Pub Date : 2023-08-29DOI: 10.3390/inorganics11090354
I. Alnaser, A. Fouly, M. Aijaz, J. A. Mohammed, M. B. Elsheniti, Sameh A. Ragab, H. S. Abdo
This research work highlights the tribomechanical investigations of using a low loading fraction of two ceramics combinations, Alumina (Al2O3) and Silicon Carbide (SiC) as reinforcement for Low-density Polyethylene (LDPE) matrix. The hybrid additives with different weight percentages (0.1 + 0.1, 0.25 + 0.25 and 0.5 + 0.5 wt%) were mixed with LDPE matrix and the degree of homogeneity was controlled using double-screw extruder prior to fabricating the composite samples via the injection molding machine. The nanoparticles fillers were characterized by field emission scanning electron microscope (FESEM), EDX and particle size analyzer to check its morphology, composition and size distribution. Thermogravimetric analyzer (TGA) and melting flow index (MFI) were performed for the fabricated nanocomposites samples. The mechanical properties of the nanocomposite were evaluated by performing tensile test, bending test and Shore-D hardness test, while the tribological performance was investigated using a ball on desk apparatus under different applied loads and sliding times. Moreover, in order to confirm the load-carrying capability of the composite, contact stresses was measured via finite element model using ANSYS software. The results show that the incorporation of low fraction hybrid ceramic nanoparticles can contributed positively in the tribological and mechanical properties. Based on the experimental results, the maximum improvement in the tensile strength was 5.38%, and 8.15% for hardness LDPE with 0.5 Al2O3 and 0.5 SiC, while the lowest coefficient of friction was noticed under normal load of 10 N, which was approximately 12.5% for the same composition. The novel approach of incorporating low fraction hybrid ceramic nanoparticles as reinforcement for LDPE matrix is investigated, highlighting their positive contributions to the tribological and mechanical properties of the resulting nanocomposites.
{"title":"Enhancing the Tribo-Mechanical Performance of LDPE Nanocomposites Utilizing Low Loading Fraction Al2O3/SiC Hybrid Nanostructured Oxide Fillers","authors":"I. Alnaser, A. Fouly, M. Aijaz, J. A. Mohammed, M. B. Elsheniti, Sameh A. Ragab, H. S. Abdo","doi":"10.3390/inorganics11090354","DOIUrl":"https://doi.org/10.3390/inorganics11090354","url":null,"abstract":"This research work highlights the tribomechanical investigations of using a low loading fraction of two ceramics combinations, Alumina (Al2O3) and Silicon Carbide (SiC) as reinforcement for Low-density Polyethylene (LDPE) matrix. The hybrid additives with different weight percentages (0.1 + 0.1, 0.25 + 0.25 and 0.5 + 0.5 wt%) were mixed with LDPE matrix and the degree of homogeneity was controlled using double-screw extruder prior to fabricating the composite samples via the injection molding machine. The nanoparticles fillers were characterized by field emission scanning electron microscope (FESEM), EDX and particle size analyzer to check its morphology, composition and size distribution. Thermogravimetric analyzer (TGA) and melting flow index (MFI) were performed for the fabricated nanocomposites samples. The mechanical properties of the nanocomposite were evaluated by performing tensile test, bending test and Shore-D hardness test, while the tribological performance was investigated using a ball on desk apparatus under different applied loads and sliding times. Moreover, in order to confirm the load-carrying capability of the composite, contact stresses was measured via finite element model using ANSYS software. The results show that the incorporation of low fraction hybrid ceramic nanoparticles can contributed positively in the tribological and mechanical properties. Based on the experimental results, the maximum improvement in the tensile strength was 5.38%, and 8.15% for hardness LDPE with 0.5 Al2O3 and 0.5 SiC, while the lowest coefficient of friction was noticed under normal load of 10 N, which was approximately 12.5% for the same composition. The novel approach of incorporating low fraction hybrid ceramic nanoparticles as reinforcement for LDPE matrix is investigated, highlighting their positive contributions to the tribological and mechanical properties of the resulting nanocomposites.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47672154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-29DOI: 10.3390/inorganics11090353
Marisa James, Madelyn R. Shevlin, Thomas B. Green, M. Smart, C. McMillen, Jared A. Pienkos
Pyrazino-phenanthroline ligands are commonly used with transition metals as DNA intercalation agents. Herein, we report the characterization of two commonly utilized pyrazino-phenanthroline ligands, dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq) and (benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), by single-crystal X-ray diffraction. Additionally, the characterization of [Ir(ppy)2(dppn)][PF6], where Hppy = 2-phenylpyridine, by single-crystal X-ray diffraction is described. Both the dpq and dppn ligands crystallize as chloroform solvates where the chloroform molecule occupies the equivalent binding pocket of a metal in metal complexes of these ligands. These pyrazino-phenanthrolines are largely planar, with the dppn ligand displaying a slight twist. When the dppn ligand is coordinated to iridium(III), the dppn ligand on the resulting complex displays a significant degree of bending along the longitudinal direction of the ligand. This iridium (III) complex crystallizes as a CH2Cl2 and Et2O solvate and due to the volatility of these solvents these crystals are only stable for a few seconds outside of the mother liquor. The structures of the free ligands and the [Ir(ppy)2(dppn)][PF6] complex all display extensive π stacking interactions.
