CrystEngComm最新文献

{"title":"Synthesis, characterization, and green to orange luminescence properties of copper(i) complexes with 3-bdppmapy ligand-containing phenanthroline and its derivatives†","authors":"Wen-Long Mou, Si-Jie Fan, Ying-Long Wang, Guo Wang, Fu-Zhen Hu, Gui-Xiong Guo, Hong-Liang Han, Xiu-Lan Xin, Jian-Ming Liu, Yu-Ping Yang, Zhong-Feng Li and Qiong-Hua Jin","doi":"10.1039/D4CE01324G","DOIUrl":"https://doi.org/10.1039/D4CE01324G","url":null,"abstract":"<p >This paper presents the successful synthesis of eight Cu(<small>I</small>) complexes <strong>1–8</strong>, [Cu(phen)(3-bdppmapy)]BF<small>₄</small>·CH<small>₃</small>OH (<strong>1</strong>), [Cu(phen)(3-bdppmapy)]ClO<small>₄</small>·CH<small>₃</small>OH (<strong>2</strong>), [Cu(phen)(3-bdppmapy)]I (<strong>3</strong>), [Cu(phen)(3-bdppmapy)]CF<small>₃</small>SO<small>₃</small> (<strong>4</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]BF<small>₄</small>·CH<small>₃</small>OH (<strong>5</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]ClO<small>₄</small>·CH<small>₃</small>OH (<strong>6</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]I·2CH<small>₃</small>OH (<strong>7</strong>), and [Cu(2,3-<em>f</em>)(3-bdppmapy)]CF<small>₃</small>SO<small>₃</small>·CH<small>₃</small>OH (<strong>8</strong>) (3-bdppmapy<img><em>N</em>,<em>N</em>-bis[(diphenylphosphino)methyl]-3-pyridinamine; phen<img>1,10-phenanthroline; 2,3-<em>f</em><img>pyrazino[2,3-<em>f</em>][1,10]phenanthroline) exhibiting luminescence properties ranging from green to orange emission. Comprehensive characterization and analysis of their structural and photophysical properties were conducted. The results demonstrate that complexes <strong>1–4</strong> and <strong>5–8</strong> possess the same nitrogen ligand, respectively. However, a notable distinction is observed in their fluorescent luminescence position, with complexes <strong>1–4</strong> exhibiting a pronounced blue-shift relative to complexes <strong>5–8</strong>. Further structural analysis demonstrated that the phosphine ligands in complexes <strong>5–8</strong> exhibited markedly disparate spatial configurations and photophysical properties compared to previously studied complexes. This finding demonstrates that the luminescence properties of the complexes can be effectively modulated by the structure of the micromodules. Finally, all the complexes were tested using terahertz time-domain spectroscopy, and the results exhibited a clear regularity, supporting our understanding of the relationship between the structure and photophysical properties of the complexes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2086-2100"},"PeriodicalIF":2.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740541","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":"UiO66-NH2@In2O3 heterostructures for improved photocatalytic CO2 reduction†","authors":"Bolin Ma, Guanghui Chen, Lingling Zhou, Chengyang Ni, Xinyu Sun, Lei Zhang, Xinguo Xi, Lanqin Tang and Yong Zhou","doi":"10.1039/D5CE00106D","DOIUrl":"https://doi.org/10.1039/D5CE00106D","url":null,"abstract":"<p >The development of highly efficient photocatalysts for CO<small>₂</small> reduction remains a critical challenge in achieving sustainable energy conversion. In this study, we report the synthesis of a UiO66-NH<small>₂</small>@In<small>₂</small>O<small>₃</small>, integrating UiO66-NH<small>₂</small> metal organic frameworks (MOFs) with indium oxide (In<small>₂</small>O<small>₃</small>) nanoparticles, forming a robust heterostructure. Characterization results demonstrated that calcination at 250 °C for 4 hours yielded a heterostructure with indium uniformly incorporated, as confirmed by XRD, SEM, TEM and ICP-OES analyses. XPS studies revealed significant electronic interactions between UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>, including shifts in binding energies of indium and zirconium, indicative of chemical bonding. This heterostructure facilitated enhanced charge separation and transfer, as evidenced by photocurrent measurements, leading to superior photocatalytic CO<small>₂</small> reduction performance. Under light irradiation, UiO66-NH<small>₂</small>@In<small>₂</small>O<small>₃</small> achieved a CO production rate of 83.68 μmol g<small>⁻¹</small> during the first hour and a cumulative yield of 485.08 μmol g<small>⁻¹</small> after 7 hours, significantly outperforming pristine UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>. The superior activity is attributed to the large surface area of UiO66-NH<small>₂</small>, facilitating CO<small>₂</small> adsorption, and the heterojunction formation with In<small>₂</small>O<small>₃</small>, enhancing charge carrier dynamics. These findings highlight the synergistic effects of UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>, providing insights into the design of advanced photocatalysts for environmental and energy applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1781-1788"},"PeriodicalIF":2.