Journal of Molecular Structure最新文献_第7页

The effective combination of tetrazoles, 1,2,4-triazole and dinitromethyl: A sensible strategy for energy and stability balance

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142109

Xianfeng Wang , Feng Yang , Jianshuo Cheng , Shuaijie Jiang , Xiaofeng Yuan , Qiuhan Lin , Pengcheng Wang , Yuangang Xu , Ming Lu

{"title":"The effective combination of tetrazoles, 1,2,4-triazole and dinitromethyl: A sensible strategy for energy and stability balance","authors":"Xianfeng Wang , Feng Yang , Jianshuo Cheng , Shuaijie Jiang , Xiaofeng Yuan , Qiuhan Lin , Pengcheng Wang , Yuangang Xu , Ming Lu","doi":"10.1016/j.molstruc.2025.142109","DOIUrl":"10.1016/j.molstruc.2025.142109","url":null,"abstract":"<div><div>The functionalization of double nitrogen-rich heterocycles as molecular frameworks represents an effective strategy for achieving a balance between high energy density and safety in energetic materials. In this study, a novel energetic compound <strong>8</strong>, characterized by its high density and low sensitivity (<em>ρ</em> = 1.88 <em>g</em>·cm⁻³, <em>D</em> = 8975 m·s⁻¹, IS = 20 J, FS = 180 N), along with its energetic salts <strong>4, 5, 6</strong> and <strong>7</strong>, were synthesized using 1<em>H</em>-tetrazole-5-hydrazinecarboxylic acid as the precursor. These compounds demonstrated remarkable energetic performance (<em>D</em>>8100 m·s⁻¹ and <em>P</em>>24.0 GPa) coupled with high stability (IS≥20 J, FS≥180 N), with compounds <strong>4, 6</strong> and <strong>7</strong> also exhibiting good thermal stability (<em>T</em><sub>dec</sub>>175 °C). Notably, hydroxylamine salt <strong>6</strong> stands out with its overall performance, featuring high density (<em>ρ</em> = 1.85 <em>g</em>·cm⁻³), excellent detonation characteristics (<em>D</em> = 8868 m·s⁻¹, <em>P</em> = 32.61 GPa), remarkable thermal stability (<em>T</em><sub>dec</sub> = 193.7 °C), and low mechanical sensitivity (IS = 25 J, FS = 220 N). This study provides valuable insights for designing and exploring novel high-energy compounds with improved stability characteristics.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142109"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Structure and optical properties of lanthanide complexes with scorpionate-like bis-carbacylamidophosphate ligand tetramethyl[pyridine-2,6-diyldi(iminocarbonyl)]diamidophosphate

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142070

N.S. Kariaka , V.A. Ovchynnikov , I.P. Olyshevets , S.S. Smola , N.V. Rusakova , V.V. Dyakonenko , S.V. Shishkina , V.M. Amirkhanov

{"title":"Structure and optical properties of lanthanide complexes with scorpionate-like bis-carbacylamidophosphate ligand tetramethyl[pyridine-2,6-diyldi(iminocarbonyl)]diamidophosphate","authors":"N.S. Kariaka , V.A. Ovchynnikov , I.P. Olyshevets , S.S. Smola , N.V. Rusakova , V.V. Dyakonenko , S.V. Shishkina , V.M. Amirkhanov","doi":"10.1016/j.molstruc.2025.142070","DOIUrl":"10.1016/j.molstruc.2025.142070","url":null,"abstract":"<div><div>The solvent free lanthanide complexes [Ln(HL)<sub>2</sub>NO<sub>3</sub>] (Ln = Eu, Gd, Tb) with scorpionate type bis-carbacylamidophosphate ligand tetramethyl[pyridine-2,6-diyldi(iminocarbonyl)]diamidophosphate (H<sub>2</sub> L) were synthesized. IR, diffuse reflectance, and luminescence spectroscopy measurements were carried out for their characterization. The crystal structure of the gadolinium complex was solved. It has been established that the ligands are coordinated to the lanthanide ion in a scorpionate way with formation of six-membered and twelve-membered metal cycles. H<sub>2</sub>L, [HL]<sup>−</sup> and NaHL were theoretically studied by DFT calculations. The analysis of the HOMO-LUMO gap has shown that the anion [HL]<sup>−</sup>is less stable than the molecular form of the ligand, however, the sodium cation in NaHL crystal structure stabilizes the deprotonated form of the ligand. The DFT quantum chemical calculations of the vibrational wavenumbers were performed for the H<sub>2</sub>L and NaHL. The europium and terbium complexes exhibit sensitized f-f luminescence with decay times at room temperature equal to 1.63 and 1.96 ms, respectively. Based on luminescence excitation spectra, the ligand-to-metal energy transfer in the europium complex was found to be strongly temperature dependent.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142070"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Piperazinium ammonium chloride hydrate: growth and physicochemical characterizations of nonlinear optical single crystal

