Crystal Growth & Design最新文献

{"title":"Kokum Butter and Sesame Oil-Based Oleogels as Novel Nutraceutical Delivery Systems","authors":"Dheerendra Kumar Suman,&nbsp;Kunal Pal,&nbsp;Biswaranjan Mohanty* and Rajeswara Reddy Erva*,&nbsp;","doi":"10.1021/acs.cgd.4c0120510.1021/acs.cgd.4c01205","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01205https://doi.org/10.1021/acs.cgd.4c01205","url":null,"abstract":"<p >Novel oleogel formulations for nutraceutical administration using sesame oil (SO) and kokum butter (KB) were presented. KB aligned and enhanced formulation by entrapping the SO. SO–KB gelation required 20% w/w. KB (22.5–35% w/w) was utilized to make oleogel formulations. Oleogels, according to various microscopes, showed fat molecules aggregating in the oil matrix. Fourier transform infrared (FTIR) spectroscopy showed no molecular interactions between the oil and butter molecules. Mechanical studies showed that oleogel formulations are viscoelastic and strengthen with increasing KB. The formulation with more KB exhibited the highest crystallization rate and nucleation process. X-ray diffraction (XRD) evaluation showed that the formulation with the highest KB concentration had the largest crystalline particle size. A drug release study explored how KB affected curcumin (CRU) release at pH 6.8 and 1.2. Finally, these oleogels showed promising nutraceutical delivery functions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585687","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":"Process Controlled Polymorphic Phase Transformation in Crystalline Solid Dispersions: Impact of Temperature, Pressure, and Shear Stress","authors":"Francheska Reyes Figueroa,&nbsp;José R. Hernández Espinell,&nbsp;Suresh Manivel,&nbsp;Lian Yu,&nbsp;Geoff G. Z. Zhang,&nbsp;Vilmalí López-Mejías* and Torsten Stelzer*,&nbsp;","doi":"10.1021/acs.cgd.4c0088010.1021/acs.cgd.4c00880","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00880https://doi.org/10.1021/acs.cgd.4c00880","url":null,"abstract":"<p >Understanding the processing boundaries to generate crystalline solid dispersions (CSDs) containing metastable polymorphs remains an untapped challenge for the application of hot-melt extrusion (HME) and three-dimensional printing (3DP) as polymer-based formulation approaches. Hence, to successfully implement CSDs as alternative solid dosage formulations, the effect of critical process parameters (CPPs) on potential polymorphic phase transformations (PPTs) needs to be examined. This study extends the current knowledge on the influence of CPPs through temperature–pressure–shear simulated extrusion (TPSS-E) using the model system flufenamic acid (FFA) and poly(ethylene glycol) (PEG). The TPSS-E results revealed a significant reduction in the average PPT induction time (53%) compared to previous temperature–pressure simulated-extrusion (TPS-E) studies without shear stress. However, TPSS-E control experiments performed at 25 °C showed no PPT. This suggests that temperature is the most critical parameter in determining whether a PPT will occur, while pressure and shear stress significantly accelerate the PPT kinetics from the metastable (FFA III) to the stable form (FFA I) at elevated temperatures. These results demonstrate that for an enantiotropic system like FFA forms I and III (transition point = 42 °C), it is possible to control the metastable polymorph in CSDs during extrusion processes if the thermodynamic and kinetic boundaries, the CPPs, and material attributes of the drug-polymer system are well understood and controlled. The work presented here expands on the application of HME and 3DP as polymer-based formulation strategies for CSDs containing metastable polymorphs.