Crystal Growth & Design最新文献

{"title":"Spontaneous Deracemization of the DMY Racemic Compound with Two Stereocenters through a Stepwise Process of Cocrystallization-Induced Resolution and Solution Racemization","authors":"Yujiang Xie,&nbsp;Shubo Liu,&nbsp;Jie Sun,&nbsp;Weiwei Tang* and Junbo Gong*,&nbsp;","doi":"10.1021/acs.cgd.4c0114410.1021/acs.cgd.4c01144","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01144https://doi.org/10.1021/acs.cgd.4c01144","url":null,"abstract":"<p >Processes that allow access to enantiomerically pure drugs are of the utmost importance to maximize pharmacological activity while minimizing the side effects. This work develops a novel diastereomeric cocrystallization-induced spontaneous deracemization process for a racemic compound, dihydromyricetin (DMY), which contains two stereocenters. A pair of diastereomeric cocrystals, (2<i>R</i>,3<i>R</i>-DMY)₂:<i>R</i>-<i>N</i>-benzyl-1-phenylethylamine and (2<i>R</i>,3<i>R</i>-DMY)₂:<i>S</i>-<i>N</i>-benzyl-1-phenylethylamine, the latter of which is equivalent to (2<i>S</i>,3<i>S</i>-DMY)₂:<i>R</i>-<i>N</i>-benzyl-1-phenylethylamine, was discovered via a complete screening of 12 chiral coformers using both slurry and liquid-assisted grinding methods. Crystal structure of these cocrystals was determined using single-crystal X-ray diffraction and reported for the first time. Enantioseparation of <i>rac</i>-DMY by virtue of diastereomeric cocrystals was designed and optimized through slurry and cooling crystallization methods, resulting in a product of 81% enantiomeric purity with a yield of only 31%. Further, the racemization process of DMY enantiomers with various influence factors was examined, and the optimal racemization condition that achieves simultaneous racemization of the two stereocenters was determined. Finally, a stepwise cocrystallization-induced deracemization process of <i>rac</i>-DMY that combines chiral resolution by cocrystallization and racemization of recycling mother liquor was developed, producing an enantiomeric purity of 97.5% and a maximal yield of 68%.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9649–9659 9649–9659"},"PeriodicalIF":3.2,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671686","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":"Streamlined In Situ X-ray Crystallography of Gas Sorption State as Realized through the De Novo Development of a Novel Crystal Mount","authors":"Kazuaki Yamanaka,&nbsp;Masayuki Moritake,&nbsp;Hiroki Takahashi and Hirohito Tsue*,&nbsp;","doi":"10.1021/acs.cgd.4c0087110.1021/acs.cgd.4c00871","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00871https://doi.org/10.1021/acs.cgd.4c00871","url":null,"abstract":"<p >In situ X-ray crystallography of gas sorption states is a powerful approach to gain profound insights into the nature of gas sorption phenomena, and its implementation is quite skillful. To broaden the range of implementation choices and also to further facilitate and generalize in situ X-ray crystallographic analysis under a gas atmosphere, we have carried out the de novo design and development of a novel crystal mount (NCM), which encompasses the following four features: (1) the NCM is designed to be as compact as possible in order not to interfere with the incident X-ray beam of a laboratory diffractometer. (2) The inside of a capillary fixed to the NCM is easily evacuated by a vacuum pump. (3) A target gas is also easily introduced into the capillary containing a single crystal. (4) Gas pressure is freely adjustable up to 3.9 atm. As a case study, the NCM was subjected to in situ X-ray crystallography under a CO₂ atmosphere, and we fully succeeded in analyzing the CO₂ sorption state of a dipeptide-based molecular crystal. The present de novo development of an NCM with versatility and ease of handling would open new opportunities for in situ X-ray crystallography.