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142117

S. Sivaraj , B. Chidambaranathan , P. Vijayamathubalan , R. Gunaseelan , P. Karuppasamy , P. Sagayaraj , S. Selvakumar

{"title":"Piperazinium ammonium chloride hydrate: growth and physicochemical characterizations of nonlinear optical single crystal","authors":"S. Sivaraj , B. Chidambaranathan , P. Vijayamathubalan , R. Gunaseelan , P. Karuppasamy , P. Sagayaraj , S. Selvakumar","doi":"10.1016/j.molstruc.2025.142117","DOIUrl":"10.1016/j.molstruc.2025.142117","url":null,"abstract":"<div><div>A nonlinear optical (NLO) single crystal of piperazinium ammonium chloride hydrate (PACH) was formed at room temperature utilizing the slow evaporation solution growth approach with double distilled water as the solvent. Single crystal X-ray diffraction examination validated the crystal's orthorhombic structure and determined unit cell characteristics (<em>a</em> = 6.52 Å, <em>b</em> = 12.91 Å, and <em>c</em> = 12.83 Å). The appearance of a prominent Bragg's peak in the powder X-ray diffraction pattern proved the developed PACH sample's crystalline nature. Hirshfeld study reveals that intermolecular interactions of N-H⋯Cl, O-H⋯Cl, and H…H contribute significantly to the molecular packing of the title molecule. Fourier transform infrared spectroscopy was used to determine the functional groups in the synthesized molecule. The UV-visible-NIR optical analysis revealed the transparency, band gap (E<sub>g</sub>), extinction coefficient (K), and linear refractive index (n<sub>0</sub>) of PACH. Using a solid-state laser (632.8 nm), a Z-scan measurement was performed to determine the selected single crystal's third-order optical susceptibility (χ<sup>(3)</sup>). A prominent emission peak was seen in the photoluminescence spectrum, indicating yellow (572.8 nm) emission. The thermal stability of the PACH single crystal was examined using thermogravimetric and differential thermal analysis (TG-DTA). The PACH crystal was subjected to Vicker's microhardness testing, and its work-hardening coefficient was determined to be 3.1. The dielectric constant and dielectric loss of the PACH crystal have been investigated. The HOMO-LUMO energy gap was calculated.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1337 ","pages":"Article 142117"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigation of binding mechanism for newly synthesized apigenin derivatives with xanthine oxidase: Spectroscopic and computational approach

