Crystal Growth & Design最新文献

{"title":"Anion- and Solvent-Mediated Crystal Phase Changes Resulting in Diverse SCO Behaviors in a Mononuclear Fe(II) Complex","authors":"Kenneth Zhang,&nbsp;Matthew J. Wallis,&nbsp;James P. Flood,&nbsp;Hyunsung Min,&nbsp;Kanta Miyake,&nbsp;Shinya Hayami,&nbsp;Daniel J. Fanna,&nbsp;Leonard F. Lindoy and Feng Li*,&nbsp;","doi":"10.1021/acs.cgd.5c0026210.1021/acs.cgd.5c00262","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00262https://doi.org/10.1021/acs.cgd.5c00262","url":null,"abstract":"<p >Spin crossover (SCO) compounds which differ only by the nature of the cocrystallizing anion(s) and solvent(s) often leads to rational modulation of their respective SCO behaviors. In the following, we report the formation of two new salts of the previously reported tripodal Fe(II) complex, tris(((((1-(pyridin-4-yl)-1<i>H</i>-imidazole-4-yl)methylene)amino)ethyl)ethane-1,2-diamine)iron(II), which was crystallized with either Br^– (<b>1</b>) or I^– (<b>2</b>) anions. The magnetic behavior following crystallization with different anions was investigated for a series of solvated, air-exposed, and desolvated forms of each compound. While the solvated and air-exposed forms of <b>2</b> only occurred in the high-spin (HS) state, the corresponding forms of <b>1</b> differed in their SCO behaviors following the substitution and/or loss of solvent from the crystal lattice. The maintained stability of <b>2</b> in the HS state was likely a reflection of the tighter crystal packing as also occurs in the previously reported and isostructural [Fe<b>L</b>](BF₄)₂ and [Fe<b>L</b>](ClO₄)₂ materials. Following crystallization of <b>1</b>, the packing arrangement was similar to that of the previously reported and SCO-active [Fe<b>L</b>]Cl₂ derivative. Despite the similarities occurring between the solvated and air-exposed forms of <b>1</b> and [Fe<b>L</b>]Cl₂, full desolvation of <b>1</b> led to a gain in SCO activity as opposed to quenching of SCO, which occurred in the previously reported air-exposed and desolvated forms of [Fe<b>L</b>]Cl₂. The interesting magnetic behavior occurring between the different solvates of <b>1</b> has been related to a single crystal to single crystal transformation mediated by solvent exchange. This study highlights the complex anion- and solvent-mediated structural changes that occur within the crystal phase of the present materials, and the marked effect they have on the resulting SCO behaviors.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3210–3218 3210–3218"},"PeriodicalIF":3.2,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911126","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":"Simultaneous Growth of Four GaN Crystal Sheets Using the Na-Flux Liquid-Phase Epitaxial Method: Under Different Solution Heights","authors":"Ronglin Pan,&nbsp;Chen Yang,&nbsp;Gemeng Huang,&nbsp;Ming Ma,&nbsp;Shiji Fan and Zhenrong Li*,&nbsp;","doi":"10.1021/acs.cgd.5c0006710.1021/acs.cgd.5c00067","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00067https://doi.org/10.1021/acs.cgd.5c00067","url":null,"abstract":"<p >The four GaN crystal sheets with an area of about 1 in. were simultaneously grown on MOCVD-GaN film seed by the Na-flux liquid-phase epitaxial (LPE) method. The effects of solution height on the growth process, thickness, morphologies, and quality of LPE-GaN crystals were researched. Two different solution heights were employed: 16 mm (abbreviated as H-16 mm) and 12 mm (abbreviated as H-12 mm). In the H-16 mm solution, the surface ridge size and growth thickness of samples #1–#3-16 mm in the top-down direction away from the gas–liquid interface show a decreasing trend, and no complete epitaxial growth is obtained for sample #4-16 mm, which indicates that there is a vertical nitrogen concentration gradient. In the H-12 mm solution, the surface morphologies of samples #1–#4-12 mm present cellular organizations of about the same size, and samples #1–#3-12 mm have approximately the same growth thickness, indicating that the vertical nitrogen concentration in the solution is relatively uniform. The FWHMs of the (0002) facet of samples #1–#3-16 mm are 598 arcsec, 174 arcsec, and 157 arcsec, respectively. Additionally, the FWHMs of the (0002) facet of samples #1–#4-12 mm are 335, 213, 224, and 220 arcsec, respectively. Therefore, by further optimizing the growth parameters, the multisheet growth method could improve growth efficiency and is feasible to achieve larger-size and higher-quality GaN single crystals in the Na-flux LPE growth method.