Pub Date : 2025-01-28DOI: 10.1021/acs.cgd.4c0170910.1021/acs.cgd.4c01709
Shi Zhang, Yudie Zhou, Anna Tuo, Shufan Chen, Qingfu Zhang, Xu Zhang, Kecai Xiong* and Yanli Gai*,
The solvothermal reaction of In3+ and 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride (H2bcbpCl2) in the presence of oxalate resulted in the formation of a 3D metal–organic framework (1) with a 65.8 topology. Compound 1 features a unique oxalate-bridged honeycomb (hcb) layer [In2(μ2-C2O4)3]∞, pillared by bcbp ligands. To the best of our knowledge, this presents the first documented 3D metal–organic coordination polymer constructed by an oxalate-bridged hcb layer. Remarkably, compound 1 demonstrates selective detection of nitroaromatics and nitrofurans in water through a fluorescence quenching mechanism, exhibiting high quenching efficiencies (Ksv) and low limits of detection (LOD). Mechanistic studies reveal that this quenching phenomenon is attributed to photoinduced electron transfer (PET), inner filter effect (IFE) and fluorescence resonance energy transfer (FRET). Moreover, compound 1 displays photochromic properties, with the structural variations and electron transfer pathways elucidated through single-crystal X-ray diffraction (SC-XRD) analysis.
{"title":"A Stable Viologen-Based Metal–Organic Framework for Fluorescence Detection of Nitroaromatics and Nitrofuran Antibiotics in Water","authors":"Shi Zhang, Yudie Zhou, Anna Tuo, Shufan Chen, Qingfu Zhang, Xu Zhang, Kecai Xiong* and Yanli Gai*, ","doi":"10.1021/acs.cgd.4c0170910.1021/acs.cgd.4c01709","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01709https://doi.org/10.1021/acs.cgd.4c01709","url":null,"abstract":"<p >The solvothermal reaction of In<sup>3+</sup> and 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride (H<sub>2</sub>bcbpCl<sub>2</sub>) in the presence of oxalate resulted in the formation of a 3D metal–organic framework (<b>1</b>) with a 6<sup>5</sup>.8 topology. Compound <b>1</b> features a unique oxalate-bridged honeycomb (hcb) layer [In<sub>2</sub>(μ<sub>2</sub>-C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sub>∞</sub>, pillared by bcbp ligands. To the best of our knowledge, this presents the first documented 3D metal–organic coordination polymer constructed by an oxalate-bridged hcb layer. Remarkably, compound <b>1</b> demonstrates selective detection of nitroaromatics and nitrofurans in water through a fluorescence quenching mechanism, exhibiting high quenching efficiencies (<i>K</i><sub>sv</sub>) and low limits of detection (LOD). Mechanistic studies reveal that this quenching phenomenon is attributed to photoinduced electron transfer (PET), inner filter effect (IFE) and fluorescence resonance energy transfer (FRET). Moreover, compound <b>1</b> displays photochromic properties, with the structural variations and electron transfer pathways elucidated through single-crystal X-ray diffraction (SC-XRD) analysis.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"494–501 494–501"},"PeriodicalIF":3.2,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126916","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}
The assembly of helical structures with artificial molecules has been one of the focuses of supramolecular chemistry, while anion-based helical structures, especially infinite helical chains, have rarely been reported. Herein we present a strategy to assemble double-strand helical chains based on the anion coordination (hydrogen bonding in nature) of a C2-symmetric bis-monourea ligand L1, with a sulfate anion (2) or dihydrogen phosphate tetramers (3). Both of the assemblies were elucidated by single-crystal structures. Moreover, a control single-crystal structure, 1, which was formed by one ligand L1 and two chloride ions, was also obtained for comparison, highlighting the necessity of the four coordination sites of the sulfate anion and dihydrogen phosphate tetramers for assembling the double-strand helical chains. The sulfate-based double-strand helix 2 was featured with absolute chirality as a result of the self-resolving crystallization. Within the chain-like structure of 2, the V-shaped configuration of L1 led to the formation of cavities that are suitable for encapsulating TEA+ cations through C–H···π interactions, thus making helix 2 appear as an infinite molecular train. Similarly, the anion-cluster dihydrogen phosphate tetramer, as an enlarged analogy of the sulfate anion, also providing four oxygen-based binding sites, induced another infinite molecular train 3 with the bigger TPA+ cations loaded in the cavities. In contrast with the chiral structure of 2, the structure of 3 is mesomeric, showing the sensitivity of the anionic helix toward the anion node.