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142112

Yan Liu, Dehong Yu, Yi Liu, Lizi Li, Can Yang, Hao Chen, Yanfang Li

{"title":"Investigation of binding mechanism for newly synthesized apigenin derivatives with xanthine oxidase: Spectroscopic and computational approach","authors":"Yan Liu, Dehong Yu, Yi Liu, Lizi Li, Can Yang, Hao Chen, Yanfang Li","doi":"10.1016/j.molstruc.2025.142112","DOIUrl":"10.1016/j.molstruc.2025.142112","url":null,"abstract":"<div><div>In this work, six apigenin derivatives were synthesized by coupling the 4′‑hydroxyl group of the B-ring of apigenin with an alkyl group. All of them displayed more inhibition potency <em>in vitro</em> than positive controls (allopurinol) and stat point (apigenin) against xanthine oxidase (XO). Further binding mechanism exploring of the two most potent inhibitors (<strong>C3</strong> and <strong>C5</strong>) with XO was performed by enzyme kinetic analysis, spectroscopic methods (including molecular steady-state fluorescence, time-resolved fluorescence, three-dimensional fluorescence, differential scanning fluorimetry), isothermal titration calorimetry (ITC), and computational approach (molecular docking and molecular dynamic simulations). The achieved results revealed that both <strong>C3</strong> (Ki of 75 nM) and <strong>C5</strong> (Ki of 91 nM) are reversible competitive inhibitors and their binding to XO exhibited static bursts. The thermodynamic information of two inhibitor-XO complexes and the impact of binding on the thermal stability of XO were unveiled. The hydrophobic substituents at the 4′-position of <strong>C3</strong> and <strong>C5</strong> play an important role in enhancing inhibition ability. The binding of <strong>C3</strong> and <strong>C5</strong> to XO caused a change in the protein conformation, affecting the microenvironment of the key amino acid residues of XO. The computational interaction justified the experimental binding interaction of two inhibitors with the current study afforded comprehensive and valuable information to understand the impacts of apigenin derivatives on the structure, activity, and function of XO, and offered ideas for the design of novel inhibitors with flavonoid skeleton that possess stronger affinity.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142112"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Exploring sulfathiourea solvate structures: A combined experimental and computational study on crystal forms, desolvation, and stability

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142124

Leonie I. Reumayr , Volker Kahlenberg , Doris E. Braun

{"title":"Exploring sulfathiourea solvate structures: A combined experimental and computational study on crystal forms, desolvation, and stability","authors":"Leonie I. Reumayr , Volker Kahlenberg , Doris E. Braun","doi":"10.1016/j.molstruc.2025.142124","DOIUrl":"10.1016/j.molstruc.2025.142124","url":null,"abstract":"<div><div>Sulfathiourea (STU), a sulfonamide derivative, underwent an extensive solvate screening program, leading to the discovery of the first solvates of this compound. Six solvates were identified, five of which were successfully solved using X-ray powder diffraction data, complemented by electronic structure calculations. Among these, three are monosolvates (with dimethyl sulfoxide, tetrahydrofuran, and dimethyl carbonate). The DMSO solvate exhibits the highest stability of all the solvates, attributed to numerous stabilizing STU···DMSO and DMSO···DMSO interactions. The remaining three solvates are 1,4-dioxane solvates, two of which are polymorphs with hemisolvate stoichiometry. Each of the solvates adopts a unique packing arrangement, with their formation dependent on the starting anhydrate and processing time. Notably, two of the 1,4-dioxane solvates act as intermediates during the formation of the most stable of the three 1,4-dioxane solvates. Pairwise intermolecular energy calculations for all structurally resolved solvates revealed that solvent molecules play a crucial role in stabilizing the lattice energy of these multicomponent solid-state forms. This study, therefore, provides valuable insights into the structural characteristics of STU solvates and their impact on solid-form stability and expands the structural knowledge of sulfonamides.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142124"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis, Characterization, and Application of Natural Occurring Hydroxy Functionalized Benzoate based Ionic Liquids as Catalyst for 2-amino-7-hydroxy-4H-chromene Derivatives under Ultrasound Irradiation

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-20 DOI: 10.1016/j.molstruc.2025.142100

Muhammad Naveed Javed , Hadeesa Batool , Mahwish Mobeen Khan , Shoaib Muhammad , Imran Ali Hashmi , Kashif Riaz , Ahmed Bari , William Henderson , Firdous Imran Ali

