Anchoring Ni(OH)2-CeOx Heterostructure on FeOOH-Modified Nickel-Mesh for Efficient Alkaline Water-Splitting Performance with Improved Stability under Quasi-Industrial Conditions.

Developing low-cost and industrially viable electrode materials for efficient water-splitting performance and constructing intrinsically active materials with abundant active sites is still challenging. In this study, a self-supported porous network Ni(OH)2-CeOx heterostructure layer on a FeOOH-modified Ni-mesh (NiCe/Fe@NM) electrode is successfully prepared by a facile, scalable two-electrode electrodeposition strategy for overall alkaline water splitting. The optimized NiCe0.05/Fe@NM catalyst reaches a current density of 100 mA cm-2 at an overpotential of 163 and 262 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0 m KOH with excellent stability. Additionally, NiCe0.05/Fe@NM demonstrates exceptional HER performance in alkaline seawater, requiring only 148 mV overpotential at 100 mA cm-2. Under real water splitting conditions, NiCe0.05/Fe@NM requires only 1.701 V to achieve 100 mA cm-2 with robust stability over 1000 h in an alkaline medium. The remarkable water-splitting performance and stability of the NiCe0.05/Fe@NM catalyst result from a synergistic combination of factors, including well-optimized surface and electronic structures facilitated by an optimal Ce ratio, rapid reaction kinetics, a superhydrophilic/superaerophobic interface, and enhanced intrinsic catalytic activity. This study presents a simple two-electrode electrodeposition method for the scalable production of self-supported electrocatalysts, paving the way for their practical application in industrial water-splitting processes.

One Stone, Three-Birds Approach: Ultra-active Ru/N, S-MoO2/CNTs Electrocatalyst for Overall Water Splitting in Wide Electrode Applications (NF, GC, and CC).

The construction of exceptionally multifunctional electrocatalysts is essential for various applications, but it poses significant challenges. A novel electrocatalyst, denoted as Ru/N, S-MoO2/CNTs, was successfully synthesized using a combination of mechano-grinding and hydrothermal/calcination techniques. The Ru/N, S-MoO2/CNTs demonstrates ultrasmall overpotentials of 12 and 163 mV in NF, 51 and 167 mV in GCE, and 54 and 173 mV in CC for HER and OER, respectively, at a current density of 10 mA/cm2 in alkaline medium. To accomplish electrocatalytic OWS, a current density of 10 mA/cm2 can be obtained by using a cell voltage of 1.446 V. Theoretical studies demonstrated that the inclusion of Ru, N, and S triggers a change in the composition of MoO2; produces oxygen vacancies; and forms Ru, N, and S-oxygen-Mo catalytic centers. The combination of Ru, N, and S nanoclusters; Ru, N, and S-oxygen-Mo catalytic centers; and OVs-enriched MoO2 would position it among the top electrocatalysts.

Synergistically Coupled Ni/CeOx@C Electrocatalysts for the Hydrogen Evolution Reaction: Remarkable Performance to Pt/C at High Current Density.

Incredibly active electrocatalysts comprising earth-abundant materials that operate as effectively as noble metal catalysts are essential for the sustainable generation of hydrogen through water splitting. However, the vast majority of active catalysts are produced via complicated synthetic processes, making scale-up considerably tricky. In this work, a facile strategy is developed to synthesize superhydrophilic Ni/CeOx nanoparticles (NPs) integrated into porous carbon (Ni/CeOx@C) by a simple two-step synthesis strategy as efficient hydrogen evolution reaction (HER) electrocatalysts in 1.0 M KOH. Benefiting from the electron transport induced by the heterogeneous interface between Ni and CeOx NPs and the superhydrophilic structure of the catalyst, the resultant Ni2Ce1@C/500 catalysts exhibit a low overpotential of 26 and 184 mV at a current density of 10 and 300 mA cm-2, respectively, for HER with a small Tafel slope of 62.03 mV dec-1 and robust durability over 300 h, and its overpotential at a high current density is much better than the benchmark commercial Pt/C. Results revealed that the electronic rearrangement between Ni and CeOx integrated into porous carbon could effectively regulate the local conductivity and charge density. In addition, the oxygen vacancies and Ni/CeOx heterointerface promote water adsorption and hydrogen intermediate dissociation into H2 molecules, which ultimately accelerate the HER reaction kinetics. Notably, the electrochemical results demonstrate that structural optimization by regulating synthesis temperature and metal concentration could improve the surface features contributing to high electrical conductivity and increase the number of electrochemically active sites on the Ni/CeOx@C heterointerface, high crystal purity, and better electrical conductivity, resulting in its exceptional electrocatalytic performance toward the HER. These results indicated that the Ni/CeOx@C electrocatalyst has the potential for practical water-splitting applications because of its controlled production strategy and outstanding Pt-like HER performance.