{"title":"Crystal Structures of DNA Intercalating Agents Dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq), (Benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), and [Ir(ppy)2(dppn)][PF6] (Where Hppy = 2-Phenylpyridine)","authors":"Marisa James, Madelyn R. Shevlin, Thomas B. Green, M. Smart, C. McMillen, Jared A. Pienkos","doi":"10.3390/inorganics11090353","DOIUrl":"https://doi.org/10.3390/inorganics11090353","url":null,"abstract":"Pyrazino-phenanthroline ligands are commonly used with transition metals as DNA intercalation agents. Herein, we report the characterization of two commonly utilized pyrazino-phenanthroline ligands, dipyrido[3,2-f:2′,3′-h]quinoxaline (dpq) and (benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn), by single-crystal X-ray diffraction. Additionally, the characterization of [Ir(ppy)2(dppn)][PF6], where Hppy = 2-phenylpyridine, by single-crystal X-ray diffraction is described. Both the dpq and dppn ligands crystallize as chloroform solvates where the chloroform molecule occupies the equivalent binding pocket of a metal in metal complexes of these ligands. These pyrazino-phenanthrolines are largely planar, with the dppn ligand displaying a slight twist. When the dppn ligand is coordinated to iridium(III), the dppn ligand on the resulting complex displays a significant degree of bending along the longitudinal direction of the ligand. This iridium (III) complex crystallizes as a CH2Cl2 and Et2O solvate and due to the volatility of these solvents these crystals are only stable for a few seconds outside of the mother liquor. The structures of the free ligands and the [Ir(ppy)2(dppn)][PF6] complex all display extensive π stacking interactions.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47121350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-27DOI: 10.3390/inorganics11090352
A. Abutaleb
Copper/sulfur co-doped titanium dioxide-carbon nanofibers (Cu,S-codoped TiO2 NPs, decorated-CNFs) catalysts were synthesized using the electrospinning process to produce composite nanofibers (NFs). These composite NFs were utilized for the hydrolysis of sodium borohydride (SBH) to generate hydrogen gas (H2), taking advantage of their catalytic properties. The experimental results demonstrated that using 100 mg of composite NFs yielded the highest catalytic activity for H2 production, generating 79 mL of H2 gas within 6 min at 25 °C and 1000 revolutions per minute (rpm) using 1 mmol of SBH. As the catalyst dosage was reduced from 100 mg to 75, 50, and 25 mg, the reaction time increased by 9, 13, and 18 min, respectively. Kinetic studies revealed that the reaction rate followed a first-order reaction, indicating a direct proportionality between the rate of reaction and the catalyst amount. Additionally, it was observed that the concentration of SBH had no influence on the reaction rate, suggesting a zero-order reaction. Increasing the reaction temperature resulted in a reduced reaction time. The activation energy was determined to be 26.16 kJ mol−1. The composite NFs maintained their superior performance over five iterations. These findings suggest that composite nanofibers have the potential to serve as a cost-effective alternative to expensive catalysts in hydrogen production.