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2986–2993 2986–2993"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910993","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":"Insights into the Structure and Electrical Properties of Bi0.5Na0.5TiO3–PbTiO3 Single Crystals near the Morphotropic Phase Boundary","authors":"Changpeng Guan,&nbsp;Yongxing Wei*,&nbsp;Siyuan Dong,&nbsp;Changqing Jin,&nbsp;Weilin Yang,&nbsp;Zhonghua Dai,&nbsp;Weiguo Liu and Li Jin*,&nbsp;","doi":"10.1021/acs.cgd.5c0010410.1021/acs.cgd.5c00104","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00104https://doi.org/10.1021/acs.cgd.5c00104","url":null,"abstract":"<p >Herein, high-quality 0.88(Bi_0.5Na_0.5)TiO₃–0.12PbTiO₃ (BNT–12PT) single crystals were successfully grown by the flux method for the first time, achieving a maximum volume of 9.3 × 9.1 × 3.3 mm³. Furthermore, the phase structure, electrical properties, and domain structure of single crystals were systematically investigated. The average phase structure of as-grown single crystals exhibits a rhombohedral–tetragonal (<i>R</i>3<i>c–P</i>4<i>mm</i>) coexistence. These specimens achieve considerable piezoelectric properties (<i>d</i>₃₃ ∼ 212 pC/N) without deteriorating the depolarization temperature (<i>T</i>_d ∼ 206 °C). The appearance of the stripe-shaped domain structure before poling and the first-cycle ferroelectric and electrostrain responses reveal that the initial state of the BNT–12PT single crystal is a long-range ferroelectric state. In addition, a rapid rise in the piezoelectric coefficient from 248 to 348 pC/N, as well as a significant increase in maximum strain from 0.11% to 0.53%, is observed within the temperature range of 100 °C to <i>T</i>_d, and the corresponding modification in relative permittivity and frequency dispersion tends to coincide. Furthermore, the disappearance of the rhombohedral phase near 300 °C was confirmed by the observation of the optical domain structure. This work further deepens the understanding of the structure and electrical properties of the BNT–PT single crystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3048–3057 3048–3057"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910991","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":"Nanocrystal Fabrication of Highly Nonlinear Optical Organic Materials and Evolution of Polar Morphology","authors":"Min Ho Rim,&nbsp;Hyungki Hong,&nbsp;Kwang-Sup Lee,&nbsp;Seung-Joo Kim,&nbsp;Seong Jun Park and Choon Sup Yoon*,&nbsp;","doi":"10.1021/acs.cgd.3c0070810.1021/acs.cgd.3c00708","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00708https://doi.org/10.1021/acs.cgd.3c00708","url":null,"abstract":"<p >3-Methyl-4-methoxy-4′-nitrostilbene (MMONS) exhibits pronounced second-order nonlinear optical effects, with its bulk crystals demonstrating efficient second-harmonic generation. Bulk MMONS crystals exhibit unidirectional growth in the [001] direction when grown from solution of polar solvents─such as methyl ethyl ketone, ethyl acetate, and acetone. This asymmetric growth may be ascribed to the differential attachment of the polar solvent molecules to the (001) and (001̅) surfaces, which is facilitated by the alignment of the dipoles of the solvent molecules at the solution–crystal interface along the Coulomb electric field emanating from both polar surfaces. Highly perfect MMONS nano- and microcrystals were fabricated using the reprecipitation technique coupled with various stirring methods, including magnetic stirring, vortex mixing, sonication, and piezoelectric nozzle application. Among these, the piezoelectric nozzle yielded the smallest particle size of approximately 3 nm, with a narrow size distribution. MMONS nanocrystals of up to 400 nm in size exhibited an isotropic morphology with a truncated rectangular parallelepiped shape, featuring eight slanted trapezoidal {111} faces at the corners of a cuboid, along with four {100} and {001} faces. Isotropic and polar morphologies coexist in crystals sized 1–2 μm, with the polar morphology becoming predominant in crystals larger than 3 μm. This transition was marked by unidirectional growth, which is due to the poisoning of the (001̅) face by solvent molecules, resulting in a truncated angular cone shape along the [001̅] direction. This morphological transformation converges toward a perfect angular cone shape in centimeter-long crystals while maintaining a normal growth morphology in the [001] direction. This research provides new insights into the morphological evolution of polar organic crystals, and is particularly relevant for applications in biological detection, pharmaceutical manufacturing, and nonlinear photonics.