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This study aims to assess the role of activated carbon nanoparticles in hydro-degumming non-edible vegetable oils. Bamboo Activated Carbon Nanoparticles (BAC-NPs) is added to oils in degumming process. Characterizations revealed mesoporous structures with specific surface area 673.298 m2/g, positive surface charge, aromatic ring cluster, and increased hydrophilicity. Magnetic moment induced by delocalized electrons in aromatic ring cluster of BAC-NPs works towards paramagnetic negatively charged oxygen around the phosphate head group of phospholipid molecule. It also works towards water molecules, changes water proton spin isomer from para to ortho, decreases intramolecular energy in water, facilitates base-promoted ester hydrolysis reaction. These phenomena, combined with heat energy and centrifugation force, trigger bonds disruption within phospholipid molecule, lead to a higher probability of phosphate head group detachment off the phospholipid molecule. As a result, there is a large reduction in phosphorus concentration (around 95%) and a slight improvement in viscosity and calorific value in treated oils.

Though Olefin-linked covalent organic frameworks (oCOFs) possess excellent π-electron delocalization, the barely reversible olefin linkage brings challenges for oCOFs’ synthesis and functionalization. Here, we synthesize new oCOFs with tertiary amine knots which have twisted configuration and electron-donating nature. Investigation into the structural variation and photoelectric performance shows that the twisted configuration of oCOF-TFPA could favor to the intramolecular charge transfer process and reduce the possibility of aggregation-caused quenching. Photoelectrical measurements and electric band structure calculation both verify the superiority of this oCOFs’ structure in photoelectric sensing.

We report the first disubstituted hetero-ten-vertex closo cluster [(CrGe9)Cr2(CO)13]4− with three adjacent Cr(CO)n units adopting both η5 and η1 coordination modes, which was synthesized through the reaction of “KGe1.67” with (MeCN)3Cr(CO)3 and Cr(CO)6 in ethylenediamine (en) solution. In contrast to the η1-Cr atoms forming localized two-center two-elelctron (2c-2e) Cr-Ge bonds, the hetero atom η5-Cr exhibits versatile bonding mechanisms including three 5c-2e and five 8c-2e delocalized bonds which account for Huckel aromaticity. Intricate multi-center bonding patterns delineate the multiple local σ-aromatic characters of the title cluster displaying explicit spherical aromaticity.

Defect sites on oxide semiconductors play a crucial role in promoting photocatalytiperformance and modulating the bandgap structure of photocatalysts. However, the role of interfacial coordinatively unsaturated defect sites between metal and oxide in photocatalysis is still under debate. So, we designed an experiment to probe the role of interfacial coordinatively unsaturated defect sites. In this work, a series of Ti/TiO2 photocatalysts with varying concentrations of interfacial Ti3+ sites were prepared through an epitaxial growth method under hydrothermal conditions. Through experimental and computational investigations, the roles of interfacial defect sites were discussed in detail. On the one hand, the interfacial coordinatively unsaturated Ti3+ sites could act as visible-light-responsive sites in photocatalytic reactions due to the overlap and hybridization of multiple electronic orbitals. On the other hand, the Ti/TiO2 interface exhibited a certain degree of metallic character near the Fermi level because of the partial delocalization and redistribution of electrons, facilitating the charge migration and separation across the metal-oxide interface. Consequently, the obtained Ti/TiO2 catalysts showed notably enhanced charge transfer efficiency and visible light photocatalytic activity compared to their pristine counterparts. This work may provide a new perspective to interfacial defect engineering in classic metal/oxide heterojunction photocatalysts and figure a more precise direction to synthesize higher effective photocatalysts for environmental governance.

The phase transition of Nd2In and Pr2In has been studied and found to be between the first-order and second-order nature. Hardly any hysteresis nor obvious cell volume changes are presented. Concurrently the field-triggered metamagnetism is demonstrated with lambda-like peak on specific heat curve. For the field change of 7 T, giant magnetic entropy changes of 13.2 J kg−1 K−1 and 19.5 J kg−1 K−1 and adiabatic temperature changes of 6.5 K and 7.4 K have been achieved in Nd2In and Pr2In alloys respectively, which is partially contributed by strong magnetoelastic coupling represented by high saturation magnetostriction of ∼450 ppm. Such unique feature is proposed to be originated from the delocalized 5d electrons, as evidenced by the negative magnetoresistance caused by the phase transition.

Theoretical and experimental investigations on the molecular structure of 2-amino-5-chloro-3-nitropyridine (2A5Cl3NP) are presented. The molecular equilibrium geometry of the title molecule is fully optimized. Quantum chemical calculations of the HOMO-LUMO energies, energy gap (ΔE), electron negativity (χ), and chemical potential (μ), global hardness (ƞ), and global softness (S) are calculated for the title molecule. The title compound has a low softness value (0.2770) and the calculated value of electrophilicity index (7.7250) describes the biological activity. The stability and charge delocalization of the title molecule are studied by Natural Bond Orbital Analysis (NBO), Non-Linear Optical (NLO) behaviour in terms of first order hyperpolarizability, dipole moment, anisotropy of polarizability are accounted. The computed values of dipole moment (μ) for 2A5Cl3NP molecule is 3.0173 Debye, polarizability (α) is 1.6017 × 10–23esu, hyperpolarizability (β) is 5.08173 × 10–30esu. The high β value and non-zero value of μ indicate that the title compound might be a good candidate for NLO material. The strength of the interaction between electron donors and electron acceptors is measured by the magnitude of energy of hyper conjugative interactions E (2). The second-order Fock matrix is calculated to study the donor–acceptor interactions in NBO analysis.