{"title":"Synthesis of Copper/Sulfur Co-Doped TiO2-Carbon Nanofibers as Catalysts for H2 Production via NaBH4 Hydrolysis","authors":"A. Abutaleb","doi":"10.3390/inorganics11090352","DOIUrl":"https://doi.org/10.3390/inorganics11090352","url":null,"abstract":"Copper/sulfur co-doped titanium dioxide-carbon nanofibers (Cu,S-codoped TiO2 NPs, decorated-CNFs) catalysts were synthesized using the electrospinning process to produce composite nanofibers (NFs). These composite NFs were utilized for the hydrolysis of sodium borohydride (SBH) to generate hydrogen gas (H2), taking advantage of their catalytic properties. The experimental results demonstrated that using 100 mg of composite NFs yielded the highest catalytic activity for H2 production, generating 79 mL of H2 gas within 6 min at 25 °C and 1000 revolutions per minute (rpm) using 1 mmol of SBH. As the catalyst dosage was reduced from 100 mg to 75, 50, and 25 mg, the reaction time increased by 9, 13, and 18 min, respectively. Kinetic studies revealed that the reaction rate followed a first-order reaction, indicating a direct proportionality between the rate of reaction and the catalyst amount. Additionally, it was observed that the concentration of SBH had no influence on the reaction rate, suggesting a zero-order reaction. Increasing the reaction temperature resulted in a reduced reaction time. The activation energy was determined to be 26.16 kJ mol−1. The composite NFs maintained their superior performance over five iterations. These findings suggest that composite nanofibers have the potential to serve as a cost-effective alternative to expensive catalysts in hydrogen production.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48825612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-26DOI: 10.3390/inorganics11090351
Paraskevi Kontomaris, Gregory M. Darone, Laura C. Paredes-Quevedo, S. Bobev
Reported are the synthesis and structural characterization of a series of quaternary lithium-alkaline earth metal alumo-silicides and alumo-germanides with the base formula A2LiAlTt2 (A = Ca, Sr, Ba; Tt = Si, Ge). To synthesize each compound, a mixture of the elements with the desired stoichiometric ratio was loaded into a niobium tube, arc welded shut, enclosed in a silica tube under vacuum, and heated in a tube furnace. Each sample was analyzed by powder and single-crystal X-ray diffraction, and the crystal structure of each compound was confirmed and refined from single-crystal X-ray diffraction data. The structures, despite the identical chemical formulae, are different, largely dependent on the nature of the alkaline earth metal. The differing cation determines the structure type—the calcium compounds are part of the TiNiSi family with the Pnma space group, the strontium compounds are isostructural with Na2LiAlP2 with the Cmce space group, and the barium compounds crystallize with the PbFCl structure type in the P4/nmm space group. The anion (silicon or germanium) only impacts the size of the unit cell, with the silicides having smaller unit cell volumes than the germanides.
{"title":"The Synthesis and Crystal Structure of Six Quaternary Lithium-Alkaline Earth Metal Alumo-Silicides and Alumo-Germanides, A2LiAlTt2 (A = Mg, Ca, Sr, Ba; Tt = Si, Ge)","authors":"Paraskevi Kontomaris, Gregory M. Darone, Laura C. Paredes-Quevedo, S. Bobev","doi":"10.3390/inorganics11090351","DOIUrl":"https://doi.org/10.3390/inorganics11090351","url":null,"abstract":"Reported are the synthesis and structural characterization of a series of quaternary lithium-alkaline earth metal alumo-silicides and alumo-germanides with the base formula A2LiAlTt2 (A = Ca, Sr, Ba; Tt = Si, Ge). To synthesize each compound, a mixture of the elements with the desired stoichiometric ratio was loaded into a niobium tube, arc welded shut, enclosed in a silica tube under vacuum, and heated in a tube furnace. Each sample was analyzed by powder and single-crystal X-ray diffraction, and the crystal structure of each compound was confirmed and refined from single-crystal X-ray diffraction data. The structures, despite the identical chemical formulae, are different, largely dependent on the nature of the alkaline earth metal. The differing cation determines the structure type—the calcium compounds are part of the TiNiSi family with the Pnma space group, the strontium compounds are isostructural with Na2LiAlP2 with the Cmce space group, and the barium compounds crystallize with the PbFCl structure type in the P4/nmm space group. The anion (silicon or germanium) only impacts the size of the unit cell, with the silicides having smaller unit cell volumes than the germanides.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42114863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-25DOI: 10.3390/inorganics11090349
Xinyi Zhou, Yang-Rong Yao, Yajing Hu, Le Yang, Shaoting Yang, Yilu Zhang, Qianyan Zhang, P. Peng, Peng Jin, Fang‐Fang Li
The reactivity of the open-shell Gd@C2v-C82 with different charge states towards benzyl bromide was investigated. [Gd@C2v-C82]3− exhibited enhanced activity relative to Gd@C2v-C82 and [Gd@C2v-C82]−. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@C2v-C82. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@C2v-C82. Theoretical studies demonstrate that only [Gd@C2v-C82]3− has a HOMO energy level that matches well with the LUMO energy level of the PhCH2 radical, providing a rationalization for the observed significantly different reactivity.