Fluorescence detection of hydrazine in an aqueous environment by a corrole derivative.

Broadly, the industrial applications of hydrazine cause environmental pollution and damage to living organisms because of the high toxicity of hydrazine. Therefore, monitoring hydrazine in the environmental system is of great significance to human health. Here, a new fluorescent probe PC-N2 H4 based on corrole dye was developed for the detection of hydrazine that had excellent specificity, low limit of detection (LOD: 88 nM), and a wide pH range (6-12). Upon addition of hydrazine into the probe solution, the strong red fluorescence was 'turned on' centred at 653 nm with a 127-fold fluorescence intensity enhancement. The detection mechanism was proved using ESI-MS, 1 H NMR, and density functional theoretical calculations. Importantly, the probe was utilized to fabricate a ready-to-use test strip to realize the visual inspection of hydrazine. Furthermore, PC-N2 H4 was successfully applied for practical detection of hydrazine in water samples with satisfactory recoveries ranging from 96.2% to 105.0%, and indicating that the designed PC-N2 H4 is highly promising for hydrazine detection in an aqueous environment. Considering the diverse toxicological functions of hydrazine, PC-N2 H4 was also successfully used to image exogenous hydrazine in HeLa cells and zebrafish.

Iron and chromium co-doped cobalt phosphide porous nanosheets as robust bifunctional electrocatalyst for efficient water splitting.

It is still a huge challenge to develop highly efficient and low-cost non-precious metal-based electrocatalysts for overall water splitting in alkaline electrolytes. Herein, Cr and Fe co-doped CoP porous mesh nanosheets (Mesh-CrFe-CoP NSs) were synthesized through hydrolysis reaction, ion exchange etching and subsequent low-temperature phosphating process. The Mesh-CrFe-CoP NSs provides overpotentials at a current density of 10 mA cm-2under alkaline electrolyte of 103.7 mV and 256.4 mV for HER and OER, respectively. Furthermore, when using Mesh-CrFe-CoP NSs as anode and cathode, the water splitting system could afford a current density of 10 mA cm-2at 1.55 V, which is better than an electrolytic cell composed of 20% Pt/C and RuO2. The excellent electrocatalytic performance of Mesh-CrFe-CoP NSs is attributed to the co-doping and porous nanostructure. Specifically, the Cr and Fe co-doped porous CoP nanosheets electrocatalyst not only provided abundant exposure active sites, accelerated the entry of liquid and the diffusion of gas, but also regulated the electronic environment of active sites, and thus enhanced the electrochemical performance. This work proposes a strategy for the rational design of highly efficient and stable non-precious metal co-doped phosphide electrocatalysts in the of electrochemical water splitting.

Stable and enhanced electrochemical performance based on hierarchical core-shell structure of CoMn2O4@Ni3S2electrode for hybrid supercapacitor.

Herein, accessible and low-cost CoMn2O4@Ni3S2core-shell nanoneedle arrays have been prepared via a two-step approach comprised with hydrothermal-calcination and electrochemical deposition procedures, successfully. In the beginning, CoMn2O4nanoneedle arrays took root on Ni foam to form the core skeleton and subsequently, hierarchical Ni3S2nanosheets uniformly overlaid on the surface of CoMn2O4nanoneedles shaping the shell structure. This CoMn2O4@Ni3S2material was measured directly as supercapacitor electrode and presented high specific capacity of 192.2 mAh g-1with current density of 1 A g-1. Besides, the electrode delivered outstanding cyclical stability as the capacity retention attained 90.2% after charge-discharge measurement at a large current density of 10 A g-1for 10 000 cycles. Furthermore, a hybrid supercapacitor assembled by CoMn2O4@Ni3S2cathode and activated carbon anode represented a high energy density of 51.2 Wh kg-1with the power density of 1030.0 W kg-1. This work shows a facile and inexpensive procedure to design high-performance and strong-stability supercapacitor electrodes.

Nanowire-assembled Co3O4@NiS core-shell hierarchical with enhanced electrochemical performance for asymmetric supercapacitors.

