Inorganic Chemistry最新文献

{"title":"An MOF-Based Composite with the Applications in Anticounterfeiting and Fluorescence Detection for 4-Nitrophenol in Water and Extracts of Rice, Soil, and Plant","authors":"Zi-Hao Xue,Bing Liu,Yu-Lin Zhu,Guan-Yu Li,Yu-Ang Liao,Ling Xu","doi":"10.1021/acs.inorgchem.6c04219","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04219","url":null,"abstract":"Toxic 4-nitrophenol (4-NP) poses risks to human health and the ecological environment, whose detection is of significance. A 3D metal–organic framework of [Zn(tr)(OAc)] (Zn-tr) (Htr = 1H-1,2,4-triazole; OAc– = acetate) and its Rh6G@Zn-tr (Rh6G = rhodamine 6G) composite were presented. Zn-tr is topologized as a (3,4,6)-connected 3,4,6T56 topological {3.72}2{32.4.73}{32.4.76.86} network. Ratiometric fluorescence Rh6G@Zn-tr sensor exhibits a high sensitivity to 4-NP with a linear relationship of I365/I554 = −0.01745C4-NP + 1.03741 (I365/I554 is the ratio of the emission intensities at 365 and 554 nm; C4-NP = 4-NP concentration) within C4-NP = 0–40 μM and limit of detection = 0.48 μM. Rh6G@Zn-tr sensing 4-NP will not be interfered by common ions and some analogues, showing high anti-interference. Rh6G@Zn-tr can accurately sense 4-NP in lake water and some environmental extracts, showing high reliability. ASCII binary code defined by blank and Rh6G@Zn-tr hydrogel in a 4 × 8 array can encrypt or decrypt information. With the two-tier secret keys of 4-NP and 254 nm UV light, a QR code becomes readable by a smartphone and returns the encrypted information. This work provides a visual fluorescence 4-NP detection method and an anticounterfeiting platform by designing an allochroic MOF-based composite.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210892","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}

{"title":"Tailoring Reactivity of Molecular Gallium Hydroxides via Chalcogen Bridging","authors":"Erandi Bernabé-Pablo,&nbsp;Alfonso Gallardo-Garibay,&nbsp;Vojtech Jancik,&nbsp;Diego Martínez-Otero,&nbsp;Roman Neufeld,&nbsp;Uvaldo Hernández-Balderas,&nbsp;Dietmar Stalke,&nbsp;Mónica Moya-Cabrera","doi":"10.1021/acs.inorgchem.6c03433","DOIUrl":"10.1021/acs.inorgchem.6c03433","url":null,"abstract":"<p>We studied the influenceof bridging chalcogen atoms(μ-E;E = S, Se) on the structure and reactivity of digallium dihydroxidecomplexes [{^MeLGa(OH)}₂(μ-E)] [E = S (<strong>4</strong>), Se (<strong>5</strong>); ^MeL = CH{CMe(NAr)}₂^–, Ar = 2,4,6-Me₃C₆H₂]. Compounds <strong>4</strong> and <strong>5</strong> weresynthesized from ^MeLGaCl₂ and sodium chalcogenide(Na₂E) in THF-NH₃(<em>l</em>), followedby controlled hydrolysis. For the sulfur system, the intermediates[{^MeLGa(Cl)}₂(μ-S)] (<strong>2</strong>) and[{^MeLGa(NH₂)}₂(μ-S)] (<strong>3</strong>) were isolated and characterized, whereas the correspondingselenium derivatives proved too reactive for isolation. The reactivityof <strong>4</strong> and <strong>5</strong> toward Group 4 metal amides,M(NR₂)₄ (M = Ti, R = Me; M = Zr, Hf, R = Et),revealed a chalcogen effect, affording both monocyclic and spirocycliccomplexes from <strong>4</strong>, while <strong>5</strong> selectively yieldedspirocyclic complexes. Likewise, the milder amide Me₂Si(NMe₂)₂ reacted exclusively with <strong>5</strong> to producea siloxide-bridged derivative. Distinct borane-dependent pathwayswere also observed. Treatment of <strong>4</strong> and <strong>5</strong> with BH₃·THF resulted in the Ga–OH protonolysisto form cyclic borates, whereas BH₃·SMe₂ promoted hydride attack at gallium, yielding gallium hydrides. Theseresults provide an insight into the ambiphilic character of <strong>4</strong> and <strong>5</strong> and establish chalcogen bridging as astrategy for tuning their bonding and reactivity.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24295–24307"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973912","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}

