Polyhedron最新文献

{"title":"Synthesis, structural elucidation, and DNA binding behavior of a ternary copper(II) complex featuring substituted bipyridyl and dicarboxylate ligands","authors":"Sk Khalid Rahaman ,&nbsp;Taposi Chatterjee ,&nbsp;Kalamoddin Shaikh ,&nbsp;Samim Khan ,&nbsp;Masoom Raza Siddiqui ,&nbsp;Saikh M. Wabaidur ,&nbsp;Md Maidul Islam ,&nbsp;Seikh Mafiz Alam ,&nbsp;Mohammad Hedayetullah Mir","doi":"10.1016/j.poly.2024.117318","DOIUrl":"10.1016/j.poly.2024.117318","url":null,"abstract":"<div><div>The present research study is centered around the synthesis, characterization, and biological application of a ternary mixed-ligand based binuclear Cu(II) complex [Cu₂(<em>trans</em>-1,4-chdc)(4,4′-Me₂-2,2′-bpy)₂(5,5′-Me₂-2,2′-bpy)₂]·2(<em>cis</em>-H₂1,4-chdc)·2(BF₄¯) (<strong>1</strong>) by meticulous incorporation of 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me₂-2,2′-bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me₂-2,2′-bpy) and <em>cis</em>- and<!--> <em>trans</em>- mixture of 1,4-cyclohexanedicarboxylic acid (H₂1,4-chdc). Hirshfeld analysis is employed to validate non-bonded interactions, demonstrating the existence of widespread π···π stacking interactions between adjacent 4,4′-Me₂-2,2′-bpy ligands at a distance of 3.757 Å, forming a one-dimensional (1D) supramolecular polymer chain. The biological activity of complex <strong>1</strong> is explored via docking study, driven by the inherent biological inclination of the Cu(II) complexes. Agreeably, the coordination complex <strong>1</strong> displays a favorable binding to DNA, specifically binds to the major groove of DNA and the aromatic pyridine ring of the ligand partially intercalates into the base pairs with a binding constant (<em>K_b</em>) of 1.98 × 10⁵ M⁻¹.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117318"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highlighting non-covalent interactions to molecular structure, electronic and vibrational spectra in a new hybrid organic–inorganic cobalt complexes: Synthesis, characterization, experimental and computational studies","authors":"Jawher Makhlouf ,&nbsp;Youness El Bakri ,&nbsp;Chin-Hung Lai ,&nbsp;Arto Valkonen ,&nbsp;Hatem A. Abuelizz ,&nbsp;Rashad Al-Salahi ,&nbsp;Wajda Smirani Sta","doi":"10.1016/j.poly.2024.117320","DOIUrl":"10.1016/j.poly.2024.117320","url":null,"abstract":"<div><div>The cobalt (II) complexes have been synthesized from the reaction of the cationic entities (1-(2-methoxyphenyl) piperazine and the 1-(4-nitrophenyl) piperazine with metallic salt CoCl₂·6H₂O, then processing the evaporation crystal growth method at room temperature. The synthesized complexes have been fully characterized by single crystal X-ray diffraction, Hirshfeld surface analysis, as well as UV–visible, FTIR spectroscopy, Photoluminescence, and TGA/TDA analysis, and theoretical studies were also performed, in addition to the antioxidant DPPH^<img>+ <!-->radical and ABTS^<img>+ <!-->radical cation assays were performed. The crystal structural analysis reveals that both complexes crystallize in the orthorhombic system. The vibrational absorption bands were identified by infrared spectroscopy. The solid-state UV–visible absorption spectrum of the title compounds was obtained at room temperature to spotlight the optical properties. In the [300–700 K] range, the thermal behaviors were investigated and showed the decomposition of the two complexes with metal complexes residues. Hirshfeld surface analysis cum 2D fingerprint plots visualize the main intermolecular interactions with their contributions in the solid-state phase. The molecular geometries of both complexes obtained from the crystal structure were used for quantum chemical calculation. DPPH^<img>+ <!-->radical and ABTS^<img>+ <!-->radical cation assays were used to highlight the interesting antioxidant activity for both complexes, where the IC₅₀ <!