{"title":"Double-Helical Chain Directed by Sulfate and Phosphate Tetramers","authors":"Xianghua Lv, Xuemin Deng, Wei Zuo, Yue Wang, Chaochao Fan* and Chuandong Jia*, ","doi":"10.1021/acs.cgd.4c0148610.1021/acs.cgd.4c01486","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01486https://doi.org/10.1021/acs.cgd.4c01486","url":null,"abstract":"<p >The assembly of helical structures with artificial molecules has been one of the focuses of supramolecular chemistry, while anion-based helical structures, especially infinite helical chains, have rarely been reported. Herein we present a strategy to assemble double-strand helical chains based on the anion coordination (hydrogen bonding in nature) of a <i>C</i><sub>2</sub>-symmetric bis-monourea ligand <b>L</b><sup>1</sup>, with a sulfate anion (<b>2</b>) or dihydrogen phosphate tetramers (<b>3</b>). Both of the assemblies were elucidated by single-crystal structures. Moreover, a control single-crystal structure, <b>1</b>, which was formed by one ligand <b>L</b><sup>1</sup> and two chloride ions, was also obtained for comparison, highlighting the necessity of the four coordination sites of the sulfate anion and dihydrogen phosphate tetramers for assembling the double-strand helical chains. The sulfate-based double-strand helix <b>2</b> was featured with absolute chirality as a result of the self-resolving crystallization. Within the chain-like structure of <b>2</b>, the V-shaped configuration of <b>L</b><sup>1</sup> led to the formation of cavities that are suitable for encapsulating TEA<sup>+</sup> cations through C–H···π interactions, thus making helix <b>2</b> appear as an infinite molecular train. Similarly, the anion-cluster dihydrogen phosphate tetramer, as an enlarged analogy of the sulfate anion, also providing four oxygen-based binding sites, induced another infinite molecular train <b>3</b> with the bigger TPA<sup>+</sup> cations loaded in the cavities. In contrast with the chiral structure of <b>2</b>, the structure of <b>3</b> is mesomeric, showing the sensitivity of the anionic helix toward the anion node.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"680–686 680–686"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127047","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}
The europium (Eu3+) ion is an important lanthanide cation for rare-earth phosphors, with red emission around 620 nm. It exhibits two typical hypersensitive transitions, namely, absorbed 7F0 → 5D2 and emitted 5D0 → 7F2, where the transition electric dipole intensities among electron levels are strongly correlated to ligands and lattices. This case indicates that Eu3+ should be an excellent fluorescence probe to investigate the weak and sensitive electron–phonon coupling effect in 4f–4f transitions. Here, we established a qualitative relation between the hypersensitive transitions and electron–phonon coupling by two parameters, bond length and average polarizability of ligand, that short length and large polarizability are beneficial for strengthened electron–phonon coupling. In addition, we grew three Eu3+-doped crystals: Eu:La2CaB10O19, Eu:Lu2O3, and Eu:Y2O(SiO4), and measured their photoluminescence-excited (PLE) and photoluminescence (PL) spectra, respectively. We found clear phonon sidebands in their PLE spectra, with some satellites at shorter wavelengths associated with phonon-assisted excitation. Based on the calculated Huang–Rhys factors, we demonstrated that the special “free-oxygen” motif in Eu:Y2O(SiO4) is beneficial for strengthening phonon-assisted excitations. This work provides a helpful guideline for searching for strong electron–phonon coupling crystals in rare-earth materials.