Developing modified carbon nitride (CN) with a multi-bonding mode remains a pivotal challenge for high-efficiency photocatalytic hydrogen evolution (PHE). Here, we fabricate a PYM-CN photocatalyst by doping pyrimethamine (PYM) in CN by a facile one-step polymerization method, which shows remarkably enhanced PHE performance in contrast with pure CN, because PYM as a cross-linked bridge in CN frameworks via a multi-bonding mode broadens the visible-light absorption range and expedites the transfer and separation of intramolecular photoproduced electron–hole pairs by π-conjugated channel expansion. Density functional theory (DFT) calculations reveal that this significant improvement is attributed to the orbital hybridization and delocalization effects resulting from the unique intramolecular cross-linked structure in PYM-CN. As expected, the PHE rate over the optimal PYM100-CN sample is about 11.6 times that of pure CN and the AQE value reaches up to 17.7% at 420 nm. Hence, this work provides a representative paradigm to exploit intramolecular cross-linked polymer photocatalysts with a multi-bonding mode for the high-efficiency PHE reaction or other photocatalytic application fields.

Understanding how Frenkel excitons efficiently split to form free-charges in low-dielectric constant organic semiconductors has proven challenging, with many different models proposed in recent years to explain this phenomenon. Here, we present evidence that a simple model invoking a modest amount of charge delocalization, a sum over the available microstates, and the Marcus rate constant for electron transfer can explain many seemingly contradictory phenomena reported in the literature. We use an electron-accepting fullerene host matrix dilutely sensitized with a series of electron donor molecules to test this hypothesis. The donor series enables us to tune the driving force for photoinduced electron transfer over a range of 0.7 eV, mapping out normal, optimal, and inverted regimes for free-charge generation efficiency, as measured by time-resolved microwave conductivity. However, the photoluminescence of the donor is rapidly quenched as the driving force increases, with no evidence for inverted behavior, nor the linear relationship between photoluminescence quenching and charge-generation efficiency one would expect in the absence of additional competing loss pathways. This behavior is self-consistently explained by competitive formation of bound charge-transfer states and long-range or delocalized free-charge states, where both rate constants are described by the Marcus rate equation. Moreover, the model predicts a suppression of the inverted regime for high-concentration blends and efficient ultrafast free-charge generation, providing a mechanistic explanation for why Marcus-inverted-behavior is rarely observed in device studies.

Polymethine fluorophores have facilitated the advance of biological and material sciences, due to their advantageous photophysical properties. However, the need to maintain a monomeric state can severely limit the utility and processability of dyes. High concentrations of fluorophore can lead to aggregation and negate the beneficial photophysical properties of monomers. Another concern is “crossing the cyanine limit” in which delocalization within the polymethine scaffold is broken, producing the presence of an asymmetric state diminishing its photophysical behavior. Herein, we attempt to overcome these limitations by exploring anion exchange on a cationic flavylium heptamethine scaffold. By increasing the size and hydrophobicity of the anion, we can effectively tune the degree of ion pairing within the polymethine dye. Interestingly, we found that the effect of ion pairing on photophysical properties was subtle for the flavylium heptamethine scaffold in comparison to the more commonly used indolenine cyanine dye. Utilizing larger weakly coordinating anions enabled solubility of the flavylium heptamethine fluorophore in nonpolar solvents, which could otherwise not be achieved. Even with more subtle effects than classic cyanine dyes, anion exchange on flavylium polymethine dyes holds potential for further manipulation of the properties of these low energy dyes.

[Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)] (1Cl) is the product of the hydrogen peroxide oxidation of the PtII anticancer agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] (1). Insights into electron delocalization and bonding in [Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]+ (1Cl+) obtained by electrochemical oxidation of 1Cl have been gained by spectroscopic and computational studies. The 1Cl/1Cl+ process is chemically and electrochemically reversible on the short time scale of voltammetry in dichloromethane (0.10 M [Bu4N][PF6]). Substantial stability is retained on longer time scales enabling a high yield of 1Cl+ to be generated by bulk electrolysis. In situ IR and visible spectroelectrochemical studies on the oxidation of 1Cl to 1Cl+ and the reduction of 1Cl+ back to 1Cl confirm the long-term chemical reversibility. DFT calculations indicate only a minor contribution to the electron density (13%) resides on the Pt metal center in 1Cl+, indicating that the 1Cl/1Cl+ oxidation process is extensively ligand-based. Published X-ray crystallographic data show that 1Cl is present in only one structural form, while NMR data on the dissolved crystals revealed the presence of two closely related structural forms in an almost equimolar ratio. Solution-phase EPR spectra of 1Cl+ are consistent with two closely related structural forms in a ratio of about 90:10. The average g value for the frozen solution spectra (2.0567 for the major species) is significantly greater than the 2.0023 expected for a free radical. Crystal field analysis of the EPR spectra leads to an estimate of the 5d(xz) character of around 10% in 1Cl+. Analysis of X-ray absorption fine structure derived from 1Cl+ also supports the presence of a delocalized singly occupied metal molecular orbital with a spin density of approximately 17% on Pt. Accordingly, the considerably larger electron density distribution on the ligand framework (diminished PtIII character) is proposed to contribute to the increased stability of 1Cl+ compared to that of 1+.

Skeleton modification on carbon nitride (g-C3N4) via organic molecules is a recognized effective strategy to improve photocatalytic performance because it can powerfully improve charge separation in the skeleton plane. Herein, a diazole with a unique conjugated structure is bonded on edge of the g-C3N4 skeleton through a moderate polymerization of urea with 4-aminoantipyrine (4AAP). Meanwhile, the Pt nanoparticles selectively deposit on edge of the g-C3N4-4AAP15 nanosheet. It reveals that the robust limbic inducted and delocalized effects of diazole not only facilitate photogenerated electrons aggregation toward skeleton edge to promote in-plane carrier separation but also effectively stabilize and delocalize photogenerated electrons to improve carrier lifetime for propelling the photocatalytic hydrogen evolution (PHE) reaction. Specifically, the PHE rate over optimal g-C3N4-4AAP15 (284.2 μmol h-1) is 10 times that of pure g-C3N4 (27.6 μmol h-1) and the apparent quantum efficiency (AQE) at 420 nm reaches up to 24.2%. Through insights into the functionalized effect of small nitrogenous heterocycles introduced into the skeleton edge of g-C3N4, this work opens a new design thought for exploiting high-efficiency g-C3N4-based photocatalysts for photocatalytic application.

