Influence of acceptor tethering on the performance of nonlinear optical properties for pyrene-based materials with A-π-D-π-D architecture

In this study, we designed a series of pyrene-based donor-π-donor-π-acceptor compounds (HPTC1-HPTC7) by structural tailoring the reference compound (HPTC) using acceptor units. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), natural bonding orbital (NBO), transition density matric (TDM) analysis, and absorption spectra of reference and proposed derivatives were calculated at M06/6-31G(d,p) functional. All the designed compounds have smaller energy bandgaps than the HPTC compound. Moreover, the designed compounds exhibited larger global softness values than the reference. The absorption maxima of HPTC2, HPTC3, and HPTC7 are blue shifted with respect to HPTC. NBO analysis revealed that prolonged hyper conjugative associations and strong interactions between the donor (π) and acceptor (π*) moieties play a crucial part in their stabilization. The FMO and NBO findings supported the NLO responses of entitled compounds, and consequently, the linear and nonlinear properties of designed derivatives elevate compared to the reference molecule. Promisingly, the NLO response for HPTC7 comprises of highest values of <α>, β_total and < γ > as 1.92 × 10^?22 esu, 1.95 × 10^?27 esu, and 4.69 × 10⁷ (a.u). This NLO behavior shows push–pull NLO chromophores for HPTC7 predicting its role in pursuing NLO materials for optoelectronic applications.     

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.     

The Decisive Role of Spin States and Spin Coupling in Dictating Selective O2 Adsorption in Chromium(II) Metal–Organic Frameworks**

The coordinatively unsaturated chromium(II)-based Cr₃[(Cr₄Cl)₃(BTT)₈]₂ (Cr−BTT; BTT³⁻=1,3,5-benzenetristetrazolate) metal–organic framework (MOF) has been shown to exhibit exceptional selectivity towards adsorption of O₂ over N₂/H₂. Using periodic density functional theory (DFT) calculations, we attempted to decipher the origin of this puzzling selectivity. By computing and analyzing the magnetic exchange coupling, binding energies, the partial density of states (pDOS), and adsorption isotherms for the pristine and gas-bound MOFs [(Cr₄(X)₄Cl)₃(BTT)₈]³⁻ (X=O₂, N₂, and H₂), we unequivocally established the role of spin states and spin coupling in controlling the gas selectivity. The computed geometries and gas adsorption isotherms are consistent with the earlier experiments. The binding of O₂ to the MOF follows an electron-transfer mechanism resulting in a Cr^III superoxo species (O₂^.−) with a very strong antiferromagnetic coupling between the two centers, whereas N₂/H₂ are found to weakly interact with the metal center and hence only slightly perturb the associated coupling constants. Although the gas-bound and unbound MOFs have an S=0 ground state (GS), the nature of spin the configurations and the associated magnetic exchanges are dramatically different. The binding energy and the number of oxygen molecules that can favorably bind to the Cr center were found to vary with respect to the spin state, with a significant energy margin (47.6 kJ mol⁻¹). This study offers a hitherto unknown strategy of using spin state/spin couplings to control gas adsorption selectivity in MOFs.     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

Comparison study of exchange-correlation functionals on prediction of ground states and structural properties

Despite significant advances in first-principles calculation methods, there is no single exchange-correlation functional which predicts the ground state of materials without an error yet. We investigated how accurately ground states of binary semiconductors are described using 16 exchange-correlation functionals (with or without van der Waals corrections). LDA, PBEsol, SCAN (with or without rVV10 correction), and PBE with D3 van der Waals correction (zero or Becke-Johnson damping) show good predicting power. The lattice constants of stable phases were slightly better described by SCAN, PBEsol, PBE+D3 (Becke-Johnson damping), and MS2. We also propose a set of functionals to double-check the stability of new materials based on the majority vote.     

Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH₂) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S₀ and S₁ states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH₂ can undergo the ESDPT process in the S₁ state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules.     