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9433–9439 9433–9439"},"PeriodicalIF":3.2,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671414","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":"Photoresponsive Halogen-Bonded Complexes of 1,3,5-Trifluoro-2,4,6-triiodobenzene and Alkoxyazopyridine Derivatives Based on Py-N···I Interactions: Synthesis, Structural, and Theoretical Insights","authors":"Jyoti Swarup Thakur,&nbsp;Omkar Dash,&nbsp;Kapil S. Ingle,&nbsp;Komal B. Lahoti,&nbsp;Athul Sudheendranath,&nbsp;Nagesh A. Bhale,&nbsp;Amol G. Dikundwar and Susanta K. Nayak*,&nbsp;","doi":"10.1021/acs.cgd.4c0078110.1021/acs.cgd.4c00781","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00781https://doi.org/10.1021/acs.cgd.4c00781","url":null,"abstract":"<p >A series of (<i>E</i>)-4-((4-alkoxyphenyl)diazenyl)pyridine (<b>AZ-<i>n</i></b>) derivatives were synthesized with varying alkoxy spacers (<i>n</i> = 8, 9, and 10), and their halogen-bonded complexes were obtained with 1,3,5-trifluoro-2,4,6-triiodobenzene in different stoichiometric ratios, which were further characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), single-crystal X-ray diffraction (SC-XRD), and powder X-ray diffraction (P-XRD) techniques. The structural analysis revealed the presence of Py-N···I halogen bond (XB) interactions in the complexes, resulting in a bent-shaped architecture rather than a star-shaped one. Hirshfeld surface analysis revealed the contribution of XB along different intermolecular interactions in the crystal packing. Computational analyses such as noncovalent index (NCI), quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), and natural bond orbital (NBO) were carried out to understand the nature, strength, and electronic characteristics of XBs in these complexes. Further, these XB complexes show excellent photoresponsive behavior upon UV illumination, introducing a new range of supramolecular photoresponsive materials self-assembled by halogen bonding, thereby broadening the scope of potential applications within their respective systems.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9391–9402 9391–9402"},"PeriodicalIF":3.2,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671351","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":"Lattice Vibrational Anisotropy in a Potentially Porous Diiron Paddle-Wheel Coordination Polymer","authors":"Aphiwe Sicwebu,&nbsp;Lonwabo Ngodwana*,&nbsp;Giovanni R. Hearne and Banele Vatsha*,&nbsp;","doi":"10.1021/acs.cgd.4c0117010.1021/acs.cgd.4c01170","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01170https://doi.org/10.1021/acs.cgd.4c01170","url":null,"abstract":"<p >A new three-dimensional potentially porous coordination polymer {[Fe₂(bdc)₄(Me₄bpz)₂]·solv}[1], where bdc = terephthalic acid and Me₄bpz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole, was successfully synthesized. Single-crystal X-ray structural elucidation confirmed that [1] comprises 2-fold interpenetrated nets with accessible pores for solvent exchange. Variable-temperature Mössbauer spectroscopy revealed a temperature dependence of relative line intensities of the quadrupole doublet spectral profile associated with the iron sites in the paddle-wheel structure. As the temperature decreased, the asymmetry in line intensities of the quadrupole doublet diminished. This is attributable to vibrational anisotropy (Goldanskii-Karyagin effect), which may be important for pore dynamics and sorption characteristics.</p><p >A new three-dimensional structure comprising diiron paddlewheel subunits and two-fold interpenetrated nets with potential porosity is reported. Probing aspects of the diiron mean square displacements in the range 300−5 K reveals lattice vibrational anisotropy, with likely implications for pore dynamics and sorption characteristics.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9324–9330 9324–9330"},"PeriodicalIF":3.2,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01170","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671650","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}