In this study, a three-dimensional (3D) hierarchical Co3O4@NiS core-shell heterostructure supported on nickel foam (NF) has been constructed. This Co3O4@NiS/NF can directly serve as a binder-free electrode for a pseudocapacitor, which could achieve a high specific capacitance of 1395.3 F g-1 at a current density of 1 A g-1 in 6 M KOH electrolyte, and an ideal rate capability of 711 F g-1 at a current density of 10 A g-1. Additionally, the electrode has a high capacitance retention of 89.9% after 5000 cycles. The asymmetric supercapacitor exhibits the maximum energy density of 61.34 W h kg-1 at a power density of 800 W kg-1, as well as an excellent cycling life of 89.3% capacitance retention. The enhanced electrochemical performance can be mainly ascribed to the special 3D core-shell nanowire arrays nanostructure with great conductivity, enlarged surface area, abundant accessible active sites and intrinsic stability. We anticipate that the present Co3O4@NiS/NF could be a promising electrode material for energy storage applications.

Tetrazine chromophore-based metal-organic frameworks with unusual configurations: synthetic, structural, theoretical, fluorescent, and nonlinear optical studies.

Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et4 N)[WS4 Cu3 (CN)2 (4,4'-pytz)0.5 ]}n (1), {[MoS4 Cu4 (CN)2 (4,4'-pytz)2 ]⋅CH2 Cl2 }n (2), and {[WS4 Cu3 (4,4'-pytz)3 ]⋅[N(CN)2 ]}n (3; 4,4'-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (4(4) ⋅6(6) ) topology constructed from T-shaped [WS4 Cu3 ](+) clusters as nodes and single CN(-) /4,4'-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (4(20) ⋅6(8) ) topology, in which the bridging 4,4'-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4 Cu3 ](+) clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted "ACS" topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5 ns pulses at λ=532 nm. The Z-scan experimental results show that the π-delocalizable tetrazine-based 4,4'-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

A coumarin-based fluorescent probe for biological thiols and its application for living cell imaging.

In this work, compound 1 has been rationally designed and synthesized as a new fluorescent probe for biological thiols. Notably, probe 1 has almost no background fluorescence (Φf < 0.0001) in aqueous solutions; however, it exhibited fluorescence turn-on response to thiols with high sensitivity (a 246-fold fluorescence enhancement and a low detection limit of 0.22 µM for Cys). Moreover, probe 1 showed excellent thiol specificity over other biologically relevant species. The kinetic studies indicated that the probe responded to thiols rapidly, and the pseudo-first-order rate constants of probe 1 reaction with Cys, Hcy, and GSH were determined to be 1.85842, 0.67656, and 0.51519 min(-1), respectively. A possible detection mechanism was proposed to involve the Michael addition of the thiol to the α,ß-unsaturated ketone, followed by a cleavage of the hemiketal group, thereby leading to the formation of a fluorescent 7-hydroxyl coumarin derivative. Furthermore, the optical responses of probe 1 to thiols were studied by TD-DFT calculations. Finally, probe 1 has been successfully applied to the detection of biological thiols in human blood serum. And the intracellular imaging applications established that probe 1 can be used to detect different concentrations of intracellular thiols in living cells.

Cooperative enhancement of optical nonlinearities in a porphyrin derivative bearing a pyrimidine chromophore at the periphery.

A novel porphyrin derivative bearing one D-π-A-π-D pyrimidine chromophore at the periphery was designed, prepared, and studied using the Z-scan technique, the results showing that this compound exhibits enhanced nonlinear optical (NLO) absorption, refraction and optical limiting responses. The significant NLO properties can be ascribed to an effective combination of distinct nonlinear mechanisms.

Synthesis and applications of a corrole-based dual-responsive fluorescent probe for separate detection of hydrazine and hydrogen sulfide.