-->of compound (<strong>1</strong>) was greater than 45 mg.mL⁻¹ <!-->and it was greater than 49 mg.mL⁻¹ for compound (<strong>2</strong>). The anticancer activities of the complexes studied were also investigated in silico by molecular docking.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117320"},"PeriodicalIF":2.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Triperiodic frameworks in the uranyl–2,5-thiophenedicarboxylate system: Effect of unidentate auxiliary ligands","authors":"Pierre Thuéry ,&nbsp;Youssef Atoini ,&nbsp;Jack Harrowfield","doi":"10.1016/j.poly.2024.117307","DOIUrl":"10.1016/j.poly.2024.117307","url":null,"abstract":"<div><div>2,5-Thiophenedicarboxylic acid (H₂tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with <em>N,N</em>-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO₂(tdc)(dma)] (<strong>1</strong>), isomorphous to the previously reported [UO₂(tdc)(nmp)] (nmp = <em>N</em>-methyl-2-pyrrolidone). With tdc²⁻ adopting the bis(μ₂-κ¹<em>O</em>:κ¹<em>O’</em>)-bridging coordination mode, complex <strong>1</strong> crystallizes as a triperiodic framework with the point symbol {4².8⁴}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh₃)₂Br₂], triphenylphosphine oxide is formed <em>in situ</em> and it binds to uranyl to give [UO₂(tdc)(OPPh₃)] (<strong>2</strong>). Complex <strong>2</strong> is also a triperiodic framework, with the point symbol {4.10²}₂{4².10⁴} and the <strong>dmd</strong> topological type with uranium as 3-coordinated (3-c) nodes and tdc²⁻ as either a 4-c node in its bis(μ₂-κ¹<em>O</em>:κ¹<em>O’</em>)-bridging mode, or a simple edge in the bis(κ²<em>O</em>,<em>O’</em>)-chelating mode. In both <strong>1</strong> and <strong>2</strong>, as in the previously described nmp complex, but not in [UO₂(tdc)(dmf)] (dmf = <em>N,N</em>-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc²⁻ and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex <strong>2</strong> has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O₅ equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117307"},"PeriodicalIF":2.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ruthenium-based macrocyclic and Schiff base complexes as prominent therapeutic agents: Their designing, synthesis and recent perspectives","authors":"Urmila Phageria ,&nbsp;Sushama Kumari ,&nbsp;Krishna Atal ,&nbsp;Swati Bugalia","doi":"10.1016/j.poly.2024.117309","DOIUrl":"10.1016/j.poly.2024.117309","url":null,"abstract":"<div><div>The role of macrocyclic and Schiff base complexes in chemistry and life sciences offers vast opportunities to the researchers. Herein, this review focuses on the recent developments in ruthenium-based macrocyclic complexes and their utilities. Nowadays, ruthenium-based macrocyclic complexes are substantially exploited in copious applications, such as antioxidant, anticancer, antimicrobial, catalysis, sensors, pigments, dyes, etc. are a few of them. This study combines innovations in modelling and employment of these macrocyclic ligands and their complexes with ruthenium that serves as an interaction between the fields of chemistry, physics and biology. Probably Ru(II) and Ru(III) complexes achieve a wider holder of a three-dimensional scaffold through octahedral bonding, which opens up the possibility for a greater level of site diversity for attaching to their biological substrates. This study also expresses a broader overview of the topic and aims to highlight developments in ligand designing, synthetic methods, and potent applications especially as prominent therapeutic agents of these metal complexes in diverse areas. Additionally, some of the Schiff bases complexes with the same metal are also highlighted with their prominent applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117309"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702204","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Robust Y and Lu TrenSal catalysts for ring-opening