Ultrafast hole transfer from solvent radical cations produced by radiolysis with ∼10 ps, 9 MeV electron pulses to solutes in tetrahydrofuran (THF) was investigated. Because of rapid fragmentation of initially produced THF+•, solute radical cations are not expected and have not previously been reported. When 9,9-dihexyl-2,7-dibromofluorene (Br2F) at 5 to 1000 mM was used, Br2F+• with radiation chemical yields up to G = 2.23/100 eV absorbed was observed. While more than half of this was the result of direct solute ionization, the results highlight the importance of capturing holes from THF+• prior to solvation and fragmentation. The observed data show a time-resolution limited (15 ps) rise in transient absorption of Br2F+•, identical in form to reports of presolvated or dry electron capture in water and a few organic liquids, including THF. The results were thus interpreted with a similar formalism, finding C37 = 1.7 M, the concentration at which 37% of holes escape capture. The yield of solvent hole capture can be accounted for by the formation of solvent holes adjacent to solute molecules reacting faster than they can fragment; however, mechanisms such as delocalized holes or rapid hopping may play a role. Low temperature results find over two times more capture, supporting the speculation that if THF+• was longer lived, the yield of capture in under 15 ps would have been at least 2 times larger at 1 M Br2F, possibly capturing nearly all available holes from the solvent.

We report a density functional non-equilibrium Green's function study of the electronic transport properties of nanoscale networks composed of Au metal clusters interconnected with thiolated molecules (1,4-benzenedithiol and 1,3,5-benzenetrithiol), connected in linear chains and branched (Y-, diamond-shaped) extended networks. Calculated current–voltage characteristics of the metal–molecular networks exhibited nonlinearities and rectification with negative differential resistance (NDR) peaks that became more pronounced with increasing chain length. A significant overlap of the energetically close delocalized molecular orbitals near the Fermi energy was observed, which likely combine and contribute to electron transport. The transmission spectra of the linear chains and branched networks showed an increase in the number and width of transmission peaks near the Fermi energy, as the structures were extended, indicating enhanced transmission. Peak-to-valley current NDR ratios as large as ~ 500 and rectification ratios of ~ 10 (0.25 V) were shown for linear and branched circuit elements, respectively, illustrating how charge transport through molecular-scale devices could be controlled with precision by modifying the structure and geometry of molecule–nanoparticle networks. These results provide a potential foundation and building block components for exploring and tailoring applications of metallic nanoparticle-molecular networks in various configurations for nanoelectronic devices and circuits, including memory, logic and sensing.

An aromatic tricoordinated organo B(III) complex of benzitriphyrin(2.1.1) was synthesized by treating the nonaromatic phlorin analogue of meso-fused benzitriphyrin(2.1.1) with BCl3 in triethylamine/toluene and refluxing for 2 h. The X-ray structure revealed that B(III) was in a trigonal-planar geometry and was coordinated to two nitrogen atoms and one carbon. Insertion of the small B(III) ion into the meso-fused phlorin analogue resulted in transforming the nonaromatic phlorin analogue to an aromatic B(III) benzitriphyrin(2.1.1) complex. Spectral and electrochemical studies supported the aromatic nature of the B(III) complex of benzitriphyrin(2.1.1). Theoretical studies supported the major contribution of the 18π delocalization pathway toward the aromatic nature of the B(III) meso-fused benzitriphyrin(2.1.1) in comparison to the 22π delocalization pathway. The B(III) benzitriphyrin(2.1.1) complex acts as a specific colorimetric and fluorogenic F-/CN- ion sensor.

Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower the excited state energy, allowing for emission well into the near-infrared regime. However, as we show here, it is not only the excited state energy modifications that J-aggregates can provide. A bay-alkylated quaterrylene was synthesized, which was found to form J-aggregates in 1,1,2,2-tetrachloroethane. A combination of superradiance and a decreased nonradiative relaxation rate made the J-aggregate four times more emissive than the monomeric counterpart. A reduced nonradiative relaxation rate is a nonintuitive consequence following the 180 nm (3300 cm–1) red-shift of the J-aggregate in comparison to the monomeric absorption. However, the energy gap law, which is commonly invoked to rationalize increased nonradiative relaxation rates with increasing emission wavelength, also contains a reorganization energy term. The reorganization energy is highly suppressed in J-aggregates due to exciton delocalization, and the framework of the energy gap law could therefore reproduce our experimental observations. J-Aggregates can thus circumvent the common belief that lowering the excited state energies results in large nonradiative relaxation rates and are thus a pathway toward highly emissive organic dyes in the NIR regime.

The different nature of the emissive states of AgI and CuI one- and three-dimensional coordination polymers is here explained by a higher covalent character of the Cu—N bond with respect to the Ag—N one., A QTAIM and IQA investigation on model compounds of two isostructural AgI and CuI coordination polymers (CPs) based on cyclic tri­imidazole (L), i.e. the [MIL] n 1D double-stranded stair chain and the [MClL] n 3D network (M = Cu, Ag), has allowed light to be shed on the different emissive behaviour associated with the two metal ions. According to a previously reported investigation [Malpicci et al. (2021). Inorg. Chem. Front. 8, 1312–1323 ▸], AgI CPs showed both fluorescence and multiple ligand-centred room-temperature phospho­rescences, whereas CuI CPs displayed non-thermally equilibrated halogen and metal-to-ligand charge transfer and two ligand-centred phospho­rescences, the latter observed only by their selective activation. Analysis of both local and integral QTAIM descriptors, including delocalization indices and source function, of the Ag—N and Cu—N bonds reveals a higher covalent and local character for the latter, explaining the greater metal–ligand electronic communication observed for the Cu compounds. Moreover, IQA investigation shows that the Cu—N bond is characterized by higher interaction energy, due to both higher electrostatic and exchange-correlation contributions. Analysis on the M—X (M = Ag, Cu; X = I, Cl) bonds, also present in these structures, highlights a much higher covalent and local character with respect to the M—N bonds.