{"title":"Reactivity of Open-Shell Metallofullerene Anions: Synthesis, Crystal Structures, and Electrochemical Properties of Benzylated Gd@C2v-C82","authors":"Xinyi Zhou, Yang-Rong Yao, Yajing Hu, Le Yang, Shaoting Yang, Yilu Zhang, Qianyan Zhang, P. Peng, Peng Jin, Fang‐Fang Li","doi":"10.3390/inorganics11090349","DOIUrl":"https://doi.org/10.3390/inorganics11090349","url":null,"abstract":"The reactivity of the open-shell Gd@C2v-C82 with different charge states towards benzyl bromide was investigated. [Gd@C2v-C82]3− exhibited enhanced activity relative to Gd@C2v-C82 and [Gd@C2v-C82]−. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@C2v-C82. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@C2v-C82. Theoretical studies demonstrate that only [Gd@C2v-C82]3− has a HOMO energy level that matches well with the LUMO energy level of the PhCH2 radical, providing a rationalization for the observed significantly different reactivity.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48759937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-25DOI: 10.3390/inorganics11090350
M. El-Naggar, M. Abu-Youssef, M. Haukka, A. Barakat, M. Sharaf, S. Soliman
The [Ag(3ADMT)(NO3)]n complex was synthesized by the self-assembly of 3-amino-5,6-dimethyl-1,2,4-triazine (3ADMT) and AgNO3. Its molecular structure was analyzed utilizing FTIR spectra, elemental analysis, and single crystal X-ray diffraction (SC-XRD). There is one crystallographically independent Ag atom, which is tetra-coordinated by two nitrogen atoms from two 3ADMT and two oxygen atoms from two nitrate anions where all ligand groups are acting as connectors between the Ag1 sites. The geometry around the Ag(I) center is a distorted tetrahedron with a AgN2O2 coordination sphere augmented by strong argentophilic interactions between Ag atoms, which assist the aggregation of the complex units in a wavy-like and coplanar pattern to form a one-dimensional polymeric chain. The O...H (37.2%) and N...H (18.8%) intermolecular interactions contributed significantly to the molecular packing based on Hirshfeld surface analysis. The [Ag(3ADMT)(NO3)]n complex demonstrates promising cytotoxicity against lung (IC50 = 2.96 ± 0.31 μg/mL) and breast (IC50 = 1.97 ± 0.18 μg/mL) carcinoma. This remarkable cytotoxicity exceeds those of 3ADMT, AgNO3, and the anticancer medication cis-platin towards the tested cancer cell lines. In addition, the complex has a wide-spectrum antimicrobial action where the high antibacterial potency of the [Ag(3ADMT)(NO3)]n complex against P. vulgaris (MIC = 6.1 µg/mL) and B. subtilis (MIC = 17.2 µg/mL) could be comparable to the commonly used drug Gentamycin (MIC = 4.8 µg/mL). These results confirm that the components of the [Ag(3ADMT)(NO3)]n complex work together synergistically, forming a powerful multifunctional agent that could be exploited as an effective antimicrobial and anticancer agent.