polymerisation","authors":"Eszter Fazekas ,&nbsp;Alvaro Etcheverry-Berrios ,&nbsp;Gary S. Nichol ,&nbsp;Stergios Piligkos ,&nbsp;Euan K. Brechin ,&nbsp;Jennifer A. Garden","doi":"10.1016/j.poly.2024.117308","DOIUrl":"10.1016/j.poly.2024.117308","url":null,"abstract":"<div><div>Mono and bimetallic cage-like TrenSal complexes based on rare-earth metals Y and Lu were synthesised and fully characterised by single crystal and powder X-ray diffraction, multinuclear NMR and IR spectroscopy, and MALDI-ToF mass spectrometry. These robust and air-stable complexes are active catalysts for the ring-opening polymerisation of <em>rac</em>-lactide. While the polymerisation activity is low, the complexes remain active in air using unpurified monomers, and are highly unusual examples of metal–organic cages applied in polymerisation. MALDI-ToF mass spectrometry studies of the obtained polymers revealed H and OBn end-capped chains suggesting that an ‘activated monomer’ mechanism predominates when BnOH is used as an exogenous initiator.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117308"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of series of transition metal-ligand (TM-L), μ2-O-TM, μ3-O-TM-L borates: Characterization and oxygen reduction reaction (ORR) activity property exploration","authors":"Zhen-Ping Liao ,&nbsp;Shu-Sheng Xin ,&nbsp;Wei Li ,&nbsp;Chun-Yang Pan","doi":"10.1016/j.poly.2024.117304","DOIUrl":"10.1016/j.poly.2024.117304","url":null,"abstract":"<div><div>A series of borates <strong>1</strong>–<strong>6</strong>, have been synthesized under mild conditions, single crystal X-ray diffraction indicates that they possess three types of metal complex configurations in borate crystalline, exemplified as TM-L for <strong>3</strong> and <strong>4</strong>, <em>μ</em>₂-O-TM for <strong>2</strong>, <em>μ</em>₃-O-TM for <strong>1</strong>, <strong>5</strong> and <strong>6</strong>. <strong>5</strong> and <strong>6</strong> exhibit both four-coordinated and six-coordinated metal ions in one single crystal lattice. <strong>1</strong> to <strong>6</strong> are further characterized by powder X-ray diffraction, elemental analysis, IR spectrum and UV–vis spectroscopy. In addition, the ORR activities of them are performed. Among them, cobalt borate-based catalyst exhibits the best catalytic performance, with a half-wave potential of 0.82 V. Furthermore, the relationship between the ORR properties of TM complex borates and their framework densities was explored.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117304"},"PeriodicalIF":2.4,"publicationDate":"2024-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polyoxometalates ionic liquids based magnetic nanocomposites as an efficient heterogeneous catalysts for oxidation of thiobenzoic acid and dibenzothiophene by employing RP-HPLC-UV","authors":"Roman Jaffar ,&nbsp;Najla AlMasoud ,&nbsp;Khurram Shahzad Munawar ,&nbsp;Sana Rauf ,&nbsp;Taghrid S. Alomar ,&nbsp;Hafiz Muhammad Asif ,&nbsp;Zeinhom M. El-Bahy ,&nbsp;Hameed Ullah ,&nbsp;Saifullah","doi":"10.1016/j.poly.2024.117311","DOIUrl":"10.1016/j.poly.2024.117311","url":null,"abstract":"<div><div>Sulfur compounds need to be effectively rejected from fuel to maintain a clean environment. The removal of sulfur compounds from thiocompounds has received increased attention due to the negative environmental and industrial consequences of sulfur emissions. We examine the effectiveness of polyoxometalate (POM) ionic liquid-based nanocomposites as catalysts for the oxidative desulfurization of thiobenzoic acid and other sulfur-containing chemicals. Na-POMIL@NCP and Cr-POMIL@NCP were synthesized and thoroughly characterized using a variety of analytical techniques, including Fourier-transform infrared spectroscopy (FT-IR), UV–visible spectroscopy, powder X-ray diffraction (P-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), fluorescence spectroscopy, and vibrating sample magnetometer (VSM). POMIL-based nanocomposites with Fe₃O₄@SiO₂ exhibit both catalytic activity and adsorption capability. To evaluate sulfur removal efficiency and investigate the transformation paths of the thio compounds, high-performance liquid chromatography (HPLC) was performed at 33 °C using a C18 column with an acetonitrile–water mobile phase (1:1 ratio). The catalytic conversion of thiobenzoic acid and dibenzothiophene occurs at temperature, oxidant O/S ratio and catalyst concentration were investigated to determine the best catalyst for a given process. Under moderate conditions, this work proposes a cost-effective and ecologically acceptable approach for thiobenzoic acid (TB) and dibenzothiophene (DBT) production employing H₂O₂ as an oxidant and Na-POMIL@NCP and Cr-POMIL@NCP as heterogeneous catalysts. They are highly effective for oxidizing sulfur compounds included in diesel to lower the sulfur levels of fuel. This study provides to the development of innovative materials for ecologically friendly sulfur removal applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117311"},"PeriodicalIF":2.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New complexes of [5,10,15,20-(tetraphenylporphyrin)] and dichloride (5,10,15,20-tetraphenylporphyrinato) antimony(V) hexachloridoantimonate(V) functionalized with polyethyleneimine: Synthesis, characterization, and application in Eriochrome Black T adsorption from water","authors":"Raoudha Soury ,&nbsp;Mahjoub Jabli ,&nbsp;Mabrouka El Oudi ,&nbsp;Khalaf M. Alenezi ,&nbsp;Ahmed Al Otaibi ,&nbsp;Fahad Abdulaziz ,&nbsp;Hind A. AlGhamdi ,&nbsp;Amor Bchetnia","doi":"10.1016/j.poly.2024.117305","DOIUrl":"10.1016/j.poly.2024.117305","url":null,"abstract":"<div><div>In the current work, new complexes namely [5,10,15,20 (tetraphenylporphyrin)] /Polyethyleneimine (H₂TPP-PEI) and Dichlorido(5,10,15,20-tetraphenylporphyrinato)antimony(V) hexachloridoantimonate(V)/Polyethyleneimine ([Sb(TPP)Cl₂][SbCl₆]-PEI) were successfully prepared and characterized. The prepared compounds were thoroughly analysed using ¹H NMR, UV, XRD, XRF, TGA-DTA, SEM, and EDAX. SEM analysis showed that the addition of polyethyleneimine to the porphyrin core clearly changed the morphological properties. The optical gap values were calculated using the tauc plot method and were equal to 1.877, 2.030, 1.862, and 2.017 eV for H₂TPP, [Sb(TPP)Cl₂] [SbCl₆], H₂TPP-PEI and ([Sb(TPP)Cl₂][SbCl₆]-PEI), respectively. The existence of sharp peaks at 2θ between 16° and 80° displayed the crystalline nature of the prepared porphyrinic compounds. The change in thermal decompositions for H₂TPP, [Sb(TPP)Cl₂][SbCl₆], H₂TPP-PEI and ([Sb(TPP)Cl₂][SbCl₆]-PEI) revealed that the addition of polyethyleneimine to porphyrin affected the thermal characteristics. The prepared complexes were, further, investigated for the adsorption of Eriochrome Black T (an anionic dye) from water. Highest adsorption capacities were accomplished using [Sb(TPP)(Cl₂)]-PEI (164 mg/g) and H₂TPP-PEI (82 mg/g) under the following experimental conditions (pH = 5, temperature = 19 °C, time = 60 min). However, the adsorption capacities remains poor for H₂TPP and Sn(TPP)(Cl₂). The adsorption data complied well with pseudo second order, Freundlich, and Temkin equations. Overall, the adsorption results had confirmed that polyethyleneimine functionalized porphyrins could be used as a proficient adsorbent of anionic dyes from water.