{"title":"Synthesis, Characterization, and Application of Natural Occurring Hydroxy Functionalized Benzoate based Ionic Liquids as Catalyst for 2-amino-7-hydroxy-4H-chromene Derivatives under Ultrasound Irradiation","authors":"Muhammad Naveed Javed , Hadeesa Batool , Mahwish Mobeen Khan , Shoaib Muhammad , Imran Ali Hashmi , Kashif Riaz , Ahmed Bari , William Henderson , Firdous Imran Ali","doi":"10.1016/j.molstruc.2025.142100","DOIUrl":"10.1016/j.molstruc.2025.142100","url":null,"abstract":"<div><div>The Hydroxy functionalized benzoate based Ionic Liquids (ILs) were synthesized and characterized by Nuclear Magnetic Resonance (NMR), High-Resolution Electrospray ionization mass spectrometry (HR-ESI-MS), Fourier transform infrared spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA) and Ultraviolet radiation (UV). All these techniques, especially NMR and HR-ESI-MS results, suggested the successful synthesis of the ILs. The electrical conductivity, viscosity, surface tension, density, and refractive index analyses of hydroxy-functionalized ILs were performed. The hydroxy-functionalized ILs were effectively employed in a one-pot synthesis of 2-amino-7-hydroxy-4H-chromene derivatives under ultrasound irradiation. These ILs demonstrated efficient catalytic performance, yielding 2-amino-7-hydroxy-4H-chromene derivatives in the 80 – 96 % range at 60°C. Upon completion of the reaction, the catalyst was easily recovered through simple filtration and reused for four additional cycles without significantly affecting product yields. Moreover, the impact of the supramolecular polymeric aggregation behavior of hydroxy-functionalized ILs on the catalytic activity was analyzed. The attained catalytic performance suggested that the synthesized catalyst is environmentally friendly, highly active, and suitable for synthesizing 2-amino-7-hydroxy-4H-chromene derivatives.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142100"},"PeriodicalIF":4.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705147","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

ZnS/MnO2 nanocomposite electrodes: A dual approach for superior supercapacitor and safety open structure lithium-ion battery

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-19 DOI: 10.1016/j.molstruc.2025.142114

Sreenivasa Kumar Godlaveeti , Razan A. Alshgari , Mohammed Mushab , Li Mingqiang , He Ying

{"title":"ZnS/MnO2 nanocomposite electrodes: A dual approach for superior supercapacitor and safety open structure lithium-ion battery","authors":"Sreenivasa Kumar Godlaveeti , Razan A. Alshgari , Mohammed Mushab , Li Mingqiang , He Ying","doi":"10.1016/j.molstruc.2025.142114","DOIUrl":"10.1016/j.molstruc.2025.142114","url":null,"abstract":"<div><div>In this study, we present a simple hydrothermal method for the synthesis of ZnS/MnO<sub>2</sub> nanocomposites (NCs) for advanced hybrid supercapacitor (SC) and safe open-system lithium-ion battery (LIB) applications. The synthesized materials—ZnS, MnO<sub>2</sub>, and ZnS/MnO<sub>2</sub> NCs—are comprehensively characterized using various techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), field emission transmission electron microscopy (FE-TEM), energy-dispersive X-ray analysis (EDAX), and X-ray photoelectron spectroscopy (XPS). The electrochemical behavior of these materials is evaluated through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) measurements, and electrochemical impedance spectroscopy (EIS). When tested in LIBs, the ZnS and ZnS/MnO<sub>2</sub> electrodes reveal promising performance, with the ZnS/MnO<sub>2</sub> composite showing an impressive specific capacitance (C<sub>sp</sub>) of 254.3 F/g and exhibiting low charge transfer resistance. This results in a high energy density of 14.12 Wh/kg and a power density of 1998.4 W/kg. Furthermore, the composite achieves a peak discharge capacity of 181.41 mAh/g at a current density of 0.5 A/g, outperforming the pure ZnS electrode. These encouraging results highlight the potential of ZnS/MnO<sub>2</sub> NCs as a superior electrode material for SCs and safer, open-system LIBs, surpassing the performance of conventional LIBs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142114"},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unlocking antidiabetic potential: Novel compounds from endophytic fungi isolated from Manihot esculenta Crantz tuberous roots