Tin chalcogenides (SnX, X = S, Se)-based heterostructures (HSs) are promising materials for the construction of low-cost optoelectronic devices. Here, we report the synthesis of a SnSe/CdSe HS using the controlled cation exchange reaction. The (400) plane of SnSe and the (111) plane of CdSe confirm the formation of an interface between SnSe and CdSe. The Type I band alignment is estimated for the SnSe/CdSe HS with a small conduction band offset (CBO) of 0.72 eV through cyclic voltammetry measurements. Transient absorption (TA) studies demonstrate a drastic enhancement of the CdSe biexciton signal that points toward the hot carrier transfer from SnSe to CdSe in a short time scale. The fast growth and recovery of CdSe bleach in the presence of SnSe indicate charge transfer back to SnSe. The observed delocalization of carriers in these two systems is crucial for an optoelectronic device. Our findings provide new insights into the fabrication of cost-effective photovoltaic devices based on SnSe-based heterostructures.

Direct dynamics simulations of chemical reactions typically require the selection of a method for generating the potential energy surfaces and a method for the dynamical propagation of the nuclei on these surfaces. The nuclear-electronic orbital (NEO) framework avoids this Born-Oppenheimer separation by treating specified nuclei on the same level as the electrons with wave function methods or density functional theory (DFT). The NEO approach is particularly applicable to proton, hydride, and proton-coupled electron transfer reactions, where the transferring proton(s) and all electrons are treated quantum mechanically. In this manner, the zero-point energy, density delocalization, and anharmonicity of the transferring protons are inherently and efficiently included in the energies, optimized geometries, and dynamics.This Account describes how various NEO methods can be used for direct dynamics simulations on electron-proton vibronic surfaces. The strengths and limitations of these approaches are discussed, and illustrative examples are presented. The NEO-DFT method can be used to simulate chemical reactions on the ground state vibronic surface, as illustrated by the application to hydride transfer in C4H9+. The NEO multistate DFT (NEO-MSDFT) method is useful for simulating ground state reactions in which the proton density becomes bilobal during the dynamics, a characteristic of hydrogen tunneling, as illustrated by proton transfer in malonaldehyde. The NEO time-dependent DFT (NEO-TDDFT) method produces excited electronic, vibrational, and vibronic surfaces. The application of linear-response NEO-TDDFT to H2 and H3+, as well as the partially and fully deuterated counterparts, shows that this approach produces accurate fundamental vibrational excitation energies when all nuclei and all electrons are treated quantum mechanically. Moreover, when only specified nuclei are treated quantum mechanically, this approach can be used to optimize geometries on excited state vibronic surfaces, as illustrated by photoinduced single and double proton transfer systems, and to conduct adiabatic dynamics on these surfaces. The real-time NEO-TDDFT method provides an alternative approach for simulating nonequilibrium nuclear-electronic dynamics of such systems. These various NEO methods can be combined with nonadiabatic dynamics methods such as Ehrenfest and surface hopping dynamics to include the nonadiabatic effects between the quantum and classical subsystems. The real-time NEO-TDDFT Ehrenfest dynamics simulation of excited state intramolecular proton transfer in o-hydroxybenzaldehyde illustrates the power of this type of combined approach. The field of multicomponent quantum chemistry is in the early stages, and the methods discussed herein provide the foundation for a wide range of promising future directions to be explored. An appealing future direction is the expansion of the real-time NEO-TDDFT method to describe the dynamics of all nuclei and electrons on the same level. Direct dynamics simulations using NEO wave function methods such as equation-of-motion coupled cluster or multiconfigurational approaches are also attractive but computationally expensive options. The further development of NEO direct dynamics methods will enable the simulation of the nuclear-electronic dynamics for a vast array of chemical and biological processes that extend beyond the Born-Oppenheimer approximation.

In polynuclear biological active sites, multiple electrons are needed for turnover, and the distribution of these electrons among the metal sites is affected by the structure of the active site. However, the study of the interplay between structure and redox distribution is difficult not only in biological systems but also in synthetic polynuclear clusters since most redox changes produce only one thermodynamically stable product. Here, the unusual chemistry of a sterically hindered trichromium complex allowed us to probe the relationship between structural and redox isomerism. Two structurally isomeric trichromium imides were isolated: asymmetric terminal imide (tbsL)Cr3(NDipp) and symmetric, μ3-bridging imide (tbsL)Cr3(μ3–NBn) ((tbsL)6− = (1,3,5-C6H9(NC6H4-o-NSitBuMe2)3)6−). Along with the homovalent isocyanide adduct (tbsL)Cr3(CNBn) and the bisimide (tbsL)Cr3(μ3–NPh)(NPh), both imide isomers were examined by multiple-wavelength anomalous diffraction (MAD) to determine the redox load distribution by the free refinement of atomic scattering factors. Despite their compositional similarities, the bridging imide shows uniform oxidation of all three Cr sites while the terminal imide shows oxidation at only two Cr sites. Further oxidation from the bridging imide to the bisimide is only borne at the Cr site bound to the second, terminal imido fragment. Thus, depending on the structural motifs present in each [Cr3] complex, MAD revealed complete localization of oxidation, partial localization, and complete delocalization, all supported by the same hexadentate ligand scaffold., Application of high-resolution Multiwavelength Anomalous Diffraction (MAD) allows the assignment of localized, partly delocalized, and fully delocalized oxidation in a series of trichromium imide isomers.