Here, a corrole-based dual-responsive fluorescent probe DPC-DNBS was rationally designed and synthesized for the separate detection of hydrazine (N2H4) and hydrogen sulfide (H2S) with high selectivity and sensitivity. The probe DPC-DNBS is intrinsically none fluorescent due to PET effect, however, addition of increasing amount of N2H4 or H2S to DPC-DNBS turned on an excellent NIR fluorescence centered at 652 nm and thereby provided a colorimetric signaling behavior. The sensing mechanism was verified by HRMS, 1H NMR and the DFT calculations. Common metal ions and anions do not interfere with the interactions of DPC-DNBS with N2H4 or H2S. Furthermore, the presence of N2H4 does not affect the detection of H2S; however, the presence of H2S interferes with the detection of N2H4. Hence, quantitative detection of N2H4 must occur in an H2S-free environment. The probe DPC-DNBS displayed some fascinating merits in separate detection of these two analytes, including large Stokes shift (233 nm), fast response (15 min for N2H4, 30 s for H2S), low detection limit (90 nM for N2H4, 38 nM for H2S), wide pH range (6-12) and outstanding biological compatibility. Significantly, DPC-DNBS was utilized to detect hydrazine in real water, soil and food samples. And its favorable performances for separate detection N2H4 and H2S were successfully demonstrated in HeLa cells and zebrafish, indicating its value of practical application in biology.

Chiral interconversions of Pd and/or Au bis-metalated [32]octaphyrins(1,0,1,0,1,0,1,0) involving Hückel and Möbius macrocyclic topologies: a theoretical prediction.

Several Pd and/or Au bis-metalated [32]octaphyrins(1,0,1,0,1,0,1,0) were theoretically designed with rich conformations of Hückel or Möbius topology. The conformations and hence properties of macrocycles were tuned by twisting the active pyrrolic ring either clockwise (through multistep reactions with several Hückel and Möbius macrocyclic intermediates) or anticlockwise (via a direct Hückel-Hückel chiral interconversion). The encapsulated metal atoms, M(1), M(2) = Pd, Au, give different impacts on these two reaction processes. Facile occurrences of chiral interconversions between two enantiomers of bis-metalated octaphyrins were predicted with the largest activation barrier less than 40 kcal/mol. Some Au-coordinated octaphyrins (M(1) = Au) were demonstrated to be thermodynamically stable with large negative nucleus-independent chemical shift (NICS) values, which are comparable to those of the synthetic Pd-coordinated complexes. The free-base [32]octaphyrins(1,0,1,0,1,0,1,0) display the characteristic absorption spectra with distinct sharp Soret-like bands. After metalation, the Soret-like bands are red-shifted in different degrees along with the appearance of rather weak Q-like band. The heterometal-coordinated complexes (i.e., M(1) ≠ M(2)) show stronger and more splitting absorptions than the homometal-coordinated ones with M(1) = M(2). The hyperpolarizabilities sharply augment with the metalation in Hückel systems due to the destruction of the centrosymmetry and the increase in polarizability by coordinated metal atoms.

Solvent effects on isomerization and spectral properties of photochromic-switching diarythene derivatives in polar and apolar solutions.

The photocyclization behavior and dynamic conformational transition of photochromic switches of diarythene derivatives in solutions are investigated by using the density functional theory (DFT) and molecular dynamics (MD) simulations. Three possible conformations, antiparallel (anti), parallel (para), and twist, for the open-ring isomers of 1,2-bis(2-methylbenzothiophene-3-yl)maleic anhydride are located. Both PCM-B3LYP/6-31G* calculations and MD simulations demonstrate that anti and twist open-ring isomers can interconvert freely in n-hexane and acetonitrile solutions at room temperature. The statistical ratio of twist to anti isomers from MD simulations is 2.09 in n-hexane and 1.07 in CH(3)CN, in qualitative agreement with those (1.18 in n-hexane and 1.05 in CH(3)CN) estimated from Arrhenius analysis of DFT activation energies. The solvent polarity has little influence on the isomerization of open-ring isomers in the ground state. Due to the evident charge transfer upon excitations, the solvent effects on the electronic structures and absorption spectra of low-lying excited states (S(1) and S(2)) are more significant. For such charge-transfer excited states, the long-range corrected functional CAM-B3LYP gives better agreement with the experimental spectra than B3LYP. The solvent polarity and polarization of the charge-transfer excited states are crucial for fabricating the novel functionalized photochromic molecular switches.

Synergistic modulation of inverse spinel Fe3O4 by doping with chromium and nitrogen for efficient electrocatalytic water splitting.