{"title":"Site-Selective Coupling of Pyridines Mediated by Low-Valent Aluminum Compounds: 4,4′- versus 2,2′-Coupling","authors":"Weixing Chen,&nbsp;Li Yang,&nbsp;Yihu Zhang,&nbsp;Fangfeng Chen,&nbsp;Zhenzhou Sun,&nbsp;Yanxia Zhao,&nbsp;Shi-Lu Chen,&nbsp;Igor L. Fedushkin,&nbsp;Biao Wu,&nbsp;Xiao-Juan Yang","doi":"10.1021/acs.inorgchem.6c03154","DOIUrl":"10.1021/acs.inorgchem.6c03154","url":null,"abstract":"<p>α-Diiminedianion ligated dialumane [L(THF)Al–Al(THF)L](<strong>1</strong>), in cooperation with Na metal, readily mediates dearomatizingC–C coupling of pyridines with high regioselectivity. Treatmentof <strong>1</strong> with pyridine (Py) and Na in a 1:1:1 molar ratioin toluene at room temperature afforded coupled complex [Na(THF)₆]₂[LAl–Al(L)(μ-C₁₀H₁₀N₂)Al(L)–AlL] (<strong>2</strong>), which featuresa bridging 4,4′-dihydro-4,4′-bipyridine-1,1′-diyl(C₁₀H₁₀N₂^2–) unitwhile retaining the Al(II)–Al(II) bond. However, when 4 equivof Py and 2 equiv of Na were used, the Al(II) center in <strong>1</strong> and Na both participated in promoting reductive coupling of Py,yielding Al(III) complex [Na(Py)₃(Et₂O)][Na⊂{LAl(μ-C₁₀H₁₀N₂)₂AlL}] (<strong>3a</strong>), which in a THF solution rearranged to a unique molecular square[Na(THF)₄]₄[{LAl(μ-C₁₀H₁₀N₂)}₄] (<strong>3b</strong>). With a relativelysmall 4-substituent on pyridine (4-Me-Py or 4-benzyl-Py), 4,4′-couplingstill occurred to form products [Na(Solv)_<em>n</em>]₂[LAl–Al(L)(μ-C₁₀H₈N₂R₂)Al(L)–AlL] (R = Me (<strong>4</strong>) or Bn (<strong>5</strong>)). In contrast, when the <em>para</em> position is equipped with a bulky group (<em>t</em>Bu) oris incorporated within a ring (tetrahydroisoquinoline), the thermodynamicallyless favored 2,2′-coupling was observed to give mononuclearcomplexes [Na(DME)₃][LAl(NC₅H₄<em>t</em>Bu)₂] (<strong>6</strong>) and [Na(DME)][LAl(NC₉H₁₁)₂] (<strong>7</strong>) with a chelating2,2′-dihydro-2,2′-bipyridine-1,1′-diyl ligand.Such selective C–C couplings of pyridines have not been reportedfor Al compounds before, and the regioselectivity of 4,4′-versus 2,2′-coupling is verified by DFT computations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24217–24227"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091542","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}

{"title":"Hierarchical Self-Assembled CuS@CdS-Pt Core-Shell Heterojunctions with Photothermal Effect for Photoelectrochemical Water Splitting","authors":"Yao Li,&nbsp;Shicheng Xu,&nbsp;Qi Lan,&nbsp;Yating Wu,&nbsp;Danhong Li,&nbsp;Huijuan Zhang,&nbsp;Yu Wang","doi":"10.1021/acs.inorgchem.6c03523","DOIUrl":"10.1021/acs.inorgchem.6c03523","url":null,"abstract":"<p>Photoelectrochemical (PEC) water splitting provides asustainablepathway for hydrogen production, yet achieving efficient and stablephotoanodes continues to be a formidable obstacle. Herein, a core-shellCuS@CdS-Pt photoanode is constructed via in situ hydrothermal self-assemblyfollowed by Pt surface modification. The Z-scheme heterojunction betweenCdS and CuS generates the built-in electric field (IEF), stimulatingspatial separation of photogenerated electron-hole pairs while preservingstrong redox capability. Building on this, a synergistic dual-thermaleffect is proposed and demonstrated. Specifically, the photothermaleffect of CuS enhances thermal conductivity via non-radiative relaxation-inducedphonon transport along the lattice, accelerating water oxidation kineticsand boosting charge separation efficiency. Meanwhile, the localizedsurface plasmon resonance (LSPR) effect of surface-decorated Pt strengthensthe local electromagnetic field, injects hot electrons, and providesadditional thermal energy, synergistically regulating carrier separationand transport. Consequently, the optimized CuS@CdS-Pt photoanode achievesa photocurrent density of 3.92 mA cm^–2 at 1.23 V_RHE under near-infrared (NIR) auxiliary irradiation, a Faradaicefficiency of 90.3%, and retains 90% initial photocurrent after 20h of uninterrupted running, to our knowledge exceeding all prior CdS-basedphotoanodes. This work integrates heterojunction engineering withthe dual-thermal effect, providing a new strategy for designing high-efficiency,durable photoanodes for PEC water splitting.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24308–24318"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091544","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}