{"title":"Growth of High-Purity CsPbBr3 Crystals for Enhanced Gamma-Ray Detection","authors":"Duck Young Chung,&nbsp;Wenwen Lin,&nbsp;Mustafa Unal,&nbsp;Quoc Vuong Phan,&nbsp;Indra R. Pandey,&nbsp;Richard Vitt,&nbsp;Yihui He and Mercouri G. Kanatzidis*,&nbsp;","doi":"10.1021/acs.cgd.4c0110910.1021/acs.cgd.4c01109","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01109https://doi.org/10.1021/acs.cgd.4c01109","url":null,"abstract":"<p >High-quality CsPbBr₃ crystals hold significant potential for gamma-ray detection due to their remarkable optoelectronic properties. This study details an optimized production process using the Bridgman method to achieve highly pure CsPbBr₃ crystals. By implementing rigorous synthesis and purification techniques, we successfully reduced the total impurity levels to 9 ppm, as confirmed by glow discharge mass spectroscopy (GDMS). The resulting CsPbBr₃ crystals demonstrate exceptional performance, including high transparency, intense photoemission, and prolonged photoluminescence decay times. These properties facilitate superior gamma-ray detection with an energy resolution of 1.4% for the ¹³⁷Cs 662 keV gamma-rays, comparable to commercial Cd_1–<i>x</i>Zn_<i>x</i>Te (CZT) detectors. Our findings underscore the critical relationship between material purity and detector performance, highlighting the potential of CsPbBr₃ as a cost-effective alternative in radiation detection applications. Further studies on defect origins and electronic states are necessary to fully leverage the capabilities of CsPbBr₃ crystals in practical high-energy radiation detection systems.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9590–9600 9590–9600"},"PeriodicalIF":3.2,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671597","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":"Formation and Markedly Enhanced Optical Properties of Large-Area Nanoporous InGaN-Based LEDs with Nanoporous GaN Distributed Bragg Mirrors","authors":"Tiantian Luo,&nbsp;Dezhong Cao*,&nbsp;Feifei Wang,&nbsp;He Wang,&nbsp;Xiaodong Yan,&nbsp;Wangxin Gao,&nbsp;Mengqi Tian,&nbsp;Yuxuan Diwu,&nbsp;Zhengquan Guo,&nbsp;Qinglong Fang,&nbsp;Ningning Feng,&nbsp;Li Ma,&nbsp;Sen Wang,&nbsp;Dingze Lu,&nbsp;Song Feng,&nbsp;Xiaohua Ma and Yue Hao,&nbsp;","doi":"10.1021/acs.cgd.4c0105110.1021/acs.cgd.4c01051","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01051https://doi.org/10.1021/acs.cgd.4c01051","url":null,"abstract":"<p >Compared with nitric acid solution, oxalic acid solution has the advantages of safety, environmental protection, and a controllable etching rate. Large-area (20.3 cm²) nanoporous InGaN-based LEDs with nanoporous GaN distributed Bragg mirrors (NP LEDs) are prepared by a combination of doping, wet etching in oxalic acid solution, and metal–organic chemical vapor deposition (MOCVD). Compared with the epitaxial growth of LEDs (EG LEDs), NP LEDs show a decreased surface roughness, an enhanced luminescence intensity, and a blue shift of the luminescence peak. The enhancement of luminescence intensity can be attributed to the enhancement of internal quantum efficiency related to the increased crystal quality of MQWs, as well as increasing light extraction efficiency caused by the light-guiding effect of nanopore arrays in MQWs and the light reflection effect of nanoporous GaN distributed Bragg mirrors. The blue shift phenomenon is due to the stress relaxation of MQWs and the decreased In content.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9556–9563 9556–9563"},"PeriodicalIF":3.2,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671510","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":"Formation of Stable Zinc-Rich Amorphous Calcium Phosphate","authors":"Jia-hua Liu,&nbsp;Haidong Bian,&nbsp;Yibo Zhang,&nbsp;Yunchen Long,&nbsp;Chuan Li,&nbsp;Rong Zhang,&nbsp;Zhengyi Mao,&nbsp;Haikun Wu,&nbsp;Bo Li,&nbsp;Chunyi Zhi,&nbsp;Jian Lu* and Yang Yang Li*,&nbsp;","doi":"10.1021/acs.cgd.4c0094110.1021/acs.cgd.4c00941","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00941https://doi.org/10.1021/acs.cgd.4c00941","url":null,"abstract":"<p >Metal ion-rich amorphous calcium phosphate (ACP) is an essential mineral component in biogenic hard tissues, such as bones and teeth. However, the formation mechanism of ion-doped ACP and the role of metal ions in this process remain elusive. Herein, taking Zn as an example, we develop a series of Zn-substituted