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2798–2808 2798–2808"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910992","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":"Bright Prospects, Lingering Challenges: CsPbBr3 Quantum Dots for Environmental Sensing","authors":"Abdulazeez M. Ogunleye,&nbsp;Mohammad Awwal Adeshina,&nbsp;GunWoo Kim,&nbsp;Hyunmin Kim and Jonghoo Park*,&nbsp;","doi":"10.1021/acs.cgd.4c0148410.1021/acs.cgd.4c01484","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01484https://doi.org/10.1021/acs.cgd.4c01484","url":null,"abstract":"<p >The quest for efficient and versatile environmental sensing technologies has led researchers to explore novel materials. The advent of CsPbBr₃ perovskite quantum dots (PQDs) has revolutionized the field of optoelectronics, offering a new paradigm for sensing applications due to their exceptional optical properties. This review paper examines the opportunities and challenges associated with using CsPbBr₃ PQDs for environmental sensing applications, focusing on their distinctive properties, synthesis methods, and practical implementations. We discuss the potential of CsPbBr₃ PQDs in various environmental sensing applications, including pollutant detection, temperature and pH monitoring, and gas and heavy-metal ion sensing. Additionally, we highlight the challenges and limitations posed by the stability and durability of these PQDs in different environments, particularly under conditions of humidity and temperature fluctuations. Lastly, we explore future perspectives and opportunities for CsPbBr₃ PQDs in environmental sensing, emphasizing the importance of addressing stability and toxicity concerns. This review provides a comprehensive overview of the current state of research on CsPbBr₃ PQDs for environmental sensing applications, offering insights into potential advancements and the challenges that remain.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3238–3252 3238–3252"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910989","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":"Flexible and Rapid Synthesis of Bimetallic Metal–Organic Framework Thin Films","authors":"Allison A. Prue,&nbsp;Adele T. Chalmers,&nbsp;Hans C. Anderson,&nbsp;Andrew D. Ralph,&nbsp;Stacey J. Smith and Kara J. Stowers*,&nbsp;","doi":"10.1021/acs.cgd.4c0146110.1021/acs.cgd.4c01461","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01461https://doi.org/10.1021/acs.cgd.4c01461","url":null,"abstract":"<p >Metal–organic frameworks (MOFs) have many applications specific to thin films including coatings, separation, and catalysts. This work presents a synthesis method for the creation of bimetallic thin-film MOFs rapidly and reproducibly at ambient conditions. A dynamic spin-coating approach is used to synthesize the MOF thin film onto inert surfaces without the use of a self-assembled monolayer and without pretreatment. These thin films are characterized for coverage, crystallinity, and size through scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. These methods are also used to confirm the MOF structure and incorporation of the secondary metal. Secondary metals zinc, nickel, and cobalt were successfully integrated into the copper HKUST-1 structure, producing three unique bimetallic MOF structures. Growth parameters such as metal precursor salts, evaporation effects on coverage and crystallinity, and substrate effect under ambient conditions were correlated with the crystal size and surface coverage of the crystallites to understand the conditions required for bimetallic MOF growth as thin films allow them to be optimized for a variety of applications in catalysis, separations, and materials science.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2849–2856 2849–2856"},"PeriodicalIF":3.