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-19 DOI: 10.1016/j.molstruc.2025.142083

Keerthana Nagarajan , Mahisha Devi Chelladurai , Sivaranjini Mani , Parasuraman Pavadai , Panneerselvam Theivendren , Ponnusamy Palanisamy , Murugesan Sankaranarayanan , Selvaraj Kunjiappan

{"title":"Unlocking antidiabetic potential: Novel compounds from endophytic fungi isolated from Manihot esculenta Crantz tuberous roots","authors":"Keerthana Nagarajan , Mahisha Devi Chelladurai , Sivaranjini Mani , Parasuraman Pavadai , Panneerselvam Theivendren , Ponnusamy Palanisamy , Murugesan Sankaranarayanan , Selvaraj Kunjiappan","doi":"10.1016/j.molstruc.2025.142083","DOIUrl":"10.1016/j.molstruc.2025.142083","url":null,"abstract":"<div><div><em>Penicillium oxalicum</em> is an endophytic fungus isolated from cassava tuberous root (<em>Manihot esculenta</em> Crantz), and their ethyl acetate extract tested for free radicals scavenging and α-amylase, β-glucosidase enzyme inhibitory assay. The profiling of molecules from endophytic fungal extract revealed thirteen volatile and four non-volatile bioactive molecules through GC–MS and LC-MS, respectively. Notably, four molecules 2-Phenylpyrido[3,4-d]-1,3-oxazin-4-one (CID: 555,390) -9.40 kcal × mol<sup>-1</sup>, Guanosine (CID: 135,398,635) -7.60 kcal × mol<sup>-1</sup>, Quercetin-3-O-sophoroside (CID: 5282,166) -7.60 kcal × mol<sup>-1</sup>, and Esculin (CID: 5281,417) -7.20 kcal × mol<sup>-1</sup> were identified for a better binding affinity against PPARγ protein. Molecular dynamics simulation studies predicted the Guanosine-PPARγ complex, which showed highly stable and better intermolecular interactions during the molecular dynamics simulation periods (500 ns). Further, the endophytic fungal extract showed excellent DPPH* and ABTS* scavenging and ferric ion-reducing potentials. Additionally, endophytic fungal extract displayed potential α-amylase and β-glucosidase enzyme inhibitory activities compared to pioglitazone. These findings showed that the ethyl acetate fraction of <em>P. oxalicum</em> is an effective source of new antioxidants and possible diabetic inhibitory properties, which can be used to generate prospective antidiabetic drugs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1337 ","pages":"Article 142083"},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Zwitterionic manganese(II) MOF based on bisimidazole tetracarboxylic acid ligand exhibiting reversible photochromism, erasable inkless printing and amine-selective sensing

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-19 DOI: 10.1016/j.molstruc.2025.142118

Xin Chen , Meng-Qiang Deng , Xiao-Shuai Ma , Huan Zhang , Peng Li , Wei Gao , Ji-Yang Li , Xiu-Mei Zhang