calcium phosphate materials that serve as models for investigating the formation process of Zn-ACP. It is found that entirely pure Zn-ACP can be successfully achieved when the precursor Zn/Ca ratio is maintained between 0.1 and 0.2. The resulting Zn-ACP nanoparticles exhibit a homogeneous distribution of Zn at the nanoscale, excellent cytocompatibility, and exceptionally high amorphous stability in aqueous media, including water and simulated body fluid. Furthermore, we fabricate monolithic Zn-ACP bioceramics through the application of pressure, resulting in remarkable hardness (1.7 GPa) and modulus (25.5 GPa) that exceed those of human bones. This work presents a novel approach to producing Zn-ACP monoliths and advances our understanding of the biomineralization processes involving Zn and ACP, thus opening potential applications in biomedicine.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9492–9501 9492–9501"},"PeriodicalIF":3.2,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671592","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":"Formation of Twin-Free Single Phase β-In2Se3 Layers via Selenium Diffusion into InP(111)B Substrate","authors":"Kaushini S. Wickramasinghe*,&nbsp;Candice R. Forrester,&nbsp;Martha R. McCartney,&nbsp;David J. Smith and Maria C. Tamargo*,&nbsp;","doi":"10.1021/acs.cgd.4c0070510.1021/acs.cgd.4c00705","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00705https://doi.org/10.1021/acs.cgd.4c00705","url":null,"abstract":"<p >Indium selenide, In₂Se₃, has recently attracted growing interest due to its remarkable properties, including room temperature ferroelectricity, outstanding photoresponsivity, and exotic in-plane ferroelectricity, which open up new regimes for next generation electronics. In₂Se₃ also provides the important advantage of tuning the electrical properties of ultrathin layers with an external electrical and magnetic field, making it a potential platform to study novel two-dimensional physics. Yet, In₂Se₃ has many different polymorphs, and it has been challenging to synthesize a single phase material, especially using scalable growth methods, as needed for technological applications. We recently reported the growth of twin-free ultrathin layers of In₂Se₃ prepared by a diffusion driven molecular beam epitaxy approach, and twin-free Bi₂Se₃ layers grown on these unique virtual substrates. In this paper, we use aberration-corrected scanning transmission electron microscopy to characterize the microstructure of these materials. We emphasize features of the In₂Se₃ layer and In₂Se₃/InP interface which provide evidence for understanding the growth mechanism that leads to the twin-free and single phase In₂Se₃. We also show that this In₂Se₃ layer provides an ideal substrate for growth of twin-free Bi₂Se₃ with a nearly defect-free interface. This approach for growing high-quality twin-free single phase two-dimensional crystals using InP substrates is likely to be applicable to other technologically important materials.</p><p >Cross-sectional scanning transmission electron microscopy image showing atomic resolution of single phase β-In₂Se₃ layer grown via selenium (Se) passivation of InP(111)B substrate. Atomic models of β-In₂Se₃ and InP(111)B are overlaid with the real lattice depicting that indium atoms remain at the same positions in both lattices as shown by yellow box with the same dimensions. This also shows the result of selenium diffusing into InP and substituting for phosphorus (P) atoms while preserving the zinc-blende InP lattice right below the In₂Se₃/InP interface. These features provided evidence to uncover the growth mechanism which led to the formation of ultrathin layers of untwinned single phase β-In₂Se₃.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9313–9317 9313–9317"},"PeriodicalIF":3.2,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c00705","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671214","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}