Earth-abundant Fe-based oxides have drawn less attention in electrocatalytic water splitting owing to the inferior intrinsic activity and poor conductivity. Therefore, developing an effective method to increase the catalytic performance of Fe-based oxides is of great importance for the practical application. Herein, a novel Cr/N co-doped Fe3O4 electrocatalyst (denoted as Cr-Fe3O4-N/NF) is designed and prepared by a simple immersion treatment followed by a calcination method for efficient water splitting. The resultant Cr-Fe3O4-N/NF shows significant catalytic activity for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) with overpotentials of 218 and 95 mV at 10 mA cm-2. Furthermore, the water splitting system using Cr-Fe3O4-N/NF could afford a current density of 10 mA cm-2 at 1.53 V, which is superior to two-electrode system composed of Pt/C and RuO2. The high activities are attributed to the synergistic effect between Cr and N element doping. Specifically, the introduction of electron-deficient Cr is conductive to accelerate the dissociation process of water, adsorption process of intermediates, adjust the electronic structure. Simultaneously, N doping can increase the adsorption of H intermediates, provide more active sites for hydrogen absorption, and improve the electrical conductivity. This study provides a new strategy for Cr and N co-doped metal oxides electrocatalysts for high-performance water splitting.

A dye-andrographolide assembly as a turn-on sensor for detection of phthalate in both cells and fish.

Phthalates can penetrate the environment and enrich various aquatic organisms through the food chain, which is involved in promoting the growth of breast cancer. It is of current interest to develop new sensors for phthalates. We herein reported a hydrogen-bond competing fluorescent sensor, BANP, for the detection of dibutyl phthalate (DBP). The BANP compound was synthesized by assembling andrographolide (Andro), nitro- and cyano-substituted BODIPY dye (BCN), and polyethylene glycol derivatives (DSPE-mPEG5000). BANP was found to be a turn-on fluorescent probe for DBP in water with a detection limit of 0.13 µg/g; the DBP-water system acts as a hydrogen bond switch to turn on the fluorescence. And BANP fluorescently detected DBP in contaminated fish meat. Moreover, BANP sensed the DBP-induced growth of human breast cancer MCF-7 cells, and the release of Andro in the DBP-cultivated cancer cells inhibited the proliferation of the MCF-7 cells. Taken together, BANP is a DBP-responsive probe for sensitive DBP detection in water, cells, and fish meats. The BANP sensor may be used in both in vitro fluorescence and cellular imaging analyses. Our results show that guest-induced reassembly brings forth significant fluorescence change, which is a promising way of designing new fluorescent probes for the analysis of phthalates in the environment and food.

Efficient charge transfer in Co-doped CeO2/graphitic carbon nitride with N vacancies heterojunction for photocatalytic hydrogen evolution.

Photocatalytic hydrogen evolution is a promising and environmentally friendly strategy to prepare renewable energy sources thus addressing the energy crisis and environmental issues, and it is crucial to develop an ideal photocatalytic for highly efficient H2 production. Herein, the Co-doped CeO2 decorated on graphitic carbon nitride with N vacancies (NVs) heterostructure photocatalyst (Co-CeO2/DCN) is prepared via a simple self-assembly method. Due to the extended light absorption range, and efficient charge separation and migration derived from the introduction of NVs and the heterojunction structure, the photocatalytic activity of the Co-CeO2/DCN is largely promoted. The optimal sample 20-Co-CeO2/DCN shows a high H2 evolution rate of 1077.02 µmol g-1h-1 (λ > 400 nm), which is 113 and 33 times higher than the bare bulk graphitic carbon nitride (BCN) and CeO2, respectively. This work will provide a new strategy to develop high-performance photocatalysts using defect engineering and heterojunction engineering for H2 evolution.

Integrating Ru-modulated CoP nanosheets binary co-catalyst with 2D g-C3N4 nanosheets for enhanced photocatalytic hydrogen evolution activity.

Developing high-efficient and low-cost photocatalysts is of great significance yet challenging for photocatalytic hydrogen evolution. Herein, we report a 2D/2D Ru-modulated CoP nanosheets (Ru-CoP-x, where x refers the Ru-to-Co molar ratio)/g-C3N4 nanosheets (GCN NSs) ternary hybrid as a photocatalyst for hydrogen evolution under visible light. The optimal photocatalyst 25% Ru-CoP-1:8/GCN NSs exhibits an excellent hydrogen evolution rate of 1172.5 µmol g-1 h-1 under visible light with a high apparent quantum efficiency (AQE) of 3.49% at 420 nm, which is close to Pt/g-C3N4 photocatalytic system and higher than most reported transition metal phosphides (TMP)/g-C3N4 photocatalytic system. Experimental results indicate that the higher photocatalytic hydrogen evolution performance can be mainly attributed to the binary Ru-CoP-x co-catalyst with efficient charge separation and promoted surface water reduction kinetics, and the 2D/2D self-assembly structure with strong interface Schottky effect and short charge transport distance. This study provides a new approach to develop cost-effective Pt-alternative co-catalysts for photocatalytic hydrogen evolution by incorporating a small amount of ruthenium into the transition metal phosphides.