{"title":"Phonon-Assisted Photoluminescence-Excited (PLE) Spectrum in Eu3+-Doped Single Crystals","authors":"Fangyan Wang, Fei Liang*, Fangli Jing, Dazhi Lu, Haohai Yu*, Huaijin Zhang* and Yicheng Wu, ","doi":"10.1021/acs.cgd.4c0165810.1021/acs.cgd.4c01658","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01658https://doi.org/10.1021/acs.cgd.4c01658","url":null,"abstract":"<p >The europium (Eu<sup>3+</sup>) ion is an important lanthanide cation for rare-earth phosphors, with red emission around 620 nm. It exhibits two typical hypersensitive transitions, namely, absorbed <sup>7</sup>F<sub>0</sub> → <sup>5</sup>D<sub>2</sub> and emitted <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>2</sub>, where the transition electric dipole intensities among electron levels are strongly correlated to ligands and lattices. This case indicates that Eu<sup>3+</sup> should be an excellent fluorescence probe to investigate the weak and sensitive electron–phonon coupling effect in 4f–4f transitions. Here, we established a qualitative relation between the hypersensitive transitions and electron–phonon coupling by two parameters, bond length and average polarizability of ligand, that short length and large polarizability are beneficial for strengthened electron–phonon coupling. In addition, we grew three Eu<sup>3+</sup>-doped crystals: Eu:La<sub>2</sub>CaB<sub>10</sub>O<sub>19</sub>, Eu:Lu<sub>2</sub>O<sub>3</sub>, and Eu:Y<sub>2</sub>O(SiO<sub>4</sub>), and measured their photoluminescence-excited (PLE) and photoluminescence (PL) spectra, respectively. We found clear phonon sidebands in their PLE spectra, with some satellites at shorter wavelengths associated with phonon-assisted excitation. Based on the calculated Huang–Rhys factors, we demonstrated that the special “free-oxygen” motif in Eu:Y<sub>2</sub>O(SiO<sub>4</sub>) is beneficial for strengthening phonon-assisted excitations. This work provides a helpful guideline for searching for strong electron–phonon coupling crystals in rare-earth materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"838–848 838–848"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127714","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}
Pub Date : 2025-01-27DOI: 10.1021/acs.cgd.4c0122810.1021/acs.cgd.4c01228
Linfeng Liang*, Yang Yin, Feng-Fan Yang, Jing Yang, Yin-Kang Ding and Wei Zhou*,
Hydrogen-Bonded Crystals (HBCs) hold potential as proton conduction materials, yet they face challenges in achieving high proton conductivity, despite their well-defined structures and abundant inherent hydrogen bonding networks. To enhance the proton conductivity, a strategy involving molecule design with cyclic steric hindrance to facilitate proton transfer is proposed. Three HBCs, named HBC-29, HBC-30, and HBC-31 are reported here. HBC-29 and HBC-31 incorporating a cyclic steric hindrance group through a cyclocondensation reaction significantly enhance proton conductivity compared with HBC-30 without a hindrance group. HBC-31 achieves high proton conductivity of 6.18 × 10–2 S cm–1 at 60 °C and 95% RH. These findings demonstrate the key role of the cyclic steric hindrance effect in augmenting proton conductivity in HBCs, offering valuable insights for future HBC material design.