Ribbon lattices are kind of transition systems in between one and two dimensions, and their study is crucial to understand the origin of different emerging properties. In this work, we study a Lieb ribbon lattice and the localization–delocalization transition occurring due to a reduction of lattice distances (compression) and the corresponding flat band deformation. We observe how above a critical compression ratio the energy spreads out and propagates freely across the lattice, therefore transforming the system from being a kind of insulator into a conductor. We implement an experiment on a photonic platform and show an excellent agreement with the predicted phenomenology. Our findings suggest and prove experimentally the use of compression or mechanical deformation of lattices to switch the transport properties of a given system.

A theoretical study was carried out on the coumarin derivatives substituted at positions 3 and 6 by means of the two quantum methods: DFT and time-dependent density functional theory (TDDFT). The compound 3-fluorophenyl 2-oxo-2H-1-benzopyran-3-carboxylate is specific. The mesomeric donor effect of fluorine creates a strong delocalization of charge generating a twisted structure with a very high dipole moment. This compound show fluorescence at 446 nm with Stokes shift of 90 nm in ethanol. The presence of two transitions of the σ–σ* type in this compound leads to the breakdown of the carbon–oxygen bond and generates the phenolate ion, a fluorescence quenching agent. Whatever the nature and position of the substituent, all the excited states of the 3,6-substituted derivatives have a high value of the dipole moment and HOMO/LUMO electronic transitions of charge transfer nature.

Salts containing the monoprotonated ethylene carbonate species of were obtained by reacting it with the superacidic systems XF/MF5 (X=H, D; M=Sb, As). The salts in terms of [C3H5O3]+[SbF6]−, [C3H5O3]+[AsF6]− and [C3H4DO3]+[AsF6]− were characterized by low‐temperature infrared and Raman spectroscopy. In order to generate the diprotonated species of ethylene carbonate, an excess of Lewis acid was used. However, this only led to the formation of [C3H5O3]+[Sb2F11]−, which was characterized by a single‐crystal X‐ray structure analysis. Quantum chemical calculations on the B3LYP/aug‐cc‐PVTZ level of theory were carried out for the [C3H5O3]+ cation and the results were compared with the experimental data. A Natural Bond Orbital (NBO) analysis revealed sp2 hybridization of each atom belonging to the CO3 moiety, thus containing a remarkably delocalized 6π‐electron system. The delocalization is confirmed by a 13C NMR‐spectroscopic study of [C3H5O3]+[SbF6]−., The protonation of ethylene carbonate succeeded in the superacidic media HF/MF5 (M=Sb, As). Surprisingly, the cation displays a highly 6π‐electron resonance stabilized CO3 moiety.

Even though metallacyclopentadienes (MCPs) are among the most common metallacycles, their electron delocalization (aromaticity) has received far less attention than other metallacycles, such as metallabenzenes. We systematically studied the aromaticity of MCPs with energetic (isomerization stabilization energy), density (delocalization index) and magnetic (current density) aromaticity indices. The indices agree that metallacyclopentadienes are, in general, weakly aromatic at most. The 18e− complexes showed the expected weak aromaticity, and only the d8 molecules are somewhat anti-aromatic. However, the theoretical account of the aromaticity of the 16e− MCPs is more convoluted. We find that the aromatic criteria for a 16e−d4 ruthenacyclopentadiene disagree. The lack of agreement shows that significant electron delocalization is not always related to great stability or to strong diatropic currents.

Graphitic carbon nitride (g-C3N4) with unique physicochemical features has garnered much attention in artificial photosynthesis, yet the photoactivity of pristine g-C3N4 (PCN) is severely restricted because of its rapid charge recombination rate and narrow visible-light absorption. To this end, for the first time, here we reported a rational one-step copolymerization strategy for the fabrication of carbon self-doped g-C3N4 (CCN) by using melamine and chitosan as the starting materials. Experimental results indicated that the bridged N atoms were substituted by C atoms in the g-C3N4 matrix, resulting in the formation of delocalized big π bonds, thereby the obviously increased the electrical conductivity, remarkably extended the visible-light absorption region, and significantly improved the mobility of photoinduced electron-hole pairs. Consequently, the as-engineered CCN with abundant mesopores structure showed a dramatically boosting photocatalytic H2-evolved activity (1224 μmol g−1 h−1), 4.5-folds than PCN powders. Eventually, the resulting CCN exhibited an extremely long-term durable stability after storing in reaction solution for 90 days. Our work will bring about potential application in designing of high-performance g-C3N4 photocatalyst for renewable solar-to-H2 conversion.

Organic small molecules doping in polymer carbon nitride (PCN) skeleton can dramatically improve photocatalytic performance owing to its effective regulation effect on molecular and electronic structure. Here, a new PCN-based photocatalyst is obtained via polymerization of urea with 1-benzyl-3-phenylthiourea (BPT). The doping effect of BPT in PCN skeleton directly adjusts the hybridization states and delocalization of molecular orbitals, so that the visible light harvest ability, adsorption capacity, charge separation efficiency and transfer kinetics are improved significantly. Consequently, the photocatalytic hydrogen evolution reaction (HER) rate reaches to 125.0 μmol h−1 over the optimal PCN-BPT15 photocatalyst, which is as 13.9 times as PCN (9.0 μmol h−1). Noteworthily, a high apparent quantum efficiency (AQE) of 24.2% is achieved at 420 nm for photocatalytic HER. This work enriches the functionalized investigations of PCN-like photocatalysts by insight into regulated effect of organic small molecules in the skeleton for photocatalytic applications.