{"title":"Synthesis, X-ray Structure, and Hirshfeld Analysis of [Ag(3-amino-5,6-dimethyl-1,2,4-triazine)(NO3)]n: A Potent Anticancer and Antimicrobial Agent","authors":"M. El-Naggar, M. Abu-Youssef, M. Haukka, A. Barakat, M. Sharaf, S. Soliman","doi":"10.3390/inorganics11090350","DOIUrl":"https://doi.org/10.3390/inorganics11090350","url":null,"abstract":"The [Ag(3ADMT)(NO3)]n complex was synthesized by the self-assembly of 3-amino-5,6-dimethyl-1,2,4-triazine (3ADMT) and AgNO3. Its molecular structure was analyzed utilizing FTIR spectra, elemental analysis, and single crystal X-ray diffraction (SC-XRD). There is one crystallographically independent Ag atom, which is tetra-coordinated by two nitrogen atoms from two 3ADMT and two oxygen atoms from two nitrate anions where all ligand groups are acting as connectors between the Ag1 sites. The geometry around the Ag(I) center is a distorted tetrahedron with a AgN2O2 coordination sphere augmented by strong argentophilic interactions between Ag atoms, which assist the aggregation of the complex units in a wavy-like and coplanar pattern to form a one-dimensional polymeric chain. The O...H (37.2%) and N...H (18.8%) intermolecular interactions contributed significantly to the molecular packing based on Hirshfeld surface analysis. The [Ag(3ADMT)(NO3)]n complex demonstrates promising cytotoxicity against lung (IC50 = 2.96 ± 0.31 μg/mL) and breast (IC50 = 1.97 ± 0.18 μg/mL) carcinoma. This remarkable cytotoxicity exceeds those of 3ADMT, AgNO3, and the anticancer medication cis-platin towards the tested cancer cell lines. In addition, the complex has a wide-spectrum antimicrobial action where the high antibacterial potency of the [Ag(3ADMT)(NO3)]n complex against P. vulgaris (MIC = 6.1 µg/mL) and B. subtilis (MIC = 17.2 µg/mL) could be comparable to the commonly used drug Gentamycin (MIC = 4.8 µg/mL). These results confirm that the components of the [Ag(3ADMT)(NO3)]n complex work together synergistically, forming a powerful multifunctional agent that could be exploited as an effective antimicrobial and anticancer agent.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48029979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-24DOI: 10.3390/inorganics11090348
Sam H Brooks, C. Richards, P. Carroll, Michael R. Gau, N. Tomson
Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (nPDI2, n = 2, 3). A series of dicopper complexes bound by the nPDI2 ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N3, NO2, OSiMe3, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the nPDI2 macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion.
{"title":"Anion Capture at the Open Core of a Geometrically Flexible Dicopper(II,II) Macrocycle Complex","authors":"Sam H Brooks, C. Richards, P. Carroll, Michael R. Gau, N. Tomson","doi":"10.3390/inorganics11090348","DOIUrl":"https://doi.org/10.3390/inorganics11090348","url":null,"abstract":"Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (nPDI2, n = 2, 3). A series of dicopper complexes bound by the nPDI2 ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N3, NO2, OSiMe3, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the nPDI2 macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48533494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-24DOI: 10.3390/inorganics11090347
A. F. Dresvyannikov, L. E. Kalugin, Ekaterina V. Petrova
This article focuses on the galvanic replacement synthesis of Ti-Ni and Zr-Ni metal systems with a “core-shell” structure, which are potential precursors for intermetallics. The authors defined effective synthesis parameters and formation features of polymetallic systems characterized by granulometric, phase, and elemental composition. X-ray fluorescence and X-ray phase analysis methods showed that the deposition of nickel on dispersed titanium and zirconium leads to the production of test samples with phase composition representing a mechanical mixture of Ni and Ti, and Ni and Zr. The method of X-ray fluorescence analysis showed that the presence of hydrofluoric acid with a 0.5-1.5 M concentration results in the formation of fixed quantitative ratios of elements in the precipitate, which allows the quantitative composition of dispersed systems “titanium-nickel” and “zirconium-nickel” to be regulated within a relatively wide range. Scanning electron microscopy proved that all synthesized systems are characterized by a highly porous structure that follows the titanium and zirconium particle surface contour and the presence of spherical nanoscale subunits on the formed particle surface.