{"title":"Proton Conductivity Variations in Hydrogen-Bonded Crystals Induced by Cyclic Steric Hindrance","authors":"Linfeng Liang*, Yang Yin, Feng-Fan Yang, Jing Yang, Yin-Kang Ding and Wei Zhou*, ","doi":"10.1021/acs.cgd.4c0122810.1021/acs.cgd.4c01228","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01228https://doi.org/10.1021/acs.cgd.4c01228","url":null,"abstract":"<p >Hydrogen-Bonded Crystals (HBCs) hold potential as proton conduction materials, yet they face challenges in achieving high proton conductivity, despite their well-defined structures and abundant inherent hydrogen bonding networks. To enhance the proton conductivity, a strategy involving molecule design with cyclic steric hindrance to facilitate proton transfer is proposed. Three HBCs, named <b>HBC-29</b>, <b>HBC-30</b>, and <b>HBC-31</b> are reported here. <b>HBC-29</b> and <b>HBC-31</b> incorporating a cyclic steric hindrance group through a cyclocondensation reaction significantly enhance proton conductivity compared with <b>HBC-30</b> without a hindrance group. <b>HBC-31</b> achieves high proton conductivity of 6.18 × 10<sup>–2</sup> S cm<sup>–1</sup> at 60 °C and 95% RH. These findings demonstrate the key role of the cyclic steric hindrance effect in augmenting proton conductivity in HBCs, offering valuable insights for future HBC material design.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"488–493 488–493"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126981","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}
Pub Date : 2025-01-27DOI: 10.1021/acs.cgd.4c0125110.1021/acs.cgd.4c01251
Bo Ding, Bo-Chen Hou, Zheng-Yu Liu, Jia-Jun Wang, Xiu-Guang Wang, Shuang Zhu and En-Cui Yang*,
Photochromic inorganic–organic hybrids with reversible color transitions under photoirradiation have exhibited promising applications in a wide variety of fields. However, the decisive factors for the photochromism assisted by metal coordination are still unclear and are a great challenge. Herein, to explore the preferred geometries between the electron donor (D) and acceptor (A) facilitating the photoinduced electron transfer (PIET), four crystalline 2,6-di(1,6-naphthyridin-2-yl)pyridine (DNP)-based Zn(II)-complexes have been designed and prepared solvothermally by varying the tethers of dicarboxylate coligands. Four anionic carboxylate pairs connected by length- and flexibility-adjustable tethers have significantly dominated the twisted carboxylate-Zn(II)-chelating DNP substructures and overall dimensionality of the resultant hybrids (three-dimensional pillared layered framework, bent and helical one-dimensional chains, and zero-dimensional binuclear entity), resulting in selective photochromism under UV lamp irradiation. More importantly, the accurate structural comparisons and theoretical calculations at the molecular level have demonstrated that the anion−π interactions within the local COO–-Zn(II)-DNP substructures strongly correlate with the through-space PIET, resulting in selective photochromism. These findings are highly informative for the rational design and skillful manipulation of crystalline redox-type photochromic materials.
{"title":"Selective Photochromism of 2,6-Di(1,6-naphthyridin-2-yl)pyridine-Based Zinc(II)-Complexes by Varying the Tethers of Dicarboxylate Coligands: Significance of Anion−π Interactions on Photo-Induced Electron Transfer","authors":"Bo Ding, Bo-Chen Hou, Zheng-Yu Liu, Jia-Jun Wang, Xiu-Guang Wang, Shuang Zhu and En-Cui Yang*, ","doi":"10.1021/acs.cgd.4c0125110.1021/acs.cgd.4c01251","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01251https://doi.org/10.1021/acs.cgd.4c01251","url":null,"abstract":"<p >Photochromic inorganic–organic hybrids with reversible color transitions under photoirradiation have exhibited promising applications in a wide variety of fields. However, the decisive factors for the photochromism assisted by metal coordination are still unclear and are a great challenge. Herein, to explore the preferred geometries between the electron donor (D) and acceptor (A) facilitating the photoinduced electron transfer (PIET), four crystalline 2,6-di(1,6-naphthyridin-2-yl)pyridine (DNP)-based Zn(II)-complexes have been designed and prepared solvothermally by varying the tethers of dicarboxylate coligands. Four anionic carboxylate pairs connected by length- and flexibility-adjustable tethers have significantly dominated the twisted carboxylate-Zn(II)-chelating DNP substructures and overall dimensionality of the resultant hybrids (three-dimensional pillared layered framework, bent and helical one-dimensional chains, and zero-dimensional binuclear entity), resulting in selective photochromism under UV lamp irradiation. More importantly, the accurate structural comparisons and theoretical calculations at the molecular level have demonstrated that the anion−π interactions within the local COO<sup>–</sup>-Zn(II)-DNP substructures strongly correlate with the through-space PIET, resulting in selective photochromism. These findings are highly informative for the rational design and skillful manipulation of crystalline redox-type photochromic materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"572–580 572–580"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127651","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}