{"title":"Halide Substitution and π-Conjugated Cation Engineering Enable Large-Hysteresis Phase-Transition-Induced Thermochromic Luminescence in Zero-Dimensional Hybrid Manganese(II) Halides","authors":"Lin-Na Tian,&nbsp;Pei-Zheng Liu,&nbsp;Zhao-Jun Lyu,&nbsp;Ruisi Yu,&nbsp;Ya-Yao Xin,&nbsp;Jia-Jia Zhao,&nbsp;Li-Zhuang Chen","doi":"10.1021/acs.inorgchem.6c03986","DOIUrl":"10.1021/acs.inorgchem.6c03986","url":null,"abstract":"<p>Zero-dimensional (0D) organic-inorganic hybrid manganese(II)halideshave attracted considerable attention for their tunable luminescenceand stimulus-responsive properties, yet simultaneously achieving high-efficiencyemission and large-hysteresis thermochromic behavior remains challenging.Herein, three 0D hybrid manganese(II) halides were constructed throughthe synergistic regulation of halide substitution and π-conjugatedcation engineering. Notably, [H(4-PipPy)]₂MnBr₄ exhibits a high photoluminescence quantum yield of 60.95% and areversible structural phase transition with a large thermal hysteresisof 94 K, among the largest values reported for 0D hybrid manganesehalides. This transition is accompanied by reversible thermochromicluminescence with an emission shift from 530 to 549 nm. Variable-temperaturephotoluminescence, differential scanning calorimetry, and variable-temperaturepowder X-ray diffraction reveal the direct relationship between structuraltransformation and luminescence switching. Moreover, the complementaryemissions of [H₂(4-PP)]MnBr₄ and [H(4-PipPy)]₂MnBr₄ enable information encryption and anti-counterfeitingapplications. This work provides new insights into the synergisticregulation of luminescence and phase transitions in zero-dimensionalhybrid manganese halides, offering a new design concept for multifunctionalthermochromic luminescent materials.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24427–24436"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091595","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}

{"title":"Ion-Exchange Strategy toward Green Energetic Dinitramide Ionic Salts with Ultralow Hygroscopicity and Low Sensitivity","authors":"Ruyi Lu,&nbsp;Ming Lu,&nbsp;Pengcheng Wang","doi":"10.1021/acs.inorgchem.6c04141","DOIUrl":"10.1021/acs.inorgchem.6c04141","url":null,"abstract":"<p>Developing chlorine-free oxidizersthat simultaneously combinehigh energy, low mechanical sensitivity, and moisture resistance remainsa major challenge for dinitramide-based energetic materials. Herein,two nitrogen-rich heterocyclic dinitramide salts, 3 and 6, were preparedthrough aqueous metathesis to investigate the influence of cationstructure on their physicochemical and energetic properties. Compound3 shows a decomposition onset temperature of 170 °C and a stepwiseexothermic decomposition process, indicating relatively high thermalrobustness. In contrast, compound 6 combines a measured density of1.83 g cm^–3 with a calculated detonation velocityof 8951 m s^–1 and a detonation pressure of 35.9GPa, comparable to those of RDX. No initiation was observed for eithersalt up to the maximum tested impact energy and friction load of 40J and 360 N, respectively. Compound 6 also exhibits minimal moistureuptake after exposure to 55% relative humidity at 25 °C for 54h. EXPLO5 calculations predict maximum specific impulses of 268.6and 270.0 s for GAP- and NEPE-based formulations containing 45 and65 wt % compound 6, respectively. These results demonstrate that nitrogen-richheterocyclic cations provide an effective strategy for balancing theenergetic performance, mechanical safety, and moisture resistanceof dinitramide-based materials.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24476–24482"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091658","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}

