Crystal Growth & Design最新文献

{"title":"Unique 3d–4f Heterometallic Networks Based on a Nitronyl Nitroxide Radical Functionalized with Additional N and O Donors","authors":"Chao-Yi Jin, Yan Zhou, Dylan Martinez, Licun Li, Jean-Pascal Sutter","doi":"10.1021/acs.cgd.4c01082","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01082","url":null,"abstract":"Three 2D heterospin radical-3d–4f networks with the formula {[Ln(hfac)₃]₂[M(hfac)₂](NIT-3Py-5-Pyoe)₂}_n (M^II = Co^II and Ln^III = Gd <b>1</b>, Dy <b>2</b>; M^II = Cu^II and Ln^III = Dy <b>3</b>; NIT-3Py-5-Pyoe = (2-(5-(4-pyridinone)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)) have been successfully constructed using a novel multidentate nitronyl nitroxide paramagnetic ligand containing mixed N- and O-donor sites. In these 2D structures, the paramagnetic ligand acts as a tridentate linker to bind two Ln^III ions by means of one aminoxyl group and one pyridinone unit and one M^II ion through the pyridine ring. The magnetic behaviors of <b>1</b>–<b>3</b> are governed by predominant ferromagnetic radical–Ln interactions.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194587","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":"Vacuum-Pumping Induced Crystallographic Anisotropy of Poly(dimethylsiloxane) Oil under Capillary Confinement","authors":"Xiang Shi*,&nbsp;","doi":"10.1021/acs.cgd.4c0091610.1021/acs.cgd.4c00916","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00916https://doi.org/10.1021/acs.cgd.4c00916","url":null,"abstract":"<p >Investigating the low-temperature crystallization behavior of liquid polysiloxanes poses a significant challenge. To address this issue, a custom low-temperature chamber with specialized sample holders was meticulously constructed and integrated with a laboratory X-ray diffraction apparatus, enabling time-resolved wide-angle X-ray diffraction (WAXD) measurements of linear poly(dimethylsiloxane) (PDMS) oil and cross-linked PDMS film during cooling and heating. Under vacuum pumping and capillary confinement, the linear silanol-terminated PDMS oil demonstrates significant crystalline orientation at low temperatures when the crystalline index surpasses 10%, with the recorded 2D diffraction patterns showing heterogeneous azimuthal intensity distributions. The presence of crystallographic anisotropy is strongly influenced by the experimental vacuum pumping rather than the millimeter-scale capillary confinement. Unlike the strain-induced alignment of crystalline planes observed in stretched PDMS film, the vacuum-pumping-induced crystallographic anisotropy in linear PDMS oil measured within a capillary only results in a minimal or partial lamellar orientation. This alignment will cause crystalline chain segments to pack parallel to the incident X-ray beam direction and fold within the <i>a-c</i> plane. These findings are expected to enhance low-temperature X-ray analysis techniques for liquid samples and facilitate future crystallographic investigations of polysiloxane materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246342","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":"Vacuum-Pumping Induced Crystallographic Anisotropy of Poly(dimethylsiloxane) Oil under Capillary Confinement","authors":"Xiang Shi","doi":"10.1021/acs.cgd.4c00916","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00916","url":null,"abstract":"Investigating the low-temperature crystallization behavior of liquid polysiloxanes poses a significant challenge. To address this issue, a custom low-temperature chamber with specialized sample holders was meticulously constructed and integrated with a laboratory X-ray diffraction apparatus, enabling time-resolved wide-angle X-ray diffraction (WAXD) measurements of linear poly(dimethylsiloxane) (PDMS) oil and cross-linked PDMS film during cooling and heating. Under vacuum pumping and capillary confinement, the linear silanol-terminated PDMS oil demonstrates significant crystalline orientation at low temperatures when the crystalline index surpasses 10%, with the recorded 2D diffraction patterns showing heterogeneous azimuthal intensity distributions. The presence of crystallographic anisotropy is strongly influenced by the experimental vacuum pumping rather than the millimeter-scale capillary confinement. Unlike the strain-induced alignment of crystalline planes observed in stretched PDMS film, the vacuum-pumping-induced crystallographic anisotropy in linear PDMS oil measured within a capillary only results in a minimal or partial lamellar orientation. This alignment will cause crystalline chain segments to pack parallel to the incident X-ray beam direction and fold within the <i>a-c</i> plane. These findings are expected to enhance low-temperature X-ray analysis techniques for liquid samples and facilitate future crystallographic investigations of polysiloxane materials.