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632285","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":"Ionization treatment of pyrazolo[4,3-c]pyrazole derivatives to achieve the low sensitivity of high-energy materials†","authors":"Lei Shi, Bangxiang Liu, Pengfei Wang, Chao Gao, Chong Zhang, Yang Du, Chengguo Sun and Bingcheng Hu","doi":"10.1039/D4CE01286K","DOIUrl":"https://doi.org/10.1039/D4CE01286K","url":null,"abstract":"<p >Low mechanical sensitivity is an evaluation index for the development of safe and stable high-energy materials. Herein, 3,6-dinitropyrazolo[4,3-<em>c</em>]pyrazole (DNPP) and its ionic salts <strong>1–4</strong> with a fused-ring backbone were synthesized based on 6-nitro-pyrazolo[4,3-<em>c</em>]pyrazole-3-carbonic acid. Their crystal structures were determined by single crystal X-ray diffraction, and the abundant hydrogen bonds and π–π stacking in the crystal contribute to decreasing the mechanical sensitivity. The synthesized ionic salts <strong>1–4</strong> present low sensitivity features (FS &gt;360 N and IS &gt;20 J), much lower than that of their precursor DNPP (FS = 160 N and IS = 15 J). The detonation performance test shows that hydroxylammonium ionic salt <strong>3</strong> with a density of 1.863 g cm<small>⁻³</small> has the highest detonation velocity of 9.06 km s<small>⁻¹</small> and detonation pressure of 34.47 GPa, which is increased by 8.9% and 20.5% as compared with that of DNPP (8.25 km s<small>⁻¹</small> and 27.4 GPa). To expand the substituents of the fused-ring backbone, 4,5-diamino-3-(6-nitro-1,4-dihydropyrazolo[4,3-<em>c</em>]pyrazol-3-yl)-4<em>H</em>-1,2,4-triazole (<strong>5</strong>) was synthesized, and its ionic salt <strong>6</strong> indicated the excellent insensitive features (FS &gt;360 N and IS &gt;40 J). Even though salt <strong>6</strong> contains water of crystallization, it still exhibits excellent detonation performance comparable to RDX.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1918-1926"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688228","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":"Mononuclear complexes of dysprosium(iii) with 2,6-diacetylpyridine bis(isonicotinoylhydrazone): synthesis, crystal structure, and magnetic properties†","authors":"Vyacheslav A. Kopotkov, Leokadiya V. Zorina, Sergey V. Simonov, Denis V. Korchagin, Mikhail V. Zhidkov, Alexei I. Dmitriev, Ghodrat Mahmoudi and Eduard B. Yagubskii","doi":"10.1039/D5CE00066A","DOIUrl":"https://doi.org/10.1039/D5CE00066A","url":null,"abstract":"&lt;p &gt;Four discrete mononuclear Dy(&lt;small&gt;III&lt;/small&gt;) coordination compounds with the pentadentate N&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt; equatorial ligand 2,6-diacetylpyridine-bis(isonicotinoylhydrazone) (H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;dapin) in different charge states, containing the strong-field ligands Ph&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO and Cy&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO at the apical positions, have been synthesized: [Dy(H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;dapin)(Ph&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;](CF&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;SO&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt; (&lt;strong&gt;1&lt;/strong&gt;), [Dy(Hdapin)(Ph&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;](ClO&lt;small&gt;&lt;sub&gt;4&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;·C&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;H&lt;small&gt;&lt;sub&gt;5&lt;/sub&gt;&lt;/small&gt;OH·1.9H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;O (&lt;strong&gt;2&lt;/strong&gt;), [Dy(Hdapin)(Cy&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;](CF&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;SO&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt; (&lt;strong&gt;3&lt;/strong&gt;) and [Dy(Hdapin)(Cy&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;] [Dy(dapin)(Cy&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;PO)&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;](CF&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;SO&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;)&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt; (&lt;strong&gt;4&lt;/strong&gt;). The crystal structures of the complexes and DC and AC magnetic properties of &lt;strong&gt;1&lt;/strong&gt; and &lt;strong&gt;3&lt;/strong&gt; have been investigated. Complexes &lt;strong&gt;1&lt;/strong&gt; and &lt;strong&gt;2&lt;/strong&gt; with triphenylphosphinoxide apical ligands are eight-coordinated, whereas &lt;strong&gt;3&lt;/strong&gt; and &lt;strong&gt;4&lt;/strong&gt; with bulkier tricyclohexylphosphinoxide ligands are rare seven-coordinated Dy(&lt;small&gt;III&lt;/small&gt;) complexes. The pyridine-substituted pentadentate N&lt;small&gt;&lt;sub&gt;3&lt;/sub&gt;&lt;/small&gt;O&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt; ligand exhibits variability in composition and charge: neutral doubly-protonated H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;dapin in complex &lt;strong&gt;1&lt;/strong&gt;, monodeprotonated negatively charged Hdapin&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt; in &lt;strong&gt;2&lt;/strong&gt; and &lt;strong&gt;3&lt;/strong&gt;, and monodeprotonated Hdapin&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt; and fully deprotonated dapin&lt;small&gt;&lt;sup&gt;2−&lt;/sup&gt;&lt;/small&gt; in &lt;strong&gt;4&lt;/strong&gt;. The proton at one of the hydrazide groups of the H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;dapin ligand in &lt;strong&gt;1&lt;/strong&gt; is transferred to the terminal pyridine N atom. The resulting neutral H&lt;small&gt;&lt;sub&gt;2&lt;/sub&gt;&lt;/small&gt;dapin ligand adopts a zwitterionic form with 1− charge localized on the enolate O atom of the deprotonated part and 1+ charge on the N atom of the protonated pyridine. The proton transfer to the pyridyl N-atom is observed in all Hdapin&lt;small&gt;&lt;sup&gt;−&lt;/sup&gt;&lt;/small&gt; ligands in &lt;strong&gt;2–4&lt;/strong&gt;. According to SHAPE analysis, complexes &lt;strong&gt;1&lt;/strong&gt; and &lt;strong&gt;3&lt;/strong&gt; have significantly different local symmetries – low &lt;em&gt;D&lt;/em&gt;&lt;small&gt;&lt;sub&gt;2d&lt;/sub&gt;&lt;/small&gt; (highly distorted 8-vertex triangular dodecahedron) and high &lt;em&gt;D&lt;/em&gt;&lt;small&gt;","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 2012-2024"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688251","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":"Visualization of level-3 latent fingerprints by surfactant-free CsPbBr3 MCs with Pb(OH)2 as a passivation layer and an anchored bridge†","authors":"Guoxin Zhuang, Yujing Li, Xiaodi Chu, Xianghui Lai, Zhiyu Liang, Xiaohui Lin, Yonglin Wen, Guosong Lin, Zhechong Zheng and Chonghui Li","doi":"10.1039/D4CE01004C","DOIUrl":"https://doi.org/10.1039/D4CE01004C","url":null,"abstract":"<p >The visualization of level 3 fingerprint features, such as pore size, spacing, and distribution, plays a crucial role in matching damaged latent fingerprints (LFPs). CsPbBr<small>₃</small> microcrystals (MCs) show great potential for LFP visualization, but the use of organic surface passivation can deteriorate their fluorescence properties and reduce imaging quality. In this study, we developed CsPbBr<small>₃</small> MCs with a Pb(OH)<small>₂</small> passivation layer formed through a methylamine vapor phase transition, replacing the need for organic passivators. Thanks to the hydrophobic nature and hydrogen bonding properties of Pb(OH)<small>₂</small>, the CsPbBr<small>₃</small> MCs demonstrate excellent structural and fluorescence properties, while also anchor effectively to amino acids. Beyond the pressure deficit mechanism, FT-IR analysis and theoretical calculations confirm that the –COOH groups in amino acids form hydrogen bonds with the OH groups of Pb(OH)<small>₂</small>, leading to the absorption of CsPbBr<small>₃</small> MCs onto fingerprint ridges. This results in superior visualization of level 3 fingerprint details, offering new insights into the development of surfactant-free inorganic materials for fluorescence imaging.