{"title":"Improved Photocatalysis in Diisocyanide-Supported Heteroleptic Four-Coordinate Copper(I) β-Diketiminate Complexes","authors":"Linh T. M. Dang,&nbsp;Yen-Chu Lu,&nbsp;Vinh Q. Dang,&nbsp;Allana C. Darrow,&nbsp;Sungwon Yoon,&nbsp;Ashish Kumar,&nbsp;Thomas S. Teets","doi":"10.1021/acs.inorgchem.6c04807","DOIUrl":"10.1021/acs.inorgchem.6c04807","url":null,"abstract":"<p>Developingrobust, sustainable molecular photosensitizers thatcombine strong visible-light absorption, long excited-state lifetimes,and potent redox reactivity remains a fundamental challenge in photoredoxcatalysis. Cu(I) complexes are promising earth-abundant alternativesto precious-metal photocatalysts, motivating fundamental investigationsinto their excited-state properties and photocatalytic reactivity.Here we report a new class of heteroleptic four-coordinate Cu(I) complexessupported by chelating diisocyanide ligands, one with a <em>m</em>-terphenyl (CNAr₃NC) core and an analogue with a <em>m-</em>quinquephenyl core (CNAr₅NC), in combinationwith a β-diketiminate ligand with 2,6-dimethylphenyl <em>N</em>-substituents (dmp-NacNac). With more sterically encumberedor electron-rich β-diketiminate ligands, diisocyanide-bridged,three-coordinate dicopper complexes are formed instead. The four-coordinatecomplex supported by the quinquephenyl-based diisocyanide CNAr₅NC, <strong>Cu2</strong>, exhibits strong visible absorption,an excited-state lifetime over twice as long as the <em>m</em>-terphenyl CNAr₃NC analogue (103 ns vs 48 ns), and a highlyreducing excited-state oxidation potential (*<em>E</em>^ox = −2.4 V vs Fc^+/0). As a result, <strong>Cu2</strong> is active for visible-light photocatalytic <em>E</em>/<em>Z</em> isomerization of stilbene and reductive photoredoxtransformations of substituted benzophenone derivatives. In the latterapplication, <strong>Cu2</strong> outperforms a related three-coordinatemonoisocyanide-terminated analogue, affording higher yields of photohydrogenationand hydrodehalogenation products with lower catalyst loadings.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24620–24630"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151416","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}

{"title":"Triplet Resting States Govern E/Z Selectivity and Chemoselectivity in Carbene-Pincer Cobalt-Catalyzed Alkyne Semihydrogenation","authors":"Zihan Zhang,Yongfang Zhang,Yi Gao,Rongyu Li,Xueqing Song,Longfei Li","doi":"10.1021/acs.inorgchem.6c03193","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03193","url":null,"abstract":"Rigid, electronically tunable carbene-based pincer ligands constitute a highly promising platform for controlling selectivity in cobalt-catalyzed alkyne semihydrogenation, but the influence of catalyst spin-state characteristics on Z/E selectivity and over-reduction remains poorly understood. Herein, we compare the mechanistic pathways governing Z-selective, E-selective, and overhydrogenation of alkynes catalyzed by the mono(carbene)-based pincer cobalt complex [(PCNHCP)Co(N2)]+. The observed chemoselectivity between Z-selective semihydrogenation and overhydrogenation is found to be primarily from the energy difference between the two triplet resting states─B2triplet and A2triplet, which has not ever been reported. The β-hydride elimination transition state, TSB5-4_Esinglet, lies at a high energy of 17.5 kcal/mol, rendering the E-selective pathway kinetically inaccessible. Steric and electronic analyses indicate that the coordinated E-alkene in the β-hydride elimination step experiences greater steric hindrance and less πC═C → π*carbene electron-transfer stabilization than the Z-alkene, thereby suppressing β-hydride elimination. Comparative analysis reveals that the carbene ligand preferentially stabilizes the singlet state relative to the triplet state in these Co systems, and the stabilizing effect of the carbene ligands can be accumulated across multiple carbene units.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218798","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}