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910988","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":"Novel Oxaprozin Cocrystals/Salts: Solubility Enhancement for Oxaprozin and Release Control for Minoxidil","authors":"Lingli Hou,&nbsp;Menglong Zhang,&nbsp;Linlin Shi,&nbsp;Xiaofang Luo,&nbsp;Ruiyu De,&nbsp;Wei Chen,&nbsp;Yuanding Jing and Ying Bao*,&nbsp;","doi":"10.1021/acs.cgd.5c0008710.1021/acs.cgd.5c00087","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00087https://doi.org/10.1021/acs.cgd.5c00087","url":null,"abstract":"<p >Oxaprozin (OXP), a commonly utilized non-steroidal anti-inflammatory drug, exhibits limited water solubility that diminishes its therapeutic efficacy. In this study, seven new OXP multicomponent crystals were successfully prepared through a multicomponent crystal strategy, including one OXP-MIN (Minoxidil) drug–drug cocrystal, one OXP-ADMP cocrystal, two OXP anionic salts (OXP-3HYP salt and OXP-3AP salt), and three OXP cationic salts (OXP-BSA salt, OXP-PTSA-ACN salt solvate, and OXP-PCBSA-ACN salt solvate). Among them, the OXP-ADMP cocrystal, OXP-3HYP salt, and OXP-3AP salt significantly improved the dissolution performance of OXP. By combining the calculations of solvation free energy and lattice energy, the intrinsic mechanism of solubilization was revealed. Initially, the hydrogen bonding sites of OXP were determined through Full Interaction Maps (FIM) analysis, and 54 coformers from different categories were selected for computational and experimental screening. Liquid-assisted grinding experiments successfully yielded 23 new OXP-based phases, and the combination of the Conductor-like Screening Model for Real Solvents (COSMO-RS) and the Molecular Complementarity (MC) method increased the computational screening success rate to 83.3%. The crystal structures of seven new OXP multicomponent crystals were structurally characterized through single crystal X-ray diffraction (SCXRD). Accelerated stability tests indicated that all multicomponent crystals exhibited excellent phase stability, providing strong support for maintaining drug efficacy and safety. Solubility and dissolution tests revealed that OXP-ADMP cocrystal, OXP-3HYP salt, and OXP-3AP salt significantly improved the solubility (by 14.66, 11.78, and 14.66%, respectively) and dissolution rate (by 3.35, 21.79, and 44.69%, respectively) of OXP in pH 6.8 buffer. Notably, the OXP-MIN drug–drug cocrystal substantially reduced the solubility (by 86.06%) and dissolution rate (by 92.20%) of MIN under the same conditions, highlighting its potential for achieving sustained release of MIN and offering a promising strategy for low-dose oral MIN treatment of alopecia. Conformational similarity analysis showed that salt formation induced more significant conformational changes in OXP molecules compared to cocrystal formation. The formation mechanisms of cocrystals, anionic salts, and cationic salts, as well as the stoichiometric ratio differences between OXP and coformers in multicomponent crystals, were elucidated through p<i>K</i>_a and Molecular Electrostatic Potential Surface (MEPS) analysis. Furthermore, the strength of intermolecular hydrogen bonds was evaluated using Independent Gradient Model analysis based on Hirshfeld Surfaces (IGMH) and Atoms in Molecules (AIM) analysis. This study not only provides critical theoretical perspectives for improving drug solubility through crystal engineering techniques but also presents a new case for the development of drug–drug cocrystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3013–3028 3013–3028"},"PeriodicalIF":3.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910970","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":"Modulating Milling-Induced Amorphization Propensity of Drug Crystals by Cocrystallization","authors":"Sayantan Chattoraj,&nbsp; and ,&nbsp;Changquan Calvin Sun*,&nbsp;","doi":"10.1021/acs.cgd.5c0016310.1021/acs.cgd.5c00163","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00163https://doi.org/10.1021/acs.cgd.5c00163","url":null,"abstract":"<p >Amorphization is a common phase transformation that occurs during stress-intensive processes, such as milling. This study aims to evaluate the impact of cocrystallization on the amorphization behavior of sulfamethazine (SMT) during cryo-milling using two SMT cocrystals: one with <i>p</i>-hydroxybenzoic acid (SMT-HBA) and the other with benzamide (SMT-BNZ). At short milling durations (<i>t</i> &lt; 30 min), the rank order of amorphous generation was SMT-BNZ &gt; SMT ≫ SMT-HBA. However, after 2 h of cryo-milling, this order shifted to SMT-HBA &gt; SMT-BNZ &gt; SMT. Both SMT and SMT-BNZ exhibited an earlier onset of amorphization than SMT-HBA. The delayed amorphization onset of SMT-HBA is attributed to its higher crystal lattice strength. The rank order of amorphization extent over longer milling (up to 2 h) aligns with the physical stability of the generated amorphous phase, as assessed using configurational entropy and structural relaxation times based on the Adam–Gibbs equation. The combination of a slow onset of amorphization and the slow crystallization of the generated amorphous phase in SMT-HBA explains the shift in the rank order of amorphization extent over the entire milling duration. Understanding the interplay between crystal lattice strength and amorphous stability in stress-induced amorphization offers valuable guidance for mitigating the stress sensitivity of certain drugs through cocrystallization.