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1763-1772"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632283","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":"Enhanced luminescence in 1D corrugated lead bromides via reduced flexibility of trivalent cations†","authors":"Chang-Chun Fan, Zi-Han Fang, Shu-Lin Jiao, Jing-Xue Yu, Cheng-Dong Liu, Wei Wang, Ming-Liang Jin, Bei-Dou Liang and Xiang-Bin Han","doi":"10.1039/D5CE00003C","DOIUrl":"https://doi.org/10.1039/D5CE00003C","url":null,"abstract":"<p >Hybrid metal halides (HMHs) have attracted considerable attention from researchers exploring broadband luminescence materials due to their low cost and excellent photophysical properties. Although lots of structures have been developed by researchers based on monovalent and bivalent cations, the importance of trivalent cations in the design of low-dimensional HMH materials with broadband luminescence has been overlooked. In our study, we obtained two new 1D corrugated structures (MPEA)PbBr<small>₅</small>·H<small>₂</small>O (MPEA is 4-methyl-1-piperazineethanammonium) and (PEA)<small>₂</small>Pb<small>₂</small>Br<small>₁₀</small>·H<small>₂</small>O (PEA is 1-piperazineethanammonium) based on trivalent cations, which can efficiently emit yellow-white light emission with CIE color coordinates of (0.35, 0.42) and (0.42, 0.47) at room temperature with a photoluminescence quantum yield of 0.6% and 10.9%, respectively. Our research underscores the advantages of utilizing low flexible trivalent cations in the development of HMHs with outstanding broadband emission performance and provides novel insight into the design of advanced solid-state luminescent materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1997-2003"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00003c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688249","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":"Microinjection-assisted synthesis of Pt–Pd hollow nanoparticles for enhanced methanol oxidation reactions†","authors":"Dan Zhao, Pan Zeng, Xinyu Wang, Fuquan Wang, Huiting Wu, Yujia Zhai, Dandan Men, Yiqiang Sun, Wenshan Qu and Haijian Li","doi":"10.1039/D5CE00080G","DOIUrl":"https://doi.org/10.1039/D5CE00080G","url":null,"abstract":"<p >A large-scale synthesis of electrocatalysts with controllable composition and a surface atomic structure is crucial for practical applications. Herein, Pt–Pd hollow nanoparticles (HNs) were prepared using a facile microinjection strategy. Owing to their high-density nanopores, atomic steps and grain boundaries, the Pt–Pd HNs exhibit a superior catalytic activity for the methanol oxidation reaction (MOR) compared with commercial Pt black. Moreover, theoretical calculation proves that compared with the Pt and Pd structures, the Pt–Pd alloy structure possesses high anti-CO poisoning capability and a low energy barrier in the rate-limiting step, both of which are favorable for the MOR. This work proposes a strategy for large-scale preparation of hollow electrocatalysts with high catalytic activity, thus promoting practical application of direct methanol fuel cells (DMFCs).</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2108-2114"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740543","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":"Triazole-derivatized ligand-directed diverse structures and polyaniline-assisted capacitive performances of two new Anderson-type [AlMo6(OH)6O18]3−-based metal–organic complexes†","authors":"Zhi-fei Zu, Ju-ju Liang, Zhi-han Chang, Yu-chun Lin and Xiu-li Wang","doi":"10.1039/D5CE00049A","DOIUrl":"https://doi.org/10.1039/D5CE00049A","url":null,"abstract":"<p >Two new polyoxometalate-based metal–organic complexes (POMOCs), namely, H{Zn<small>₂</small>(Hpytty)<small>₂</small>[AlMo<small>₆</small>(OH)<small>₆</small>O<small>₁₈</small>](H<small>₂</small>O)<small>₈</small>}·6H<small>₂</small>O (<strong>1</strong>), H{Zn<small>₂</small>(Hpyttz)<small>₂</small>[AlMo<small>₆</small>(OH)<small>₆</small>O<small>₁₈</small>](H<small>₂</small>O)<small>₈</small>}·6H<small>₂</small>O (<strong>2</strong>) (H<small>₂</small>pytty = 3-(pyrazin-2-yl)-5-(1<em>H</em>-1,2,4-triazol-3-yl)-1,2,4-triazolyl, H<small>₂</small>pyttz = 3-(pyrid-2-yl)-5-(1<em>H</em>-1,2,4-triazol-3-yl)-1,2,4-triazolyl), were obtained under hydrothermal conditions using different N-rich triazole-derivatized ligands and they were characterized through powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, and infrared spectroscopy. Both the title POMOCs show 2D supramolecular structures formed through hydrogen bonds, except that the [AlMo<small>₆</small>(OH)<small>₆</small>O<small>₁₈</small>]<small>³⁻</small> anions