{"title":"cross-[B20H18]2– in Copper(I), Silver(I), and Cadmium(II) Complexation: Formation of [a2-B20H18]4– and [B20H16]4– Tetraanions","authors":"Varvara V. Avdeeva,&nbsp;Albina E. Gerusova,&nbsp;Alexey S. Kubasov,&nbsp;Aleksei V. Golubev,&nbsp;Ilya N. Klyukin,&nbsp;Nikolay T. Kuznetsov","doi":"10.1021/acs.inorgchem.6c04528","DOIUrl":"10.1021/acs.inorgchem.6c04528","url":null,"abstract":"<p>The <em>cross</em>-[B₂₀H₁₈]^2– anion, a synthetic challenge for decades, isintroduced into coordinationchemistry for the first time. Contrary to the well-behaved <em>trans</em> and <em>iso</em> isomers, the <em>cross</em>-[B₂₀H₁₈]^2– exhibits unprecedentedreactivity toward d¹⁰ metal ions (Cu⁺, Ag⁺, Cd²⁺), undergoing spontaneous reduction underambient conditions in acetonitrile affording the reduced <em>a</em>²-[B₂₀H₁₈]^4– anionin copper(I) and cadmium(II) complexes, and─remarkably─thepreviously unknown [B₂₀H₁₆]^4– species in the silver(I) system. The resulting complexes, [Ag₄(Ph₃P)₄[B₂₀H₁₆]] (<strong>1</strong>), (Et₃NH)₂[Cu₂(PPh₃)₂[<em>a</em>²B₂₀H₁₈]] (<strong>2</strong>), and [Ph₃PCH₂Naph][Cd₂(phen)₂(CF₃COO)[<em>a</em>²-B₂₀H₁₈]] (<strong>3</strong>), were characterized by single-crystal X-ray diffraction, ¹¹B NMR (only for <strong>2</strong>), and IR spectroscopy. Density functionaltheory calculations at the B97MD4/def2-TZVPP level confirm <em>a</em>²-[B₂₀H₁₈]^4– as the thermodynamically most stable reduced form, with the strongestintercage B–B bond. This work not only establishes the <em>cross</em> isomer as a distinct entry point to boron clusterchemistry but also provides a remarkably simple, one-pot route toreduced boron-rich ligands.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24097–24102"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091946","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}

{"title":"Integrating Hypergolic Metal–Organic Frameworks (HMOFs) into High-Energy Fuels Toward Dense Composite Solid Fuels","authors":"Xin-Feng Chen,&nbsp;Jiao-Lin Weng,&nbsp;Mei-Feng Huang,&nbsp;Pin-Cheng Chen,&nbsp;Ning-Xin Zhang,&nbsp;Ming-Long Luo,&nbsp;Zu-Jin Lin,&nbsp;Meng Cui,&nbsp;Guo-Cong Guo,&nbsp;Jian-Gang Xu","doi":"10.1021/acs.inorgchem.6c03993","DOIUrl":"10.1021/acs.inorgchem.6c03993","url":null,"abstract":"<p>Hypergolic metal–organic frameworks (HMOFs), constructedby coordinating reactive metal centers with energetic ligands, arepromising alternatives to carcinogenic, storage-demanding hydrazinefuels. However, the gravimetric energy densities (<em>E</em>_g) of reported HMOFs are generally below 30 kJ g^–1. Here, a strategy is proposed to combine hypergolic HMOFs, [M(2-Mim)₂(DCA)₂]_<em>n</em> (2-Mim = 2-methylimidazole,DCA = dicyanamide; M = Co <strong>1</strong>, Ni <strong>2</strong>), withhigh-energy yet nonhypergolic paraffin wax (PW), thereby achievinghypergolic materials with high energy density. The corresponding 20wt % type II grains (type II = grain configuration containing an axialcavity filled with HMOF), <strong>1-20%-PW-II</strong> and <strong>2-20%-PW-II</strong>, achieved high energy densities of 42.29 and 42.30 kJ g^–1, respectively, representing &gt;72% increases over the neat HMOFs.Meanwhile, these composite materials retain reliable ignition andsubsequent reignition capability. Compound <strong>1</strong> and itscomposite fuel both ignite faster than <strong>2</strong> and its correspondingcomposite. Calculations attribute this difference to the greater electronicresponsiveness of the Co coordination node, stronger HNO₃ binding, and enhanced charge transfer from <strong>1</strong> to HNO₃. This strategy provides a reference for the design and preparationof hypergolic fuels with high energy density and reignition capability.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24445–24455"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151424","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}