0D ultrafine ruthenium quantum dot decorated 3D porous graphitic carbon nitride with efficient charge separation and appropriate hydrogen adsorption capacity for superior photocatalytic hydrogen evolution.

Designing a Pt-alternative cocatalyst capable of dissociating HO-H bonds is of great significance yet challenging for the development of high-efficiency and cost-effective water splitting photocatalytic systems. In this study, we designed and constructed a 0D ultrafine ruthenium (U-Ru) quantum dot decorated 3D porous g-C3N4 (3DpCN) nanohybrid (U-Ru/3DpCN) for photocatalytic hydrogen evolution, in which the U-Ru quantum dots act as cocatalysts accelerating the surface proton reduction reaction, and the 3D porous architecture assembled by 2D ultrathin nanosheets inherits a short charge diffusion distance and has a large specific surface area. Owing to these structural and physicochemical merits, the optimal photocatalyst U-1Ru/3DpCN achieves a superior hydrogen evolution performance of 2945.47 µmol g-1 h-1 under visible light with a high apparent quantum efficiency (AQE) of 9.5% at 420 nm, which is close to Pt-cocatalyst/3DpCN and better than most reported co-catalysts/g-C3N4 photocatalytic systems. Experimental results indicate that the formed Schottky junction between U-Ru and 3DpCN contributes to efficient charge separation, and DFT calculations show that the Ru-cocatalyst/g-C3N4 system has an appropriate hydrogen adsorption Gibbs free energy (ΔGH*) of 0.24 eV, which are both responsible to improve the photocatalytic performance. This study provides a new way to develop excellent photocatalysts for hydrogen evolution by the integration of cost-effective Ru quantum dot cocatalysts with nanostructured semiconductors.

Solvatochromic shift of donor-acceptor substituted bithiophene in solvents of different polarity: quantum chemical and molecular dynamics simulations.

The dependence of excitation energies of the solvatochromic dye, 5-dimethylamino-5'-nitro-2,2'-bithiophene (Me(2)N-2T-NO(2)) on the solvent polarity is demonstrated by time-dependent density functional theory (TD-DFT) calculations in combination with molecular dynamics (MD) simulations. Three kinds of solvation models, namely, the continuum dielectric model, the discrete approach, and the combined discrete/continuum strategy, are employed to calculate the lowest dipole-allowed excitation energies of Me(2)N-2T-NO(2) in seven solvents with the dielectric constant, epsilon, ranging from 2.23 to 111.00. Our calculations demonstrate the limitations of the continuum dielectric model in predicting the solvatochromic shift of Me(2)N-2T-NO(2) in very polar solvents with epsilon > 35. The accuracy of the explicit solvent model is largely limited by the size of supermolecular cluster. The combined discrete/continuum solvent model gives a satisfactory description of the bathochromic shift of Me(2)N-2T-NO(2) with increasing solvent polarity, in agreement with the experimental observations.

Solvent effects on electronic structures and chain conformations of alpha-oligothiophenes in polar and apolar solutions.

Solvent effects on electronic structures and chain conformations of alpha-oligothiophenes nTs (n = 1 to 10) are investigated in solvents of n-hexane, 1,4-dioxane, carbon tetrachloride, chloroform, and water by using density functional theory (DFT) and molecular dynamics (MD) simulations. Both implicit and explicit solvent models are employed. The polarized continuum model (PCM) calculations and MD simulations demonstrate the weak solvent effects on the electronic structures of alpha-oligothiophenes. The lowest dipole-allowed vertical excitation energies of nTs, obtained from time-dependent DFT/PCM calculations at the B3LYP/6-31G(d) level, exhibit a red shift as the solvent polarity increases, in agreement with experiments. The studied solvents have little impact on the state order of the low-lying excited states provided that the nTs are kept in C2h or C2v symmetry. The MD simulations demonstrate that the chain conformations are distorted to some extent in polar and nonpolar solvents. A qualitative picture of the distribution of solvent molecules around the solvated nTs is drawn by means of radial and spatial distribution functions. The S...H-O and pi...H-O solute-solvent interactions are insignificant in aqueous solution.