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117305"},"PeriodicalIF":2.4,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of tetraphenylphosphonium/polysulfide hybrids and their temperature-induced switchable WORM/flash electrical memory behavior","authors":"Zhaoxun Lian,&nbsp;Ning Zhao","doi":"10.1016/j.poly.2024.117301","DOIUrl":"10.1016/j.poly.2024.117301","url":null,"abstract":"<div><div>The development of innovative non-volatile storage materials is essential for the progression of next-generation high-performance storage devices. In this study, a hybrid material (Ph₄P)₂S₇ was synthesized, and single crystal structure analysis demonstrated that the organic tetraphenylphosphonium cation (Ph)₄P⁺ adopts a regular tetrahedral conformation and forms one-dimensional chains through C<img>H···π interactions. The (S₇)^2- anion, characterized by quasi-bicentric symmetry and a right-handed helical cluster, is confined within the one-dimensional quantum well established by the (Ph)₄P⁺ cation chain in the organic matrix. A device composed of FTO/(Ph₄P)₂S₇/Ag was fabricated through spin-coating, demonstrating remarkable temperature-induced switchable binary write-once-read-many-times (WORM)/Flash electrical memory behavior. At room temperature, the material demonstrated nonvolatile binary WORM-type resistance switching behavior with a switching ratio of 1.95 × 10³ and an onset voltage of 1.01 V. Conversely, at 150 °C, it transits into binary Flash-type resistance switching behavior characterized by current ratio of 3.34 × 10² and onset/reset voltages of 1.05/−1.99 V. The mechanism underlying binary resistive switching is identified as spatial charge-limited charge capture. Furthermore, the observed reversible transition between WORM- and Flash- type electrical memory behavior at elevated temperatures can be attributed to lattice expansion of the (Ph)₄P⁺ cations at high temperatures, resulting in denser packing of organic molecules and deeper trapping potential wells for electrons within the active layer. This study provides theoretical insights into developing novel high-performance information storage materials.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"266 ","pages":"Article 117301"},"PeriodicalIF":2.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142702203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sensitivity of pure and Ni-decorated boron nitride B12N12 nanocages toward CH4, H2S, and N2 biogases: A DFT study","authors":"Tamer H.A. Hasanin ,&nbsp;Manar H.A. Hamad ,&nbsp;Nayra A.M. Moussa ,&nbsp;Asmaa M.M. Mahmoud ,&nbsp;Mohamed Y. El-Sayed ,&nbsp;Al-shimaa S.M. Rady ,&nbsp;Mahmoud A.A. Ibrahim","doi":"10.1016/j.poly.2024.117302","DOIUrl":"10.1016/j.poly.2024.117302","url":null,"abstract":"<div><div>The sensitivity of pure and Ni-decorated boron nitride (B₁₂N₁₂) nanocages toward CH₄, H₂S, and N₂ biogases was adequately unveiled by employing versatile density functional theory (DFT) calculations. In this regard, the Gas∙∙∙B₁₂N₁₂ and ∙∙∙Ni@B₁₂N₁₂ complexes were studied within all possible configurations. Based on the energetic quantities, the Ni@B₁₂N₁₂ nanocage exhibited higher sensitivity than the pure one toward the investigated gases. Among all studied complexes, the H₂S∙∙∙Ni@B₁₂N₁₂ complex exhibited the most favorable adsorption (<em>E</em>_ads) and interaction (<em>E</em>_int) energies with values of –29.25 and –29.46 kcal/mol, respectively. According to the outlines of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index analyses, the closed-shell nature of the interactions within the investigated complexes was ensured. Substantial alterations in the molecular orbitals distribution patterns of pure and Ni-decorated B₁₂N₁₂ nanocages were observed, announcing the occurrence of the adsorption process within the investigated complexes. The obtained negative values of thermodynamic parameters ensured the spontaneous exothermic nature of the investigated Ni-decorated complexes. Upon density of states (DOS) analysis, the influence of adsorbed gases on the electronic characteristics of the pure and Ni-decorated B₁₂N₁₂ nanocages was highlighted. According to the emerging findings, the pure and Ni-decorated B₁₂N₁₂ nanocages are promising sensing materials for biogas components, especially CH₄, H₂S, and N₂ gases.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117302"},"PeriodicalIF":2.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}