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585688","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":"Fine-Tuning of Magnetic Anisotropy in Tetranuclear M2Dy2 Complexes with Zig-Zag Topology: The Impact of 3d Metal Selection","authors":"Guan-Lin Lu,&nbsp;Shih-Ting Chiu,&nbsp;Jérôme Long* and Po-Heng Lin*,&nbsp;","doi":"10.1021/acs.cgd.4c0120910.1021/acs.cgd.4c01209","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01209https://doi.org/10.1021/acs.cgd.4c01209","url":null,"abstract":"<p >This study presents the design, synthesis, and magnetic characterization of two novel heterometallic tetranuclear complexes, [M₂Dy₂(Hheb)₂(heb)₄]·4MeOH (H₂heb = (E)-N′-(1-(2-hydroxyphenyl)ethylidene)benzohydrazide; M = Ni (<b>1</b>), Cu(<b>2</b>)). These complexes exhibit a rare zig-zag core topology induced by the rigid Hheb/heb^2– ligands. A subtle interplay between the incorporated 3d metal ions (Ni²⁺ and Cu²⁺) and the magnetic properties is evidenced. Notably, the choice of the 3d metal plays a crucial role in modulating the Dy³⁺ ion’s coordination environment and axiality, as supported by theoretical calculations. While both complexes exhibit rapid Quantum Tunneling of Magnetization (QTM), complex <b>1</b> (Ni²⁺) demonstrates markedly enhanced slow relaxation dynamics compared to complex <b>2</b>. This difference is attributed to the stronger axiality indirectly induced by Ni²⁺ in complex <b>1</b>, whereas the Cu²⁺-induced distortions and ferromagnetic interactions in complex <b>2</b> negatively affect the slow relaxation behavior.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585673","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":"[5,6,5]-Tricyclic Energetic Compounds with Piperazine, Triazole, and 1,2,5-Oxadiazole Rings in Framework","authors":"Teng Zhu,&nbsp;Chengchuang Li,&nbsp;Jie Tang,&nbsp;Chuan Xiao,&nbsp;Luyao Chen,&nbsp;Guangbin Cheng* and Hongwei Yang*,&nbsp;","doi":"10.1021/acs.cgd.4c0082110.1021/acs.cgd.4c00821","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00821https://doi.org/10.1021/acs.cgd.4c00821","url":null,"abstract":"<p >In this work, a series of [5,6,5]-tricyclic fused ring energetic compounds <b>1–9</b> were synthesized utilizing triazole, furazan, and piperazine as basic units. A thorough analysis of the newly synthesized compounds was carried out, and the structures of compounds <b>2</b>, <b>6</b>, and <b>7</b> were further validated using single-crystal X-ray diffraction. The physicochemical properties and energetic characteristics of newly synthesized compounds <b>1–9</b> were determined by experimental and theoretical methods. Compared with the previously reported tricyclic fused ring compounds, the newly synthesized fused energetic compounds exhibit better comprehensive characteristics including moderate detonation performance and good stability. The hydrazine salt <b>4</b> (<i>T</i>_d = 211 °C, <i>D</i>_v = 8702 m s^–1) is comparable to 1,3,5-trinitroperhydro-1,3,5-triazine (RDX: <i>T</i>_d = 204 °C, <i>D</i>_v = 8975 m s^–1) in terms of the calculated detonation velocity and thermostability. Besides, hydrazine salt <b>4</b> (<i>IS</i> = 30 J, <i>FS</i> = 288 N) is more stable than RDX (<i>IS</i> = 7.4 J, <i>FS</i> = 120 N) in mechanical sensitivity. Moreover, the carbonyl compound [1,2,5]oxadiazolo[3,4-<i>e</i>][1,2,4]triazolo[4,3-<i>a</i>]pyrazine-5,8(4H,7H)-dione (<b>6</b>, <i>T</i>_d = 304 °C) exhibits similar thermal stability to that of 2-bis(2,4,6-trinitrophenyl) ethene (HNS: <i>T</i>_d = 318 °C) and has a higher calculated detonation velocity (<b>6</b>: <i>D</i>_v = 7984 m s^–1, HNS: <i>D</i>_v = 7647 m s^–1). Based on the properties mentioned above, carbonyl compound <b>6</b> is a promising candidate for a new heat-resistant explosive.