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194774","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":"Light-Triggered Rolling and Unrolling of Molecular Crystal Microsheets","authors":"Pranaya P. Ghate, Cody J. Perry, Veronica Carta, Ibraheem Bushnak, Yahya J. Almuallem, Gregory J. O. Beran, Christopher J. Bardeen, Rabih O. Al-Kaysi","doi":"10.1021/acs.cgd.4c00996","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00996","url":null,"abstract":"The anthracene derivative (<i>E</i>)-3-(3-(anthracen-9-yl)allylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione (<i><b>E</b></i><b>-ADUD</b>) undergoes an E → Z photoisomerization in solution but not in crystals prepared by standard methods like solvent diffusion. However, the lipophilic cyclohexyl group facilitates precipitation of crystalline microsheets with submicron thicknesses from an aqueous solution containing sodium dodecyl sulfate and 1-dodecanol. These microsheets have horizontal dimensions on the order of 200 μm and are composed of a metastable crystal polymorph that permits the E → Z isomerization to proceed. Photoisomerization using visible light caused these microsheets to rapidly roll up into multilayer microcylinders with diameters ranging from 20 to 40 μm. If the light was removed at this point, then the microscrolls were stable indefinitely. Continued exposure to visible light uncurled these cylindrical structures, reversing the mechanical process but not the photochemical reaction. The unrolled microsheets retained their crystallinity and could bend and twist under alternating UV and visible light but could not be rolled up again. The initial high curvature rolling up can be attributed to the creation of a surface layer of the Z-isomer that interacts with the underlying E-isomer crystal layer to generate a bimorph structure. Prolonged irradiation distributes the photoproduct more uniformly throughout the crystal and relieves this interfacial stress. The photoinduced rolling and unrolling could prove useful for applications like antenna or stent opening in hard-to-reach environments.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194773","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":"Unique 3d–4f Heterometallic Networks Based on a Nitronyl Nitroxide Radical Functionalized with Additional N and O Donors","authors":"Chao-Yi Jin,&nbsp;Yan Zhou,&nbsp;Dylan Martinez,&nbsp;Licun Li* and Jean-Pascal Sutter*,&nbsp;","doi":"10.1021/acs.cgd.4c0108210.1021/acs.cgd.4c01082","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01082https://doi.org/10.1021/acs.cgd.4c01082","url":null,"abstract":"<p >Three 2D heterospin radical-3d–4f networks with the formula {[Ln(hfac)₃]₂[M(hfac)₂](NIT-3Py-5-Pyoe)₂}_n (M^II = Co^II and Ln^III = Gd <b>1</b>, Dy <b>2</b>; M^II = Cu^II and Ln^III = Dy <b>3</b>; NIT-3Py-5-Pyoe = (2-(5-(4-pyridinone)-3-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)) have been successfully constructed using a novel multidentate nitronyl nitroxide paramagnetic ligand containing mixed N- and O-donor sites. In these 2D structures, the paramagnetic ligand acts as a tridentate linker to bind two Ln^III ions by means of one aminoxyl group and one pyridinone unit and one M^II ion through the pyridine ring. The magnetic behaviors of <b>1</b>–<b>3</b> are governed by predominant ferromagnetic radical–Ln interactions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237343","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":"Light-Triggered Rolling and Unrolling of Molecular Crystal Microsheets","authors":"Pranaya P. Ghate,&nbsp;Cody J. Perry,&nbsp;Veronica Carta,&nbsp;Ibraheem Bushnak,&nbsp;Yahya J. Almuallem,&nbsp;Gregory J. O. Beran,&nbsp;Christopher J. Bardeen* and Rabih O. Al-Kaysi*,&nbsp;","doi":"10.1021/acs.cgd.4c0099610.1021/acs.cgd.4c00996","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00996https://doi.org/10.1021/acs.cgd.4c00996","url":null,"abstract":"<p >The anthracene derivative (<i>E</i>)-3-(3-(anthracen-9-yl)allylidene)-1,5-dioxaspiro[5.5]undecane-2,4-dione (<i><b>E</b></i><b>-ADUD</b>) undergoes an E → Z photoisomerization in solution but not in crystals prepared by standard methods like solvent