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3128–3136 3128–3136"},"PeriodicalIF":3.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910973","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":"Crystallization of NaCl-NaNO₃-H₂O in Porous Media During Drying.","authors":"Leo Pel, Sebastiaan Godts, Amelie Stahlbuhk, Noushine Shahidzadeh, Michael Steiger","doi":"10.1021/acs.cgd.4c01446","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01446","url":null,"abstract":"<p><p>In this study, we investigated the crystallization of a salt mixture during drying in a porous medium. Specifically, we focused on the ternary system of NaCl-NaNO₃-H₂O, which is also encountered in situ. In order to study the crystallization, we use a specialized 4.7 T NMR setup that allows us to directly measure the NaCl and NaNO₃ concentrations in a porous medium and track their ratio during drying, providing direct insight into the phase diagram. The measurements indicate that the equilibrium phase diagram alone is not sufficient to describe the physical processes that occur in porous media during drying experiments. In the case of forced drying in this study, where advection of the ions is dominant (<i>Pe</i> > 5), the measurements indicate that we need to take supersaturation into account and that crystallization is driven by transport. As a result, the ratio of a salt mixture will remain constant in the porous medium throughout the experiments, as was seen for this ternary system Na⁺, Cl^-, NO₃ ^- resulting in the formation of both NaCl and NaNO₃. These results indicate that the rate of evaporation, in combination with the effect of supersaturation and solution transport in the pore system, allows the saturation degree given by the phase diagram to be surpassed. This phenomenon is critical when assessing mixed salt systems in porous media and should be considered when evaluating phase diagrams alone.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2843-2848"},"PeriodicalIF":3.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12063039/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143954930","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":"Peripheral Ligand Modification to Tune Spin Crossover Behavior of Fe(III) Complexes","authors":"Bijoy Dey,&nbsp;Jordi Cirera,&nbsp;Liliana P. Ferreira,&nbsp;Paulo N. Martinho* and Vadapalli Chandrasekhar*,&nbsp;","doi":"10.1021/acs.cgd.5c0011210.1021/acs.cgd.5c00112","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00112https://doi.org/10.1021/acs.cgd.5c00112","url":null,"abstract":"<p >Two major factors governing the spin crossover (SCO) behavior are the electronic and steric aspects of the ligand. The electronic effects directly alter the energy gap between the frontier molecular (t_2g and e_g) orbitals, whereas the steric effects can lead to a distorted structure, which then can change the electronic properties of the complex, leading to a change in the spin state. Here, we investigated how the steric modulation of the ligand by its peripheral modification affects the spin states of the corresponding Fe(III) complexes. We chose three different amines, <i>N</i>-ethylethylenediamine, <i>N</i>-phenylethylenediamine, and <i>N</i>-benzylethylenediamine, and condensed them with salicylaldehyde and 3-methoxysalicylaldehyde to afford the corresponding Schiff base ligands, HL1, HL3, and HL2, respectively. Interaction of these ligands with Fe(III) salts afforded [Fe(L1)₂]NCS (<b>1</b>), [Fe(L2)₂NCS]·H₂O (<b>2·H</b>_<b>2</b><b>O</b>), and [Fe(L3)₂]NCS (<b>3</b>), respectively. 3-Methoxysalicylaldehyde with <i>N</i>-phenylethylenediamine afforded ligand HL2 and complex <b>2·H</b>_<b>2</b><b>O</b>. <b>1</b> and <b>3</b> exhibit SCO behavior, while complex <b>2·H</b>_<b>2</b><b>O</b> remains in the high spin state. These results were rationalized by a combination of experimental and theoretical studies.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3065–3074 3065–3074"},"PeriodicalIF":3.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911446","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}