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585675","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":"Correction to “Nanocrystal Preparation: Low-Energy Precipitation Method Revisited”","authors":"Shahzeb Khan,&nbsp;Marcel de Matas,&nbsp;Jiwen Zhang and Jamshed Anwar*,&nbsp;","doi":"10.1021/acs.cgd.4c0099310.1021/acs.cgd.4c00993","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00993https://doi.org/10.1021/acs.cgd.4c00993","url":null,"abstract":"","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585712","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":"Structural Design of Zinc-Directed Heterometallic Uranyl Organic Frameworks: Multifunction Detection of Cr2O72– and Metamitron Contaminants from Water","authors":"Wensu Yang,&nbsp;Pei Lv,&nbsp;Jiayi Li,&nbsp;Xiaoping Jin*,&nbsp;Ke Yang,&nbsp;Huan Dai and Wei Xu*,&nbsp;","doi":"10.1021/acs.cgd.4c0115310.1021/acs.cgd.4c01153","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01153https://doi.org/10.1021/acs.cgd.4c01153","url":null,"abstract":"<p >Based on the hard and soft acid and base (HSAB) theory, three heterometallic uranyl organic frameworks (UOFs), namely, [Zn(UO₂)(npa)₂(2,2′-bpy)(H₂O)] (<b>1</b>), [Zn(UO₂)(nip)₂(2,9-dm-1,10-phen)] (<b>2</b>), and [Zn(UO₂)(ntp)₂(4,7-dm-1,10-phen)(H₂O)]·(H₂O) (<b>3</b>), have been solvothermally synthesized by using a variety of different substituted nitro-benzenedicarboxylic acid (H₂npa = 3-nitrophthalic acid, H₂nip = 5-nitroisophthalic acid, H₂ntp = 2-nitroterephthalic acid) and uranyl zinc acetate, in the presence of N-bearing coligands, including 2,2′-bipyridine (2,2′-bpy), 2,9-dimethyl-1,10-phenanthroline (2,9-dm- 1,10-phen), and 4,7-dimethyl-1,10-phenanthroline (4,7-dm-1,10-phen). The results of single-crystal X-ray diffraction analysis show that each of them presents a heterometallic interaction between the uranyl and Zn²⁺ centers. UOFs <b>2</b> and <b>3</b> adopt three-dimensional (3D) frameworks with different architectures, while UOF <b>1</b> exhibits a one-dimensional (1D) chain assembly. Furthermore, <b>1</b> can be used as a bifunctional luminescent sensor for the detection of metamitron (MMT) and Cr₂O₇^2– in aqueous solution with the limit of detection (LOD) for 4.06 × 10^–6 and 2.52 × 10^–6 M, respectively. The sensing mechanism was also investigated in detail through ultraviolet–visible (UV–vis) absorption spectroscopy, density functional theory calculations (DFT), and fluorescence lifetime analysis. This work provides valuable guidance for the facile and effective design and construction to employ UOFs as multiresponsive fluorescence sensors for the detection of environmental pollutants in aqueous solution.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585672","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":"Investigation of Supramolecular Self-Assembly in Sn(IV)-5,10,15,20-tetra(4-bromo-2,6-difluorophenyl) Porphyrins Mediated through Activated Sigma Hole","authors":"Rohith Phaneendra Bandaru,&nbsp;Anil Rajnath Singh,&nbsp;Hatem M. Titi,&nbsp;Sudip Mandal,&nbsp;Ranjan Patra* and Bharat Kumar Tripuramallu*,&nbsp;","doi":"10.1021/acs.cgd.4c0104410.1021/acs.cgd.4c01044","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01044https://doi.org/10.1021/acs.cgd.4c01044","url":null,"abstract":"<p >The article presents the design, synthesis, characterization, and investigation of halogen-bonding interactions in a series of six-coordinated Sn(IV) complexes based on 5,10,15,20-tetra(4-bromophenyl) porphyrin [Sn(IV)TBrPr] and 5,10,15,20-tetra(4-bromo-2,6-difluoro phenyl) porphyrin [Sn(IV)TBrFPr] with symmetrical axial linkers 3,5-dibromobenzoic acid (3,5-DiBrBA) and 4-bromobenzoic acid (4-BrBA) and nonsymmetrical axial linker 5-bromo nicotinic acid (5-BrNA). Four compounds, namely, Sn(5-BrNA)₂(TBrPr) <b>(1)</b>, Sn(5-BrNA)₂(TBrFPr)·2DMF <b>(2)</b>, Sn(3,5-DiBrBA)₂(TBrFPr) <b>(3)</b>, Sn(4-BrBA)₂(TBrFPr) <b>(4)</b>, were synthesized and characterized by single-crystal X-ray crystallography. All of the compounds were characterized by ¹H NMR, UV–vis absorption, emission, scanning electron microscopy, and cyclic voltammetry. Diverse supramolecular interactions involving bromine and fluorine atoms like Br···Br, Br···F, Br···π, and F···F are successfully manifested in our systems. The single-crystal analysis