Electrochemical CO2 reduction (CO2RR) in a product-orientated and energy-efficient manner relies on rational catalyst design guided by mechanistic understandings. In this study, the effect of conducting support on the CO2RR behaviors of semi-conductive metal-organic framework (MOF) — Cu3(HITP)2 are carefully investigated. Compared to the stand-alone MOF, adding Ketjen Black greatly promotes C2H4 production with a stabilized Faradaic efficiency between 60-70% in a wide potential range and prolonged period. Multicrystalline Cu nano-crystallites in the reconstructed MOF are induced and stabilized by the conducting support via current shock and charge delocalization, which is analogous to the mechanism of dendrite prevention through conductive scaffolds in metal ion batteries. Density functional theory calculations elucidate that the contained multi-facets and rich grain boundaries promote C–C coupling while suppressing HER. This study underlines the key role of substrate-catalyst interaction, and the regulation of Cu crystalline states via conditioning the charge transport, in steering the CO2RR pathway., The substrate-catalyst interaction plays a critical role in steering the pathway of electrochemical CO2 reduction. Here the authors show the crystalline states of copper in reconstructed metal-organic frameworks were induced and stabilized by Ketjen Black conducting support, promoting C2H4 production.

Structural DNA nanotechnology is a promising approach to create chromophore networks with modular structures and Hamiltonians to control the material's functions. The functional behaviors of these systems depend on the interactions of the chromophores' vibronic states, as well as interactions with their environment. To optimize their functions, it is necessary to characterize the chromophore network's structural and energetic properties, including the electronic delocalization in some cases. In this study, parameters of interest are deduced in DNA-scaffolded Cyanine 3 and Cyanine 5 dimers. The methods include steady-state optical measurements, physical modeling, and a genetic algorithm approach. The parameters include the chromophore network's vibronic Hamiltonian, molecular positions, transition dipole orientations, and environmentally induced energy broadening. Additionally, the study uses temperature-dependent optical measurements to characterize the spectral broadening further. These combined results reveal the quantum mechanical delocalization, which is important for functions like coherent energy transport and quantum information applications.

Despite the fact that the positron annihilation has been used in biomedical applications, the detailed mechanism of the positron annihilation on biological molecules remains poorly understood so far. In this work, we investigated the positron binding and positron annihilation properties for both global minimum and hydrogen-bonded structures of 20 amino acid molecules using the multicomponent molecular orbital method. By regression analysis, we confirmed that positron affinity can increase with an increase of the permanent dipole moment of the parent amino acids as reported in previous studies, while the annihilation rate linearly increases with respect to the square root of positron affinity. By the one-particle property analyses for probabilities of electron–positron contacts, we found that delocalization characteristics of both electrons and positrons play key roles to enhance the positron annihilation rate arising from both the valence electrons in σ- and π-type molecular orbitals from 2p atomic orbitals but not from the highest occupied molecular orbital electrons, particularly for comparatively weakly bound positronic amino acid systems.

A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.

We theoretically analyze the case of noisy Quantum walks (QWs) by introducing four qubit decoherence models into the coin degree of freedom of linear and cyclic QWs. These models include flipping channels (bit flip, phase flip and bit-phase flip), depolarizing channel, phase damping channel and generalized amplitude damping channel. Explicit expressions for the probability distribution of QWs on a line and on a cyclic path are derived under localized and delocalized initial states. We show that QWs which begin from a delocalized state generate mixture probability distributions, which could give rise to useful algorithmic applications related to data encoding schemes. Specifically, we show how the combination of delocalzed initial states and decoherence can be used for computing the binomial transform of a given set of numbers. However, the sensitivity of QWs to noisy environments may negatively affect various other applications based on QWs.

Polycyclic aromatic hydrocarbons (PAHs) are widely used in organic electronic devices. The electronic, magnetic, and optical properties of PAHs can be tuned by structural modifications to the aromatic backbone to introduce an inherent distortion from planarity, such as bending or twisting. However, it remains difficult to isolate and control the effects of such distortions. Here, we sought to understand how backbone twisting and bending affect the electronic properties of acenes, as models for larger PAHs. We found that, even when highly distorted from planarity (30° per ring), acenes maintain their aromatic character and π orbital delocalization with minor mixing of the σ and π orbitals. In addition, the energy gap between the HOMO and LUMO decreases with increasing twist, while the gap is hardly affected by bending, since the energy of both orbitals increase to a similar extent. For bent acenes in the triplet state, the spin becomes more localized with increasing bend, whereas twisting produces an evenly distributed spin delocalization. These findings can guide the synthesis of PAHs with tailored properties., A computational study performed on nonplanar acenes demonstrates the different effects of bending and twisting on the effect on their electronic properties.

Trinuclear all-metal aromatic clusters are an original class of molecules with a cyclic and planar metal core. Characterized by peculiar metal-metal delocalized bonds, they represent a new frontier in transition-metal catalysis. We report a study on C-C-forming reactions of polyunsaturated substrates catalyzed by trinuclear all-metal aromatic palladium clusters. The synthesis of two new families of tricyclic compounds was obtained with a broad functional group tolerance under mild reaction conditions. A peculiar regio- and diastereoselectivity characterized the method, demonstrating that trinuclear palladium complexes are complementary to their popular mononuclear peers. Furthermore, preliminary studies on the mechanism of these polycyclization reactions revealed unique features of the homogeneous catalytic system.

Six-valence-electron planar pentacoordinate beryllium (ppBe) is explored herein as a global minimum, which is only constructed by s-block metals in BeM5+ (M = Cu, Ag, Au). The bonding in ppBe can be regarded as the excited-stated Be with a 2px12py1 electronic configuration, forming electron sharing with doublet M5+ motifs followed by two sets of Be(p∥) → [M5+] σ donations and one Be(s) ← [M5+] σ back-donation. Thus, the σ aromaticity originating from three delocalized σ orbitals gives rise to the whole stability of the high D5h-symmetry ppBe and strongly enriches s-block planar hypercoordinate bonding.