diffusion. However, the lipophilic cyclohexyl group facilitates precipitation of crystalline microsheets with submicron thicknesses from an aqueous solution containing sodium dodecyl sulfate and 1-dodecanol. These microsheets have horizontal dimensions on the order of 200 μm and are composed of a metastable crystal polymorph that permits the E → Z isomerization to proceed. Photoisomerization using visible light caused these microsheets to rapidly roll up into multilayer microcylinders with diameters ranging from 20 to 40 μm. If the light was removed at this point, then the microscrolls were stable indefinitely. Continued exposure to visible light uncurled these cylindrical structures, reversing the mechanical process but not the photochemical reaction. The unrolled microsheets retained their crystallinity and could bend and twist under alternating UV and visible light but could not be rolled up again. The initial high curvature rolling up can be attributed to the creation of a surface layer of the Z-isomer that interacts with the underlying E-isomer crystal layer to generate a bimorph structure. Prolonged irradiation distributes the photoproduct more uniformly throughout the crystal and relieves this interfacial stress. The photoinduced rolling and unrolling could prove useful for applications like antenna or stent opening in hard-to-reach environments.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237920","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":"Dual-Defect Modified 2D/2D TiO2/g-C3N4 Heterojunction for Photocatalytic H2 Production","authors":"Jiahui Wang, Li Li, Xiangju Ye, Yang Yang, Wei Ren, Jingbiao Ge, Sujuan Zhang, Xiuzhen Zheng, Shifu Chen","doi":"10.1021/acs.cgd.4c00826","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00826","url":null,"abstract":"In order to solve the current energy and environmental crisis, the design of efficient catalyst materials is a highly effective solution. In this paper, the photocatalytic performance of TiO₂/g-C₃N₄ composites was improved by regulating their microstructure, such as by constructing nanosheet structures, defect sites, and contact interfaces. Although TiO₂ had limited activity in H₂ production under visible light irradiation, it could serve as an electron acceptor of g-C₃N₄, and it greatly increased the photocatalytic activity of g-C₃N₄. The optimal TiO₂/g-C₃N₄ composite showed good photocatalytic performance (436.3 μmol h^–1 g^–1), which was 23.8 and 3 times that of T400 and g-C₃N₄, respectively. The increased photocatalytic activity of the TiO₂/g-C₃N₄ composite could be attributed to the higher separation rate of the photogenerated charge carriers (PCCs), more active sites for the reaction, and a lower energy barrier than that of g-C₃N₄. Through many characterization and testing technologies, this work deeply studies the relationship between the fine structure and reaction mechanism of 2<i>D</i>/2D TiO₂/g-C₃N₄, providing a new direction and understanding for the design and development of 2D materials with highly efficient activity.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194776","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":"Tailored Air Annealing Strategy to Promote the Photoelectric Performance of AZO-Based Multilayer Films","authors":"Shan Gao, Lin Li, Yunqing Tang, Ping Yang","doi":"10.1021/acs.cgd.4c00339","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00339","url":null,"abstract":"We investigated the effects of air annealing on the photoelectric performance of aluminum-doped zinc oxide (AZO)/Al₂O₃/Ag/AZO. Transparent conductive films (TCFs) of AZO (55 nm)/Al₂O₃ (1.5 nm)/Ag (10 nm)/AZO (55 nm) were deposited on glass substrates via RF/DC magnetron sputtering at room temperature. The Al₂O₃ seed layer was proved to promote Ag wetting in the multilayers structure. The result shows that the optimum annealing condition for the multilayer film was determined as annealing for 30 min at 300 °C. The smooth surface obtained effectively reduced the light absorption and scattering, and the Ag layer with continuous growth and a high degree of crystallization contributed to the conductivity. The films exhibited a sheet resistance of 5.80 Ω/sq, an average transmittance of 93.43% in the 400–800 nm range, and a figure of merit (FOM) that was enhanced by 26.9% to 87.3 × 10^–3 Ω^–1 via air annealing. Remarkably, this is the highest FOM reported for analogous TCFs with an AZO/Ag/AZO configuration. The TCFs of this structure prepared by our method have potential applications in photovoltaic devices.