Synthesis,computational quantum chemical study,in silico ADMET and molecular docking analysis,in vitro biological evaluation of a novel sulfur heterocyclic thiophene derivative containing 1,2,3-triazole and pyridine moieties as a potential human topoisomerase IIα inhibiting anticancer agent

Computational quantum chemical study and biological evaluation of a synthesized novel sulfur heterocyclic thiophene derivative containing 1,2,3-triazole and pyridine moieties namely BTPT [2-(1-benzyl-5-methyl-1H-1,2,3-triazol-4-yl)-6-methoxy-4-(thiophen-2-yl) pyridine] was presented in this study. The crystal structure was determined by SCXRD method. For the title compound BTPT, spectroscopic characterization like ¹H NMR, ¹³C NMR, FTIR, UV–vis were carried out theoretically by computational DFT method and compared with experimental data. Druglikeness parameters of BTPT were found through in silico pharmacological ADMET properties estimation. The molecular docking investigation was performed with human topoisomerase IIα (PDB ID:1ZXM) targeting ATP binding site. In vitro cytotoxicity activity of BTPT/doxorubicin were examined by MTT assay procedure against three human cancer cell lines A549, PC-3, MDAMB-231 with IC50 values of 0.68/0.70, 1.03/0.77 and 0.88/0.98 μM, respectively. Our title compound BTPT reveals notable cytotoxicity against breast cancer cell (MDAMB-231), moderate activity with human lung cancer cell (A-549) and less inhibition with human prostate cancer cell (PC-3) compared to familiar cancer medicine doxorubicin. From the results, BTPT could be observed as a potential candidate for novel anticancer drug development process.     

First principles investigations of Fe,Co, Ni in model honeycomb carbon networks

The behaviors of ferromagnetic transition metals of the first period: Fe, Co and Ni are examined within density functional theory calculations in two dimensional carbon extended networks using model structure LiC₆. Around geometry optimized structures, the energy-volume equations of states considering non magnetic and spin polarized configurations established ferromagnetic ground states with magnetizations –reduced with respect to the metals’– of 2 μ_B for FeC₆ and 1 μ_B for CoC₆ while no magnetic solution could be identified for NiC₆. In the D_6h point group of the P6/mmm space group l_m decomposition of the d states results with increasing energy into doublet state E_1g with d(x²-y²) and d(xy); singlet state A_1g d(z²) and doublet state E_2g d(xz) and d(yz) lying on E_F and responsible of the onset of magnetic moments. This was mirrored via molecular orbital approach with a construct of Fe embedded between two extended carbon networks thus validating the model structure proposed for TC₆ compounds. The 100% polarization in one spin channel allows proposing potential uses in spintronics applications.     

Enhancing hydrogen evolution of MoS2 basal planes by combining single-boron catalyst and compressive strain

MoS₂ is a promising candidate for hydrogen evolution reaction (HER), while its active sites are mainly distributed on the edge sites rather than the basal plane sites. Herein, a strategy to overcome the inertness of the MoS₂ basal surface and achieve high HER activity by combining single-boron catalyst and compressive strain was reported through density functional theory (DFT) computations. The ab initio molecular dynamics (AIMD) simulation on B@MoS₂ suggests high thermodynamic and kinetic stability. We found that the rather strong adsorption of hydrogen by B@MoS₂ can be alleviated by stress engineering. The optimal stress of −7% can achieve a nearly zero value of ΔG_H (~ −0.084 eV), which is close to that of the ideal Pt–SACs for HER. The novel HER activity is attributed to (i) the B– doping brings the active site to the basal plane of MoS₂ and reduces the band-gap, thereby increasing the conductivity; (ii) the compressive stress regulates the number of charge transfer between (H)–(B)–(MoS₂), weakening the adsorption energy of hydrogen on B@MoS₂. Moreover, we constructed a SiN/B@MoS₂ heterojunction, which introduces an 8.6% compressive stress for B@MoS₂ and yields an ideal ΔGH. This work provides an effective means to achieve high intrinsic HER activity for MoS₂.