Pub Date : 2025-01-27DOI: 10.1021/acs.cgd.4c0134610.1021/acs.cgd.4c01346
Gautier Duroux, Matheus De Souza Lima Mendes, Iryna Makarchuk, Théo Lucante, Céline Kiefer, Sonia Buffière, François Weill, Walid Baaziz, Thierry Buffeteau, Sylvain Nlate, Reiko Oda, Patrick Rosa, Elizabeth A. Hillard*, Benoit P. Pichon* and Emilie Pouget*,
The integration of chiral and magnetic properties has gained increasing interest due to its potential for enabling magneto-chiral phenomena. However, the development of nanoscale chiral systems that exhibit strong responsiveness to both light and magnetic fields remains largely underexplored. In this context, we investigate the use of silica nanohelices as a chiral platform for inducing circular dichroism (CD) in iron oxide nanoparticles (NPs). Two strategies are compared: an ex situ approach, where the NPs are synthesized independently and then grafted onto the helices, and an in situ approach, where the NPs are directly formed on the surface of the helices. This comparison enables us to evaluate the chirality induction arising from helicoidal assembly versus chiral shape, respectively. The efficiency of each strategy was assessed by electronic CD (ECD) and magnetic CD (MCD) spectroscopies. The results show that chirality induction on iron oxide nanocrystals is negligible with the ex situ method, whereas weak but unambiguous ECD signals are observed following the in situ approach. Furthermore, a comparative analysis of chirality induction in magnetite (Fe3O4) vs. maghemite (γ-Fe2O3) with both strategies is presented and discussed.
{"title":"Challenges in Chirality Induction in Iron Oxide Nanoparticles: In Situ vs Ex Situ Growth on Helical Nanoplatforms","authors":"Gautier Duroux, Matheus De Souza Lima Mendes, Iryna Makarchuk, Théo Lucante, Céline Kiefer, Sonia Buffière, François Weill, Walid Baaziz, Thierry Buffeteau, Sylvain Nlate, Reiko Oda, Patrick Rosa, Elizabeth A. Hillard*, Benoit P. Pichon* and Emilie Pouget*, ","doi":"10.1021/acs.cgd.4c0134610.1021/acs.cgd.4c01346","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01346https://doi.org/10.1021/acs.cgd.4c01346","url":null,"abstract":"<p >The integration of chiral and magnetic properties has gained increasing interest due to its potential for enabling magneto-chiral phenomena. However, the development of nanoscale chiral systems that exhibit strong responsiveness to both light and magnetic fields remains largely underexplored. In this context, we investigate the use of silica nanohelices as a chiral platform for inducing circular dichroism (CD) in iron oxide nanoparticles (NPs). Two strategies are compared: an <i>ex situ</i> approach, where the NPs are synthesized independently and then grafted onto the helices, and an <i>in situ</i> approach, where the NPs are directly formed on the surface of the helices. This comparison enables us to evaluate the chirality induction arising from helicoidal assembly versus chiral shape, respectively. The efficiency of each strategy was assessed by electronic CD (ECD) and magnetic CD (MCD) spectroscopies. The results show that chirality induction on iron oxide nanocrystals is negligible with the <i>ex situ</i> method, whereas weak but unambiguous ECD signals are observed following the <i>in situ</i> approach. Furthermore, a comparative analysis of chirality induction in magnetite (Fe<sub>3</sub>O<sub>4</sub>) vs. maghemite (γ-Fe<sub>2</sub>O<sub>3</sub>) with both strategies is presented and discussed.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"603–611 603–611"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127587","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}
Pub Date : 2025-01-27DOI: 10.1021/acs.cgd.4c0168010.1021/acs.cgd.4c01680
Ritobroto Sikdar, Balaranjan Selvaratnam, Vidyanshu Mishra and Arthur Mar*,
Laves phases AB2, which represent the largest group of intermetallic compounds, have many applications as structural and functional materials, whose properties can be optimized through the tuning of solid solutions such as (A1,A2)B2 or A(B1,B2)2. Although they are known to be governed by size and electronic factors, there is no universal set of rules that is able to predict which arbitrary combination of elements will lead to Laves structures. Models have been recently developed that can predict Laves structures accurately based on conventional machine learning algorithms, but more interpretable models would be desirable. Through application of the sure independence screening and sparsifying operator (SISSO) method, modified using decision trees as the scoring function, simple descriptors based on elemental properties were sought to classify Laves vs non-Laves structures within a data set consisting of 534 binary and 3833 ternary experimentally known intermetallic phases reported in Pearson’s Crystal Data. A model based on a one-dimensional descriptor was proposed that depends on elemental properties of the A and B components, with the electron density at the boundary of the Wigner–Seitz cell for the B component playing an important role. This model gave an accuracy of 90% in predicting Laves vs non-Laves structures among binary and ternary phases. As a test of the model, the solid solubility limits for Dy(AgxAl1–x)2 and Er(AgxAl1–x)2 Laves phases were predicted and then experimentally validated through arc-melting reactions and structural characterization.