To investigate the capability of π-π stacking motifs to enable spin-spin coupling, we designed and synthesized three pairs of regio-isomers featuring two radical moieties joined by a [2.2]paracyclophane (CP) unit. By fusing indeno units to CP, two partially stacked fluorene radicals are covalently linked, exhibiting evident antiferromagnetic (AFM) coupling regardless of the orientation of two spins. Remarkably, while possessing high diradical indices of 0.8 and 0.9, the two molecules demonstrate good air stability by virtue of their singlet ground state. Single crystals help unravel the structural basis of their AFM coupling behaviors. When two radical centers are arranged at the pseudometa-positions around CP, the face-to-face stacked phenylene rings intrinsically confer orbital interactions that promote AFM coupling. On the other hand, if two radicals are directed in the pseudopara-orientation, significant orbital overlapping is observed between the radical centers (i.e., C9 of fluorene) and the aromatic carbons laid on the side, rendering AFM coupling between the two spins. In contrast, when two fluorene radicals are tethered to CP via C9 through a single C-C bond, ferromagnetic (FM) coupling is manifested by both diradical isomers featuring pseudometa- and pseudopara-connectivity. With minimal spin distributed on CP and thus limited contribution from π-π stacking, their spin-spin coupling properties are more similar to a pair of nitroxide diradical analogues, in which the two spins are dominantly coupled via through-space interactions. From these results, important conclusions are elucidated such as that although through-space interactions may confer FM coupling, with weakened strength shown by PAH radicals due to their lower polarity, face-to-face stacked π-frameworks tend to induce AFM coupling, because favorable orbital interactions are readily achieved by PAH systems hosting delocalized spins that are capable of adopting varied stacking motifs.

A series of Gd3+ complexes (Gd1-Gd3) with the general formula GdL3(EtOH)2, where L is a β-diketone ligand with polycyclic aromatic hydrocarbon substituents of increasing size (1-3), was studied by combining time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and DFT calculations to rationalize the anomalous spectroscopic behavior of the bulkiest complex (Gd3) through the series. Its faint phosphorescence band is observed only at 80 K and it is strongly red-shifted (∼200 nm) from the intense fluorescence band. Moreover, the TR-EPR spectral analysis found that triplet levels of 3/Gd3 are effectively populated and have smaller |D| values than those of the other compounds. The combined use of zero-field splitting and spin density delocalization calculations, together with spin population analysis, allows us to explain both the large red shift and the low intensity of the phosphorescence band observed for Gd3. The large red shift is determined by the higher delocalization degree of the wavefunction, which implies a larger energy gap between the excited S1 and T1 states. The low intensity of the phosphorescence is due to the presence of C-H groups which favor non-radiative decay. These groups are present in all complexes; nevertheless, they have a relevant spin density only in Gd3. The spin population analysis on NaL models, in which Na+ is coordinated to a deprotonated ligand, mimicking the coordinative environment of the complex, confirms the outcomes on the free ligands.

A stereogenic π-system based on dimer (2) and trimer (3) of [2.2]paracyclophane (PC) and biphenyl was prepared and its structural, photophysical, and chiroptical properties were investigated. X-ray analysis revealed that the quaterphenyl moieties in 2 adopt a double helical structure anchoring [2.2]PC from both sides. Furthermore, 3 forms a isosceles triangle structure with a large chiral cavity. A homodesmotic reaction using DFT calculations revealed that 2 has a larger strain energy than 3 owing to its highly twisted phenylene linkers. Electronic and circular dichroic (CD) spectra were recorded in CH2 Cl2 solution. The spectra of both 2 and 3 are similar, and their longest absorption band accompanying a remarkable Cotton effect is attributed to the transition from HOMO to LUMO, which is delocalized to the quaterphenyl moiety. These compounds exhibit fairly high fluorescence quantum yields (ϕ=0.70-0.83) and moderate dissymmetry factor (|gCPL |=1.6×10-3 ) in circularly polarized luminescence (CPL).

A combined anion photoelectron spectroscopic and quantum chemical investigation was performed to explore the structures and bonding properties of ternary [O, Ta, 2C]- anions. The atomic bonding connectivity of the ternary anion was found to be (O-Ta-C2)- rather than (Ta-O-C2)-. The photoelectron spectrum using 266 nm photons was measured, and the theoretical simulated spectrum was calculated, with good agreement between experimental and theoretical results being found. Computations obtained electronic energies and low-energy structures and enabled chemical bonding analyses. The experimental vertical detachment energies of OTaC2- were measured to be 2.85 ± 0.08 eV. OTaC2- exhibits π aromaticity with two delocalized π electrons and σ antiaromaticity.

Bimetallic sulfides display good electroconductibility and more redox active sites for sodium ion storage, which are expected to realize fast charging/discharging of sodium ion hybrid capacitors (SIHCs) integration. Herein, Sb was introduced into SnS2 on graphene (ATS/GNS) to enhance the kinetics of Na+ storage. The introduction of Sb at Sn site in SnS2 leads to a residual delocalized s electron and forms a half-filled and delocalized intermediate band, which can effectively improve electroconductivity. ATS possesses a high adsorption energy (-3.13 eV) and low diffusion energy barrier (0.26 eV) of Na+ by density functional theory calculations. ATS/GNS with remarkable stability possesses a reversible capacity of 507 mAh g−1 at 1 A g−1 after 3000 cycles. The ATS/GNS//N, S doped porous carbon SIHC delivers high energy/power densities (115 Wh kg−1/351 W kg−1 and 41 Wh kg−1/18750 W kg−1), and an excellent capacity retention of 70% after 10000 cycles at 5 A g−1. This work may present a feasible approach to design high-rate and long-term stability of sodium-based devices.