{"title":"Zwitterionic manganese(II) MOF based on bisimidazole tetracarboxylic acid ligand exhibiting reversible photochromism, erasable inkless printing and amine-selective sensing","authors":"Xin Chen , Meng-Qiang Deng , Xiao-Shuai Ma , Huan Zhang , Peng Li , Wei Gao , Ji-Yang Li , Xiu-Mei Zhang","doi":"10.1016/j.molstruc.2025.142118","DOIUrl":"10.1016/j.molstruc.2025.142118","url":null,"abstract":"<div><div>As chromic materials, viologen-based metal-organic frameworks (MOFs) with the electron-deficient bipyridinium have received enormous attentions. The imidazole nitrogen atoms possess the high basicity, which tends to be protonated, leading to the electron-deficient imidazolium that also may induce color changes. Along this line, by using the bisimidazole tetracarboxylic acid, a three-dimensional (3D) zwitterionic Mn-MOF was synthesized under solvothermal conditions, namely [Mn(H<sub>4</sub>L)(H<sub>2</sub>O)<sub>2</sub>]·2H<sub>2</sub>O (Mn-MOF<strong>-1</strong>) (H<sub>6</sub>L = 4,4′,4″,4‴- (1,4-phenylenebis (1H-imidazole-2,4,5-triyl))tetrabenzoic acid). Mn-MOF<strong>-1</strong> shows reversible color changes with high contrast color from light yellow to green under visible light irradiation, which can be attributed to the generations of radicals through photoinduced intermolecular electron transfer (ET) between carboxylate and imidazolium, which can be confirmed by the electron paramagnetic resonance (EPR) and the density function theory (DFT) calculations. To advance the practical application, we have fabricated [Mn-MOF<strong>-1</strong>]-filter paper and [Mn-MOF-<strong>1</strong>]-PMMA films, which can be used for inkless and erasable printing. Besides, Mn-MOF<strong>-1</strong> can also show color changes for the small primary amines such as ethylamine (EA), <em>n</em>-propylamine (PA) and <em>n</em>-butylamine (BA). This size-selective chromic behaviors can be interpreted with host-guest electron transfer generating radicals in the specific confined space. This work provides a promising strategy to promote the development of stimulus-responsive multifunctional MOF-based materials.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142118"},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigations on molecular structures and excited state dynamics of 5-cholorouracil

IF 4 2区化学

Journal of Molecular Structure Pub Date : 2025-03-19 DOI: 10.1016/j.molstruc.2025.142115

Jinming Liu , Xinli Song , Jinyou Long , Song Zhang

{"title":"Investigations on molecular structures and excited state dynamics of 5-cholorouracil","authors":"Jinming Liu , Xinli Song , Jinyou Long , Song Zhang","doi":"10.1016/j.molstruc.2025.142115","DOIUrl":"10.1016/j.molstruc.2025.142115","url":null,"abstract":"<div><div>The excited-state dynamics of photosensitizers dictate their phototoxicity and photostability in photodynamic therapy (PDT), thereby influencing their applicability. The heavy-atom and electron-withdrawing effects of chlorine in 5-chlorouracil (5-ClU) endow its photosensitive potential. However, the excited-state dynamics of 5-ClU remain poorly understood, which hinders its broader applications. To address this gap, accurate electronic structure and rate constant calculations at the XMS-CASPT2 level were performed to elucidate the deactivation mechanisms of 5-ClU in both singlet and triplet manifolds. Upon photoexcitation to the bright <sup>1</sup>ππ* state, rapid relaxation occurs either through internal conversion (IC) to the <sup>1</sup>nπ* state or via the <sup>1</sup>ππ*/S<sub>0</sub> conical intersection back to the ground state (S<sub>0</sub>) within several picoseconds. The intersystem crossing processes from the <sup>1</sup>ππ* state to <sup>3</sup>nπ* state, and from the <sup>1</sup>nπ* state to <sup>3</sup>ππ* occur within tens of picoseconds, indicating that relaxation to the S<sub>0</sub> state predominates. The prolonged lifetime of <sup>1</sup>ππ* state in 5-ClU results from weakened nonadiabatic coupling with the S<sub>0</sub> state due to chlorine-induced π-electron cloud modifications and enhanced geometric relaxation. These findings suggest that 5-ClU possesses a certain degree of phototoxicity and photostability, making it a promising candidate for PDT and a valuable tool for structural biology research.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142115"},"PeriodicalIF":4.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0