moieties) compared with tetramers (two inner moieties).

Ultralow-Molecular-Weight Stimuli-Responsive and Multifunctional Supramolecular Gels Based on Monomers and Trimers of Hydrazides.

The simpler, the better. A series of simple, neutral and ultralow-molecular-weight (MW: 140-200) hydrazide-derived supramolecular gelators have been designed and synthesized in two straightforward steps. For non-conjugated cyclohexane-derived hydrazides, their monomers can self-assemble to form gels through intermolecular hydrogen bonds and dipole-dipole interactions. Significantly, conjugated phthalhydrazide can self-aggregate into planar and circular trimers through intermolecular hydrogen bonds and then self-assemble to form gels through intermolecular π-π stacking interactions. It is interesting that these simple gelators exhibit unusual properties, such as self-healing, multi-response fluorescence, and visual and selective recognition of chiral (R)/(S)-1,1'-binaphthalene-2,2'-diamine and S2- through much different times of gel re-formation and blue-green color change, respectively. These results underline the importance of supramolecular gels and extend the scope of supramolecular gelators.

Dipole-Phonon Quantum Logic with Trapped Polar Molecular Ions.

The interaction between the electric dipole moment of a trapped molecular ion and the phonon modes of the confined Coulomb crystal couples the orientation of the molecule to its motion. We consider the practical feasibility of harnessing this interaction to initialize, process, and read out quantum information encoded in molecular ion qubits without ever optically illuminating the molecules. We present two schemes wherein a molecular ion can be entangled with a cotrapped atomic ion qubit, providing, among other things, a means for molecular state preparation and measurement. We also show that virtual phonon exchange can significantly boost the range of the intermolecular dipole-dipole interaction, allowing strong coupling between widely separated molecular ion qubits.

Thermally Induced Chiral Aggregation of Dihydrobenzopyrenone on Au(111).

The realization of chiral supramolecular architectures on solid surfaces has triggered much interest due to its potential enantiospecific applications. An in-depth study of chiral aggregation on surfaces is significant for developing functional chiral surfaces. Herein, we report thermally induced chiral aggregation of dihydrobenzopyrenone on Au(111). By high-resolution low-temperature scanning tunneling microscopy, a racemate monolayer consisting of levorotatory and dextrorotatory dihydrobenzopyrenones was found to aggregate into conglomerate domains after moderate annealing treatment. Combined with first-principles calculations, we suggest that the intermolecular dipole-dipole interaction plays an important role in chiral aggregation, which takes place via molecular in-plane diffusion rather than molecular out-of-plane flipping. This work unveils one underlying mechanism of thermally induced chiral aggregation, thus enabling potential applications such as fabricating supramolecular architectures for functional chiral surfaces.

Cross-linked polydimethylsiloxane colloid as novel contrast agent for gastrointestinal magnetic resonance imaging: Transient nuclear Overhauser effect within the interface.

With good contrast in T1 and T2 weighted imaging as well as low toxicity in 3- (4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay, this work proposes the cross-linked polydimethylsiloxane colloids as a novel non-ionic contrast agent for gastrointestinal magnetic resonance imaging. The experiments of nuclear magnetic resonance spectra and relaxation show that within the interface of the colloids, there are nuclear Overhauser effect and transient nuclear Overhauser effect (cross-relaxation). Regarding the longitudinal relaxation experiments of CH2CH2O segments of Tween 80, a two spins system is found and modeled well by the equation which is deduced based on the transient nuclear Overhauser effect proposed by Solomon. The arbitrary constant X is additionally added with the initial conditions (Iz - I0)t=0 = -2XS0 and (Sz - S0)t=0 = -2S0. For the two spins system, D1 and T1 are corresponding to longitudinal relaxation times of the bound water and the CH2CH2O respectively. Concerning the transverse relaxation experiments of the CH2CH2O, they agree with the equation with three exponential decays, defined by three relaxation times, likely corresponding to three mechanisms. These mechanisms possibly are intramolecular and intermolecular dipole-dipole (DD) interactions and scalar coupling. Within the interface, hydrogen bonding causes the positive nuclear Overhauser effect of the CH2CH2O's nuclear magnetic resonance spectra, the transient nuclear Overhauser effect of the CH2CH2O's longitudinal relaxation experiments and the intermolecular dipole-dipole interactions of the CH2CH2O's transverse relaxation experiments.

Superior Energy Dissipation by Ultrathin Semicrystalline Polymer Films Under Supersonic Microprojectile Impacts.

Distinct deformation mechanisms that emerge in nanoscale enable the nanostructured materials to exhibit outstanding specific mechanical properties. Here, we present superior microstructure- and strain-rate-dependent specific penetration energy (up to ∼3.8 MJ kg-1) in semicrystalline poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) thin films subjected to high-velocity (100 m s-1 to 1 km s-1) microprojectile (diameter: 9.2 μm) impacts. The geometric-confinement-induced nanostructural evolutions enable the sub-100 nm thick P(VDF-TrFE) films to achieve high specific penetration energy with high strain delocalization across the broad impact velocity range, superior to both bulk protective materials and previously reported nanomaterials. This high specific penetration energy arises from the substantial stretching of the two-dimensionally oriented highly mobile polymer chains that engage abundant viscoelastic and viscoplastic deformation mechanisms that are further enhanced by the intermolecular dipole-dipole interactions. These key findings provide insights for using nanostructured semicrystalline polymers in the development of lightweight, high-performance soft armors for extreme engineering applications.