reveals that the self-assembly in compound <b>3</b> displays the shortest type II Br···Br contact of 3.401(3) Å in the realm of porphyrin assemblies, which leads to the formation of a porphyrin dimer. An interesting example of the shortest Br···F contact of 2.937(2) Å is found in compound <b>4</b>, which facilitates the formation of 3D supramolecular architecture with well-defined hexagonal voids. The shortest contacts observed in our systems are persuaded by the cooperative interactions of the bromine atoms and by the most electron-withdrawing fluorine atoms on the porphyrin skeleton. Electrostatic potential surface analyses show that the σ-hole potential in the bromine atoms is increased by 6.5 kcal by the fluorine atoms. Optical and electrochemical studies detail the electronic structure of the title compounds under the influence of fluorine atoms and axial linkers, while theoretical studies were conducted to calculate the highest occupied molecular orbital–least unoccupied molecular orbital gap to relate with the experimental values.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585674","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":"Thermodynamics of Magnesium Binding at Calcite Kink Sites and Implications for Growth inhibition","authors":"Julie Aufort*,&nbsp;Blake I. Armstrong,&nbsp;Paolo Raiteri and Julian D. Gale,&nbsp;","doi":"10.1021/acs.cgd.4c0099510.1021/acs.cgd.4c00995","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00995https://doi.org/10.1021/acs.cgd.4c00995","url":null,"abstract":"<p >The standard dissolution free energies of magnesium binding at each of the eight distinct calcite cation kinks were computed from classical molecular dynamics simulations using alchemical methods to transform magnesium into calcium at each site. The preferred calcite kink site for magnesium binding is found to correspond to one of the two symmetry inequivalent cation sites at the acute step along the kink direction that forms an obtuse angle between the end of the row and terrace (<i>AO</i>_<i>a</i> according to our notation system). Incorporation of magnesium at this site is found to inhibit growth along the step edge. However, this effect occurs not due to destabilization of the addition of the next carbonate immediately adjacent to Mg but instead by altering the thermodynamics of the subsequent cation. The binding free energy of this calcium site is reduced by more than 10 kJ/mol once magnesium has been incorporated in the step edge. Our results support and provide a mechanistic explanation for the experimental observation that acute steps are more affected by the presence of magnesium in the growth solution relative to obtuse steps.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585711","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":"Terphenyl-Tricarboxylate Coordination Polymers: From Hydrothermal Assembly to Structural Diversity and Catalytic Application","authors":"Hongrui Zhang,&nbsp;Jinzhong Gu*,&nbsp;Marina V. Kirillova and Alexander M. Kirillov*,&nbsp;","doi":"10.1021/acs.cgd.4c0122110.1021/acs.cgd.4c01221","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01221https://doi.org/10.1021/acs.cgd.4c01221","url":null,"abstract":"<p >An aromatic tricarboxylic acid building block, [1,1′:3′,1″-terphenyl]-4,4″,5′-tricarboxylic acid (H₃tptca), was used as a versatile linker for assembling, under hydrothermal conditions, a series of 12 new coordination polymers (CPs) in the presence of supporting <i>N</i>-donor ligands acting as mediators of crystallization. The obtained products were formulated as [Mn(μ-Htptca)(phen)₂]_<i>n</i>·<i>n</i>H₂O (<b>1</b>), [Zn(μ-Htptca)(2,2′-bipy)(H₂O)]_<i>n</i>·<i>n</i>H₂O (<b>2</b>), [Ni(μ₃-Htptca)(μ-4,4′-bipy)]_<i>n</i>·2<i>n</i>H₂O (<b>3</b>), [Co(μ₃-Htptca)(μ-bpe)]_<i>n</i> (<b>4</b>), [M₃(μ₃-tptca)₂(phen)₃(H₂O)₂]_<i>n</i>·2<i>n</i>H₂O (M = Co (<b>5</b>), Zn (<b>6</b>)), [Co₂(μ₄-tptca)(μ-OH)(2,2′-bipy)₂]_<i>n</i> (<b>7</b>), [Zn₃(μ₃-tptca)₂(2,2′-bipy)₃(H₂O)₂]_<i>n</i>·4<i>n</i>H₂O (<b>8</b>), {[Cd(H₂biim)₃][Cd₂(μ₃-tptca)(μ₅-tptca)]}_<i>n</i> (<b>9</b>), [Co₂(μ₄-tptca)(μ-bpa)(μ₃-OH)(H₂O)₂]_<i>n</i>·<i>n</i>H₂O (<b>10</b>), [Ni₃(μ₃-tptca)₂(μ-bpa)₃(H₂O)₄]_<i>n</i>·5<i>n</i>H₂O (<b>11</b>), and [Co₂(μ₄-tptca)(μ-bpb)(μ-OH)]_<i>n</i> (<b>12</b>), wherein phen, 2,2′-bipy, 4,4′-bipy, bpe, H₂biim, bpa, and bpb are 1,10-phenanthroline, 2,2′- and 4,4′-bipyridine, 1,2-di(4-pyridyl)ethane, 2,2′-biimidazole, bis(4-pyridyl)amine, and 1,4-bis(pyrid-4-yl)benzene, respectively. Crystal structures of CPs <b>1</b>–<b>12</b> reveal a broad diversity metal–organic networks that range from 1D chains (<b>1</b>, <b>2</b>, <b>5</b>, <b>6</b>, and <b>8</b>) to 2D layers (<b>3</b>, <b>4</b>, <b>7</b>, <b>9</b>, and <b>11</b>) and 3D nets (<b>10</b> and <b>12</b>), including the examples of interpenetrated, polycatenated, and topologically unique architectures. Structural features and catalytic properties of the obtained CPs were studied and discussed. In particular, a Zn(II) CP <b>8</b> acts as an efficient and recyclable heterogeneous catalyst for the mild cyanosilylation of benzaldehydes, leading to the formation of the corresponding cyanohydrin products in up to 99% yields. The obtained compounds widen a growing family of functional CPs driven by terphenyl-tricarboxylate linkers.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585614","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":"Cu(II)-Based Coordination Polymers Containing 1,4-Bis(1H-imidazol-1-yl)benzene and Monovalent Fluorinated Anions","authors":"Giulio Bresciani*,&nbsp;Massimo Guelfi,&nbsp;Melodj Dosa,&nbsp;Virginia Guiotto,&nbsp;Valentina Crocellà,&nbsp;Marco Lessi and Marco Taddei*,&nbsp;","doi":"10.1021/acs.cgd.4c0103810.1021/acs.cgd.4c01038","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01038https://doi.org/10.1021/acs.cgd.4c01038","url":null,"abstract":"<p >The design of the organic linker is one of the most important steps in driving the formation of the desired crystal structure in coordination polymers. Imidazole derivatives exhibit wide and interesting coordination capabilities. This property makes these π-conjugated ligands suitable linkers in the synthesis of metal–organic frameworks (MOFs). Despite these considerations, few examples of two-dimensional (2D) materials based on the 1,4-bis(1<i>H</i>-imidazol-1-yl)benzene (<b>bib</b>) ligand, which can be seen as a topological analogue of 4,4′-bipyridine, have been reported so far, and there is a lack of literature on the exploration of their gas adsorption properties. The combination of <b>bib</b> ligand with Cu(BF₄)₂ led us to obtain a doubly interpenetrated three-dimensional (3D) material (<b>UdP-1</b>) of minimal formula [Cu(<b>bib</b>)_2.5(BF₄)]·(BF₄)·1.5H₂O that loses 0.5 equiv of <b>bib</b> upon heating and undergoes a phase transition to a new material named <b>UdP-2</b>. <b>UdP-2</b> was obtained as a microcrystalline powder by direct synthesis, but its crystal structure could not be elucidated. Attempts to obtain single crystals of <b>UdP-2</b> led us to discover four new compounds, named <b>UdP-3</b>, <b>UdP-3-i</b>, <b>UdP-4</b>, and <b>UdP-5</b>, displaying both 2D and 3D structures. Using Cu(CF₃SO₃)₂ instead of Cu(BF₄)₂ allowed us to prepare a 2D layered material of the formula [Cu(<b>bib</b>)₂(CF₃SO₃)₂]·2MeOH (<b>UdP-6</b>), where the methanol molecules are trapped in the pores of the structure as in the ELM-12 structure, which contains 4,4′-bipyridine as the organic ligand. Different from ELM-12, <b>UdP-6</b> displays a Type I CO₂ adsorption isotherm, with no evidence of a gating phenomenon. This behavior is attributed to the larger number of supramolecular interactions existing between adjacent layers in <b>UdP-6</b>.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585626","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}