Density functional theory method at the B3LYP/6-31G level was used to determine the structure of 12mer single-strand guanine oligomers. The length and width of the optimized structure are 38.7 and 18.2 A, respectively, and the observed high-resolution transmission electron microscopy image of the 12mer single-strand guanine sample shows similar oligomer dimensions with the calculated ones. Both HOMO and LUMO are significantly delocalized, and the calculated HOMO-LUMO gap is 3.31 eV. A total of 96 muonium trapping sites at C2, C4, C5, C6, C8, N3, N7, and O6 were investigated. All 12 C8 sites have lower energy than the other 84 sites and are clustered in the energy-muon hyperfine coupling constant scatter plot. The calculated muon hyperfine coupling constant at C8 sites range from 384.6 to 481.1 MHz, and the corresponding estimated ALC-μSR resonance for |ΔM| = 1 range from 1.419 to 1.775 T.

In this work, we synthesized and characterized two quinoidal small molecules based on benzothiophene modified and original isatin terminal units, benzothiophene quinoidal thiophene (BzTQuT) and quinoidal thiophene (QuT), respectively, to investigate the effect of introducing a fused ring into the termini of quinoidal molecules. Extending the terminal unit of the quinoidal molecule affected the extension of π-electron delocalization and decreased the bond length alternation, which led to the downshifting of the collective Raman band and dramatically lowering the band gap. Organic field-effect transistor (OFET) devices in neat BzTQuT films showed p-type transport behavior with low hole mobility, which was ascribed to the unsuitable film morphology for charge transport. By blending with an amorphous insulating polymer, polystyrene, and poly(2-vinylnaphthalene), an OFET based on a BzTQuT film annealed at 150 °C exhibited improved mobility up to 0.09 cm2 V–1 s–1. This work successfully demonstrated that the extension of terminal groups into the quinoidal structure should be an effective strategy for constructing narrow band gap and high charge transporting organic semiconductors.

Valence band spectra of a polycrystalline Pt3Co alloy were measured with photon energies near Co L 3 absorption edge. On the absorption edge, Co L 3 M 4 , 5 M 4 , 5 Auger signals are superimposed on the valence band spectra. Prior to the absorption maximum, the Auger signals display constant binding energy corresponding to radiationless Raman Auger process. After the absorption maximum, normal Auger process occurs, showing characteristics of constant kinetic energy. The transition of Auger process in Pt3Co is carefully discussed, which is deviating to that in Co metal and other 3d transition metals. Our analysis of resonant Auger spectra confirmed the strong delocalization of Co 3d band in Pt3Co alloy.

The failure of many density functional approximations can be traced to their behavior under fractional (spin)population redistributions in the asymptotic limit toward infinite bonding distances, which should obey the flat-plane conditions. However, such errors can only be characterized sufficiently in terms of those redistributions if exact energies are available for many possible (spin)population redistributions at different bonding distances. In this study, we propose to model such redistributions by imposing (spin)populations on atomic domains by constraining full configuration interaction wave functions. The resulting N-representable descriptions of small hydrogen chains at different bonding distances allow us to computationally illustrate the effects of the flat-plane conditions in the limit to infinite bond distances, leading to more chemical insight into those flat-plane conditions. As the proposed methodology is able to capture the effects of the flat plane conditions, it could be used to generate the reference data that is required to measure the extent to which approximate methods violate the requirements of the exact functional, leading to a quantification of the delocalization and static correlation error of such methods.

The X chromosome inactivation is an essential mechanism in mammals' development, that despite having been investigated for 60 years, many questions about its choice process have yet to be fully answered. Therefore, a theoretical model was proposed here for the first time in an attempt to explain this puzzling phenomenon through a quantum mechanical approach. Based on previous data, this work theoretically demonstrates how a shared delocalized proton at a key base pair position could explain the random, instantaneous, and mutually exclusive nature of the choice process in X chromosome inactivation. The main purpose of this work is to contribute to a comprehensive understanding of the X inactivation mechanism with a model proposal that can complement the existent ones, along with introducing a quantum mechanical approach that could be applied to other cell differentiation mechanisms.

Inspired by the recent observation of $\chi_{c0}(3930)$, $X(4685)$ and $X(4630)$ by the LHCb Collaboration and some exotic resonances such as $X(4350)$, $X(4500)$, etc. by several experiment collaborations, the $cs\bar{c}\bar{s}$ tetraquark systems with $IJ^{P}=00^+$, $01^+$ and $02^+$ are systematically investigated in the framework of the quark delocalization color screening model(QDCSM). Two structures, the meson-meson and diquark-antidiquark structures, as well as the channel-coupling of all channels of these two configurations are considered in this work. The numerical results indicate that the molecular bound state $\bar{D}_{s}D_{s}$ with $IJ^{P}=00^+$ can be supposed to explain the $\chi_{c0}(3930)$. Besides, by using the stabilization method, several resonant states are obtained. There are four $IJ^{P}=00^{+}$ states around the resonance mass 4035 MeV, 4385 MeV, 4524 MeV, and 4632 MeV, respectively; one $IJ^{P}=01^{+}$ state around the resonance mass 4327 MeV; and two $IJ^{P}=02^{+}$ states around the resonance mass 4419 MeV and 4526 MeV, respectively. All of them are compact tetraquarks. Among these states, $X(4350)$, $X(4500)$ and $X(4700)$ can be explained as the compact tetraquark state with $IJ^{P}=00^{+}$, and the $X(4274)$ is possible to be a candidate of the compact tetraquark state with $IJ^{P}=01^{+}$. More experimental tests are expected to check the existence of all these possible resonance states., Comment: 10 pages, 3 figures