Исследование диэлектрических параметров нематических жидких кристаллов в приграничных слоях

This article presents the results of a study of the dielectric properties of thin liquid crystal layer systems. To study the dielectric parameters of nematic liquid crystals in the boundary layers, the frequency and temperature dependences of the real (ε') and imaginary (ε'') parts of the dielectric constant were determined. We studied samples that are in macroscopic layers and samples located in flat capillary layers (d ~ 0.1 μm). In both cases, the measurement is performed by the same method, namely, the method of temporary dielectric spectroscopy. The entire procedure for measuring, recording, accumulating and processing data was carried out automatically. In this case, the results of dielectric measurements could be presented both in the frequency and time domains. For measurements, a plane-parallel measuring cell made of brass and titanium electrodes was used. It should be noted that the surface of a solid body has a strong influence on the phase state of liquids and liquid crystals in the boundary layer. For example, in such a layer, liquid molecules acquire a mesophase ordering. In the case of NLC, the nematic potential increases and, as a result, the temperature of the nematic-isotropic phase transition increases. However, a shift in the bleaching temperature in the NLC mixture studied by us did not appear due to the smallness of the effect. The substance enclosed in the microspace between the surfaces of the mica has a higher dielectric constant than the corresponding bulk sample. Moreover, such a difference is observed both in the isotropic and in the nematic phases. This can be explained as follows. In a thick layer, a dipole-dipole intermolecular interaction takes place, which reduces the effective dipole moment of the molecules.

Core Structure Engineering in Hole-Transport Materials to Achieve Highly Efficient Perovskite Solar Cells.

In this work, the thiadiazolopyridine (PT) unit was introduced as the core structure, with N3 ,N3 ,N6 ,N6 -tetrakis(4-methoxyphenyl)-9-phenyl-9 H-carbazole-3,6-diamine as the peripheral group, to obtain a new compound, JY8, for use as a hole-transport material (HTM) in planar perovskite solar cells (PSCs). Compared with the previously reported JY5 with benzothiadiazole as the core structure, the PT unit with stronger electron-withdrawing ability enhanced the intermolecular dipole-dipole interaction. Moreover, the introduction of the PT unit made the central part in JY8 more planar than its analogue JY5, which is conducive to charge transport. Field-emission (FE)-SEM images suggested a smooth and condense morphology of the JY8 film, which could improve the contact between the perovskite layer and the metal electrode. Space-charge limitation of current results, steady-state, and time-resolved photoluminescence decay curves indicated that JY8 as HTM facilitated hole extraction and hole transport. Consequently, planar PSCs fabricated with JY8 as the HTM exhibited a decent efficiency of 19.14 % with a high fill factor of 81 %.

Liquid crystalline epoxy resin with improved thermal conductivity by intermolecular dipole–dipole interactions

ABSTRACTTo address tremendous needs for developing efficiently heat dissipating materials with lightweights, a series of liquid crystalline epoxy resins (LCEs) are designed and synthesized as thermally conductive matrix. All prepared LCEs possess epoxies at the molecular side positions and cyanobiphenyl mesogenic end groups. Based on several experimental results such as differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction, it is found that the LCEs exhibited liquid crystalline mesophases. When LCE is cured with a diamine crosslinker, the cured LCE maintains the oriented LC domain formed in the uncured state, ascribing to a presence of dipole–diploe and π–π interactions between cyanobiphenyl mesogenic end groups. Due to the anisotropic molecular orientation, the cured LCE exhibits a high thermal conductivity of 0.46 W m−1 K−1, which is higher than those of commercially available crystalline or amorphous epoxy resins. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 708–715

Effect of substituent position on aggregation-induced emission, customized self-assembly, and amine detection of donor-acceptor isomers: Implication for meat spoilage monitoring

We synthesized a class of positional isomers by attaching electron donor and acceptor units in different sites of a conjugated core. These isomers exhibit both aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) effects, which are proved by adequate spectroscopic analysis. Their structure-property relationships were systematically studied. We found that relocation of the D/A units would have remarkable impact on the intermolecular dipole-dipole interaction, further controlling the shape and color of the self-assembled architectures. With D/A units shifting to different sites, four types of the structures appear sequentially, including quadrate microsheets, microrods, nanofilaments and nanowires. Furthermore, the A unit (benzoic acid moiety) of the AIE isomers is easy to adsorb amines, leading to changes in both emission wavelength and intensity. Then a portable sensor is prepared on solid support based on the self-assembled architecture of HMBA-4, which has been proved to be the most sensitive to amines. It affords fast spectral responses as well as a low detection limit of 186 Pa (vapour pressure). The sensing mechanism was revealed by density functional theory (DFT) calculation, which indicates that the spectral responses stem from the weakened ICT effect. The sensor is able to detect amine vapours generated by meat, and thus succeeds in detecting the spoiled pork samples, offering high potential for meat spoilage monitoring in real-world applications.