{"title":"Is There a Simple Descriptor to Predict Laves Phases?","authors":"Ritobroto Sikdar, Balaranjan Selvaratnam, Vidyanshu Mishra and Arthur Mar*, ","doi":"10.1021/acs.cgd.4c0168010.1021/acs.cgd.4c01680","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01680https://doi.org/10.1021/acs.cgd.4c01680","url":null,"abstract":"<p >Laves phases AB<sub>2</sub>, which represent the largest group of intermetallic compounds, have many applications as structural and functional materials, whose properties can be optimized through the tuning of solid solutions such as (A1,A2)B<sub>2</sub> or A(B1,B2)<sub>2</sub>. Although they are known to be governed by size and electronic factors, there is no universal set of rules that is able to predict which arbitrary combination of elements will lead to Laves structures. Models have been recently developed that can predict Laves structures accurately based on conventional machine learning algorithms, but more interpretable models would be desirable. Through application of the sure independence screening and sparsifying operator (SISSO) method, modified using decision trees as the scoring function, simple descriptors based on elemental properties were sought to classify Laves vs non-Laves structures within a data set consisting of 534 binary and 3833 ternary experimentally known intermetallic phases reported in Pearson’s Crystal Data. A model based on a one-dimensional descriptor was proposed that depends on elemental properties of the A and B components, with the electron density at the boundary of the Wigner–Seitz cell for the B component playing an important role. This model gave an accuracy of 90% in predicting Laves vs non-Laves structures among binary and ternary phases. As a test of the model, the solid solubility limits for Dy(Ag<sub><i>x</i></sub>Al<sub>1–<i>x</i></sub>)<sub>2</sub> and Er(Ag<sub><i>x</i></sub>Al<sub>1–<i>x</i></sub>)<sub>2</sub> Laves phases were predicted and then experimentally validated through arc-melting reactions and structural characterization.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"849–857 849–857"},"PeriodicalIF":3.2,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127000","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}
Pub Date : 2025-01-25DOI: 10.1021/acs.cgd.4c0152810.1021/acs.cgd.4c01528
Wenhao Zhang, Chao Dong, Meiyan Cui, Tianyu Zhu, Zhiying Zhao, Junfeng Wang and Zhangzhen He*,
New compounds M3(SeO3)2(Mo2O6F2) (M = Co, Ni, Cu) were obtained by a hydrothermal method, showing a linear trimeric structure composed of twisted MO5F octahedra and MO4F2 octahedra. The trimers are connected by [MoSeO6F] clusters formed by (SeO3) trigonal cones and (MoO5F) octahedra. The magnetic measurements demonstrated that all three compounds exhibited an antiferromagnetic order at low temperatures, where a 1/3 magnetization plateau can be observed for the Cu compound, while two field-induced magnetic transitions can be observed for the Co compound, and no anomaly was observed for the Ni compound, indicating such magnetization behaviors dependent on different magnetic ions.