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.8,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142194775","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":"Tailored Air Annealing Strategy to Promote the Photoelectric Performance of AZO-Based Multilayer Films","authors":"Shan Gao,&nbsp;Lin Li,&nbsp;Yunqing Tang* and Ping Yang*,&nbsp;","doi":"10.1021/acs.cgd.4c0033910.1021/acs.cgd.4c00339","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00339https://doi.org/10.1021/acs.cgd.4c00339","url":null,"abstract":"<p >We investigated the effects of air annealing on the photoelectric performance of aluminum-doped zinc oxide (AZO)/Al₂O₃/Ag/AZO. Transparent conductive films (TCFs) of AZO (55 nm)/Al₂O₃ (1.5 nm)/Ag (10 nm)/AZO (55 nm) were deposited on glass substrates via RF/DC magnetron sputtering at room temperature. The Al₂O₃ seed layer was proved to promote Ag wetting in the multilayers structure. The result shows that the optimum annealing condition for the multilayer film was determined as annealing for 30 min at 300 °C. The smooth surface obtained effectively reduced the light absorption and scattering, and the Ag layer with continuous growth and a high degree of crystallization contributed to the conductivity. The films exhibited a sheet resistance of 5.80 Ω/sq, an average transmittance of 93.43% in the 400–800 nm range, and a figure of merit (FOM) that was enhanced by 26.9% to 87.3 × 10^–3 Ω^–1 via air annealing. Remarkably, this is the highest FOM reported for analogous TCFs with an AZO/Ag/AZO configuration. The TCFs of this structure prepared by our method have potential applications in photovoltaic devices.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237781","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":"Development of a Dual-State Emissive Naphthalimide-Based Organic Probe: Interesting Synergistic Effects from the Solid State to the Solution Phase","authors":"Aditi Garg,&nbsp;Umesh R. Pratap,&nbsp;Abhishek Banerjee* and Sujit Kumar Ghosh*,&nbsp;","doi":"10.1021/acs.cgd.4c0086710.1021/acs.cgd.4c00867","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00867https://doi.org/10.1021/acs.cgd.4c00867","url":null,"abstract":"<p >Luminescent compounds have garnered significant interest for their wide range of applications in light harvesting, cell imagining, LASERs, light-emitting diodes, etc. Conventional luminescent organic molecules show their emissive properties in the solution phase; however, in the solid state, a quenching of the fluorescence intensity occurs. Researchers have been able to overcome such challenges using the phenomenon of aggregation-induced emission (AIE), which enhances the solid-state emissive properties through close packing aided by nonbonded interactions. Such molecules, conventionally referred to as AIE luminogens, are observed to show phase-exclusive emissive properties, i.e., emissive in the solid state but nonemissive in the solution phase. Such drawbacks have prompted us to investigate molecules having emissive properties in both solution and solid phase, viz., dual-state emissive molecules [dual-state emission (DSE) luminogens]. Among these, naphthalimides, owing to their versatile conformational arrangements, are of prime interest. In this article, we present the design, synthesis, structural characterization, and detailed spectroscopic studies of a naphthalimide-based luminogen molecule, 6-(4-(2-hydroxyethyl)piperazin-1-yl)-2-(6-methoxybenzothiazol-2-yl)-1<i>H</i>-benzoisoquinoline-1,3(2<i>H</i>)-dione (<b>HPMTB</b>). Single-crystal X-ray diffraction studies in the solid state have provided detailed structural information as well as the molecular packing arrangement of the molecule <b>HPMTB</b> along three dimensions. Solution-phase and solid-state fluorescence studies have revealed the existence of aggregation-induced emissive and mechanofluorochromic properties within the molecule. Detailed solution-phase photophysical investigations of <b>HPMTB</b> have revealed the existence of aggregates in a protic polar solvent (water) via the accumulation of flakes. Solid-state emission also shows the existence of reversible mechanofluorochromism in <b>HPMTB</b>. The current work develops materials that can attain DSE and mechanofluorochromism and sets up the foundation for the development of naphthalimide-based organic molecules for use as luminescent smart materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142237780","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}