in complex <strong>2</strong> are immobilized between the metal–organic units <em>via</em> coordination interaction. The capacitive performances of the carbon paper-based electrodes modified by complexes <strong>1–2</strong> were investigated, in which complex <strong>2</strong> achieved a larger specific capacitance of 1362 F g<small>⁻¹</small> than that of <strong>1</strong> (1836 F g<small>⁻¹</small>) at a charge–discharge current density of 1 A g<small>⁻¹</small>. The enhancement in intramolecular bond strength is beneficial for improving the capacitance performance of complexes. In addition, after electrochemical conditioning with polyaniline, the electron–ion transfer rate, along with the pseudocapacitive activity of complexes <strong>1–2</strong> is also significantly improved.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1904-1909"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688226","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":"On the pK of crystal surfaces: molecular modeling of crystallite protonation, local reorganization, and solute dissociation†","authors":"Patrick Duchstein, Moritz Macht and Dirk Zahn","doi":"10.1039/D4CE01292E","DOIUrl":"https://doi.org/10.1039/D4CE01292E","url":null,"abstract":"<p >We demonstrate the application of the ‘instantaneous p<em>K</em>’ approach to the molecular dynamics simulation of crystallite models exposed to an acidic solvent environment. For this, the bulk solution properties pH and p<em>K</em> are scrutinized into local aspects and effectively characterized for individual molecules of crystal faces, edges and steps, respectively. To illustrate this concept, we introduce two prototype cases: the acid-induced dissociation of i) calcite and ii) carbamazepine (CBZ, form III) drugs. We find acid-induced calcite dissociation follows a rather intuitive mechanism, namely the protonation of crystal edges/steps leading to ion-by-ion dissociation of HCO<small>₃</small><small>⁻</small> and Ca<small>²⁺</small> species into water. In contrast, our simulations of CBZ solvation at pH = 3 and pH = 2, respectively, reveal a more complex dissolution behavior. The molecular crystals were found to accommodate a substantial degree of CBZ protonation without drug release to the solvent. Instead, the crystallite edges and corners are re-arranged in favor of a surprisingly stable core–shell structure featuring a CBZ core and a mixed CBZ/CBZH shell of +0.005 and +0.03 C m<small>⁻²</small> surface charge at pH = 3 and pH = 2, respectively. The resulting crystallite models are persistent and even more drastic acidity is needed to enable actual dissociation of CBZH into water.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1392-1398"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01292e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535720","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":"Tb–TATAB crystalline organic framework material based on triazine tricarboxylic acid ligand: photophysical properties and fluorescence sensing applications†","authors":"Yuan Liu, Jin Long Li, Na Zhang, Yue Zhao, Qing Lin Guan, Yong Heng Xing and Feng Ying Bai","doi":"10.1039/D4CE01294A","DOIUrl":"https://doi.org/10.1039/D4CE01294A","url":null,"abstract":"<p >A Tb-MOF complex based on triazine tricarboxylic acid ligands (2,4,6-tri(4-carboxylaniline)-1,3,5-triazine (H<small>₃</small>TATAB)) was constructed through the reaction of the rare earth metal Tb(<small>III</small>) and H<small>₃</small>TATAB. The complex featured a three-dimensional non-interpenetrating network structure constructed by the binuclear secondary building unit [Tb<small>₂</small>(CO<small>₂</small>)<small>₆</small>] and the H<small>₃</small>TATAB ligand. The complex exhibited excellent solvent stability, acid–base stability and thermal stability. Based on the fluorescence characteristics of the complex, it was found that the complex exhibited a sensitive fluorescence response and was recyclable for 7 kinds of nitroaromatic compounds (NACs) with different substituted groups, as well as heavy metal anions and cations (Cr<small>₂</small>O<small>₇</small><small>²⁻</small> and Fe<small>³⁺</small>). The fluorescence quenching behavior was preliminarily attributed to the synergistic effect of the CA and PET mechanisms.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1939-1949"},"PeriodicalIF":2.6,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688230","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}