{"title":"New Selenite–Molybdate Family M3(SeO3)2(Mo2O6F2) (M = Co, Ni, Cu): Structure and Magnetism","authors":"Wenhao Zhang, Chao Dong, Meiyan Cui, Tianyu Zhu, Zhiying Zhao, Junfeng Wang and Zhangzhen He*, ","doi":"10.1021/acs.cgd.4c0152810.1021/acs.cgd.4c01528","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01528https://doi.org/10.1021/acs.cgd.4c01528","url":null,"abstract":"<p >New compounds <i>M</i><sub>3</sub>(SeO<sub>3</sub>)<sub>2</sub>(Mo<sub>2</sub>O<sub>6</sub>F<sub>2</sub>) (<i>M</i> = Co, Ni, Cu) were obtained by a hydrothermal method, showing a linear trimeric structure composed of twisted MO<sub>5</sub>F octahedra and MO<sub>4</sub>F<sub>2</sub> octahedra. The trimers are connected by [MoSeO<sub>6</sub>F] clusters formed by (SeO<sub>3</sub>) trigonal cones and (MoO<sub>5</sub>F) octahedra. The magnetic measurements demonstrated that all three compounds exhibited an antiferromagnetic order at low temperatures, where a 1/3 magnetization plateau can be observed for the Cu compound, while two field-induced magnetic transitions can be observed for the Co compound, and no anomaly was observed for the Ni compound, indicating such magnetization behaviors dependent on different magnetic ions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"734–739 734–739"},"PeriodicalIF":3.2,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126889","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}
Pub Date : 2025-01-25DOI: 10.1021/acs.cgd.4c0126610.1021/acs.cgd.4c01266
Yilin Cao, Zhixiang Zhang, Tao Yu, Bo Chen, Yuanjing Wang, Qin Lv, Zihui Meng*, Yingzhe Liu* and Chuan Xiao*,
The most recent global research developments concerning pentazolate salts (CA+N5–) have been reviewed, which mainly include the structural creation concept of synthesized CA+N5–, the structural design methods of novel CA+N5–, and the application of performance prediction methods for CA+N5–. The creation of CA+N5– relies on trial-and-error experiments with a long development cycle and high cost. However, the work driven by computation is rarely performed and difficult to support the experimental exploration, due to the limited ability of cation design and poor accuracy of performance prediction. Finally, the future development of CA+N5– was prospected. With the aid of data mining, high-throughput molecular-designing, quantum chemistry, and machine learning, it is expected to deeply understand the structure–activity relationships and accelerate the design of cations with excellent performances in the future.
{"title":"Structure Design and Property Prediction of Energetic Pentazolate Salt: An Overview","authors":"Yilin Cao, Zhixiang Zhang, Tao Yu, Bo Chen, Yuanjing Wang, Qin Lv, Zihui Meng*, Yingzhe Liu* and Chuan Xiao*, ","doi":"10.1021/acs.cgd.4c0126610.1021/acs.cgd.4c01266","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01266https://doi.org/10.1021/acs.cgd.4c01266","url":null,"abstract":"<p >The most recent global research developments concerning pentazolate salts (CA<sup>+</sup>N<sub>5</sub><sup>–</sup>) have been reviewed, which mainly include the structural creation concept of synthesized CA<sup>+</sup>N<sub>5</sub><sup>–</sup>, the structural design methods of novel CA<sup>+</sup>N<sub>5</sub><sup>–</sup>, and the application of performance prediction methods for CA<sup>+</sup>N<sub>5</sub><sup>–</sup>. The creation of CA<sup>+</sup>N<sub>5</sub><sup>–</sup> relies on trial-and-error experiments with a long development cycle and high cost. However, the work driven by computation is rarely performed and difficult to support the experimental exploration, due to the limited ability of cation design and poor accuracy of performance prediction. Finally, the future development of CA<sup>+</sup>N<sub>5</sub><sup>–</sup> was prospected. With the aid of data mining, high-throughput molecular-designing, quantum chemistry, and machine learning, it is expected to deeply understand the structure–activity relationships and accelerate the design of cations with excellent performances in the future.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"581–592 581–592"},"PeriodicalIF":3.2,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126886","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}