{"title":"Formation of Twin-Free Single Phase β-In₂Se₃ Layers via Selenium Diffusion into InP(111)B Substrate.","authors":"Kaushini S Wickramasinghe, Candice R Forrester, Martha R McCartney, David J Smith, Maria C Tamargo","doi":"10.1021/acs.cgd.4c00705","DOIUrl":"10.1021/acs.cgd.4c00705","url":null,"abstract":"<p><p>Indium selenide, In₂Se₃, has recently attracted growing interest due to its remarkable properties, including room temperature ferroelectricity, outstanding photoresponsivity, and exotic in-plane ferroelectricity, which open up new regimes for next generation electronics. In₂Se₃ also provides the important advantage of tuning the electrical properties of ultrathin layers with an external electrical and magnetic field, making it a potential platform to study novel two-dimensional physics. Yet, In₂Se₃ has many different polymorphs, and it has been challenging to synthesize a single phase material, especially using scalable growth methods, as needed for technological applications. We recently reported the growth of twin-free ultrathin layers of In₂Se₃ prepared by a diffusion driven molecular beam epitaxy approach, and twin-free Bi₂Se₃ layers grown on these unique virtual substrates. In this paper, we use aberration-corrected scanning transmission electron microscopy to characterize the microstructure of these materials. We emphasize features of the In₂Se₃ layer and In₂Se₃/InP interface which provide evidence for understanding the growth mechanism that leads to the twin-free and single phase In₂Se₃. We also show that this In₂Se₃ layer provides an ideal substrate for growth of twin-free Bi₂Se₃ with a nearly defect-free interface. This approach for growing high-quality twin-free single phase two-dimensional crystals using InP substrates is likely to be applicable to other technologically important materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9313-9317"},"PeriodicalIF":3.2,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11583199/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142708568","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}

{"title":"Solvent-Induced Magnetic Properties of a Series of Dy-Based MOFs from Two Different Precursor Complexes","authors":"Wen-Kang Jiang,&nbsp;Ting-Ting Huang,&nbsp;Dong-Xiu Lv,&nbsp;Zhong-Hong Zhu*,&nbsp;Hua-Hong Zou* and Fu-Pei Liang*,&nbsp;","doi":"10.1021/acs.cgd.4c0119010.1021/acs.cgd.4c01190","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01190https://doi.org/10.1021/acs.cgd.4c01190","url":null,"abstract":"<p >It is still challenging for Dy-MOFs to modulate the single-molecule magnet (SMM) behavior through guest molecules. Dy-MOFs with different guest molecules, secondary building units, and linkers were synthesized by precursors and bridging carboxylic acid ligands, and the magnetic properties of Dy-MOFs were regulated by guest molecules. These differentiated Dy-MOFs are [Dy₂(C₉H₄Cl₂NO)₂(L1)₂(H₂O)(DMA)]_n·DMA (<b>MOF-3</b>, L1 = terephthalate), [Dy(C₉H₄Cl₂NO)₂(L1)(DMSO)(H₂O)]_n (<b>MOF-4</b>), [Dy₂(C₉H₄Br₂NO)₂(L1)₂(H₂O)(DMA)]_n·DMA (<b>MOF-5</b>), [Dy(C₉H₄Cl₂NO)₂(L2)(H₂O)]_n·DMA (<b>MOF-6</b>, L2 = isophthalate), and [Dy(C₉H₄Cl₂NO)₂(L2)(H₂O)]_n·DMF (<b>MOF-7</b>), [Dy(C₉H₄Br₂NO)₂(L2)(H₂O)]_n·DMA (<b>MOF-8</b>). The single-crystal X-ray diffraction showed that <b>MOF-3</b> and <b>MOF-5</b> are two-dimensional MOFs with square holes. <b>MOF-4</b> is a two-dimensional MOF formed by hydrogen–halogen bonds, and <b>MOF-6</b>, <b>MOF-7</b>, and <b>MOF-8</b> are one-dimensional chains. The magnetic test results show that <b>MOF-4</b>, <b>MOF-6</b>, and <b>MOF-8</b> show SMM behavior under zero field, and <b>MOF-3</b> and <b>MOF-5</b> exhibit field-induced SMM behavior. In the zero field, the effective energy bases of <b>MOF-4</b>, <b>MOF-6</b>, and <b>MOF-8</b> are 37.09, 19.56, and 15.73 K, and relaxation times τ₀ were 4.66 × 10^–6, 2.35 × 10^–6, and 9.95 × 10^–6 s, respectively. This work provides a vivid example of regulating the molecular magnetism of Dy-MOFs and promotes the progress of Dy-MOF crystal engineering.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"24 22","pages":"9692–9700 9692–9700"},"PeriodicalIF":3.2,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671407","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}