Pub Date : 2025-01-24DOI: 10.1021/acs.cgd.4c0154210.1021/acs.cgd.4c01542
Yoshihiro Kangawa*, Akira Kusaba, Takahiro Kawamura, Pawel Kempisty, Kana Ishisone and Mauro Boero,
We investigate theoretically the formation mechanisms of the unintentional compositional gradient layer occurring at AlGaN/AlN heterointerfaces during metal–organic chemical vapor deposition (MOCVD). The study of heterointerface morphology is crucial for developing AlGaN deep-ultraviolet light-emitting laser diodes. After studying the stability of the surface reconstructions with intrinsic point defects in their subsurface layers using an ab initio-based approach, we inspect the impact of defects on the atomic interdiffusion at the heterointerfaces by Monte Carlo simulation. The relationship between MOCVD conditions and the type of dominant intrinsic point defects is clarified. We find that (i) cation and anion vacancy complexes are dominant in the subsurface layers above 1000 °C and (ii) they accumulate near the AlGaN/AlN heterointerface during growth, causing cation interdiffusion, i.e., the formation of compositional gradient layers. Controlling the type of intrinsic point defects incorporated during the surface growth in MOCVD is a key factor in preserving atomically flat heterointerfaces.
The formation mechanisms of the unintentional compositional gradient layer occurring at AlGaN/AlN heterointerfaces during metal−organic chemical vapor deposition (MOCVD) have been investigated. AlGaN/GaN heterointerface degradation mechanism includes the following: (1) Cation−anion vacancy pairs are incorporated from the reconstructed surface. (2) The vacancy pairs diffuse along the AlGaN/AlN heterointerface during growth. (3) As a result, an unintended interdiffusion layer (composition gradient layer) is formed.
{"title":"Influence of Intrinsic Point Defects Incorporated from Growth Surface on Atomic Interdiffusion and Unintentional Compositional Gradient in AlGaN/AlN Heterointerfaces","authors":"Yoshihiro Kangawa*, Akira Kusaba, Takahiro Kawamura, Pawel Kempisty, Kana Ishisone and Mauro Boero, ","doi":"10.1021/acs.cgd.4c0154210.1021/acs.cgd.4c01542","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01542https://doi.org/10.1021/acs.cgd.4c01542","url":null,"abstract":"<p >We investigate theoretically the formation mechanisms of the unintentional compositional gradient layer occurring at AlGaN/AlN heterointerfaces during metal–organic chemical vapor deposition (MOCVD). The study of heterointerface morphology is crucial for developing AlGaN deep-ultraviolet light-emitting laser diodes. After studying the stability of the surface reconstructions with intrinsic point defects in their subsurface layers using an ab initio-based approach, we inspect the impact of defects on the atomic interdiffusion at the heterointerfaces by Monte Carlo simulation. The relationship between MOCVD conditions and the type of dominant intrinsic point defects is clarified. We find that (i) cation and anion vacancy complexes are dominant in the subsurface layers above 1000 °C and (ii) they accumulate near the AlGaN/AlN heterointerface during growth, causing cation interdiffusion, i.e., the formation of compositional gradient layers. Controlling the type of intrinsic point defects incorporated during the surface growth in MOCVD is a key factor in preserving atomically flat heterointerfaces.</p><p >The formation mechanisms of the unintentional compositional gradient layer occurring at AlGaN/AlN heterointerfaces during metal−organic chemical vapor deposition (MOCVD) have been investigated. AlGaN/GaN heterointerface degradation mechanism includes the following: (1) Cation−anion vacancy pairs are incorporated from the reconstructed surface. (2) The vacancy pairs diffuse along the AlGaN/AlN heterointerface during growth. (3) As a result, an unintended interdiffusion layer (composition gradient layer) is formed.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 3","pages":"740–746 740–746"},"PeriodicalIF":3.2,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01542","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127201","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}