{"title":"Synthesis of Ti-Ni and Zr-Ni Core–Shell Particles Using Galvanic Replacement","authors":"A. F. Dresvyannikov, L. E. Kalugin, Ekaterina V. Petrova","doi":"10.3390/inorganics11090347","DOIUrl":"https://doi.org/10.3390/inorganics11090347","url":null,"abstract":"This article focuses on the galvanic replacement synthesis of Ti-Ni and Zr-Ni metal systems with a “core-shell” structure, which are potential precursors for intermetallics. The authors defined effective synthesis parameters and formation features of polymetallic systems characterized by granulometric, phase, and elemental composition. X-ray fluorescence and X-ray phase analysis methods showed that the deposition of nickel on dispersed titanium and zirconium leads to the production of test samples with phase composition representing a mechanical mixture of Ni and Ti, and Ni and Zr. The method of X-ray fluorescence analysis showed that the presence of hydrofluoric acid with a 0.5-1.5 M concentration results in the formation of fixed quantitative ratios of elements in the precipitate, which allows the quantitative composition of dispersed systems “titanium-nickel” and “zirconium-nickel” to be regulated within a relatively wide range. Scanning electron microscopy proved that all synthesized systems are characterized by a highly porous structure that follows the titanium and zirconium particle surface contour and the presence of spherical nanoscale subunits on the formed particle surface.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42847501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-21DOI: 10.3390/inorganics11080345
E. Malinina, I.I. Myshletsov, G. A. Buzanov, I. Kozerozhets, N. Simonenko, T. Simonenko, S. Nikiforova, V. Avdeeva, K. Zhizhin, N. Kuznetsov
The thermal reduction of the copper(II) complexes [CuII(N2H4)3][B10H10]·nH2O (I·nH2O) and [CuII(NH3)4][B10H10]·nH2O (II·nH2O) has been studied in an argon atmosphere at 900 °C. It has been found that the annealing of both compounds results in a Cu@BN boron-containing copper composite. It has been shown that this process leads to the formation of a boron nitride matrix doped with cubic copper(0) nanoparticles due to the copper(II)→copper(I)→copper(0) thermal reduction. The phase composition of annealing products I900 and II900 has been determined based on powder X-ray diffraction, IR spectroscopy and thermal analysis data. The morphology, average particle size and composition of the composite have been determined by TEM and high-resolution TEM + EDS. The average particle size has been found to be about 81 nm and 52 nm for samples I900 and II900, respectively. Comparison of the results obtained using physicochemical studies has shown the identity of the composition of the products of annealing I900 and II900. The electrical properties of a coating based on an I900 sample modified with Cu0→Cu2O in situ during deposition on a chip at 300 °C in air have been studied. As a result, with increasing temperature, an increase in the electrical conductivity characteristic of semiconductors has been observed.
{"title":"Physicochemical Fundamentals of the Synthesis of a Cu@BN Composite Consisting of Nanosized Copper Enclosed in a Boron Nitride Matrix","authors":"E. Malinina, I.I. Myshletsov, G. A. Buzanov, I. Kozerozhets, N. Simonenko, T. Simonenko, S. Nikiforova, V. Avdeeva, K. Zhizhin, N. Kuznetsov","doi":"10.3390/inorganics11080345","DOIUrl":"https://doi.org/10.3390/inorganics11080345","url":null,"abstract":"The thermal reduction of the copper(II) complexes [CuII(N2H4)3][B10H10]·nH2O (I·nH2O) and [CuII(NH3)4][B10H10]·nH2O (II·nH2O) has been studied in an argon atmosphere at 900 °C. It has been found that the annealing of both compounds results in a Cu@BN boron-containing copper composite. It has been shown that this process leads to the formation of a boron nitride matrix doped with cubic copper(0) nanoparticles due to the copper(II)→copper(I)→copper(0) thermal reduction. The phase composition of annealing products I900 and II900 has been determined based on powder X-ray diffraction, IR spectroscopy and thermal analysis data. The morphology, average particle size and composition of the composite have been determined by TEM and high-resolution TEM + EDS. The average particle size has been found to be about 81 nm and 52 nm for samples I900 and II900, respectively. Comparison of the results obtained using physicochemical studies has shown the identity of the composition of the products of annealing I900 and II900. The electrical properties of a coating based on an I900 sample modified with Cu0→Cu2O in situ during deposition on a chip at 300 °C in air have been studied. As a result, with increasing temperature, an increase in the electrical conductivity characteristic of semiconductors has been observed.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48819757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-08-21DOI: 10.3390/inorganics11080346
Song Wang, Xianming Zhang, Xi Tan, Hongzhen Li, Songxin Dai, B. Yao, Xingyan Liu, Youzhou He, Fei Jin
Functionalization of endohedral metallofullerenes (EMFs) plays an important role in exploring the reactivity of EMFs and stabilizing missing EMFs, thus conferring tunable properties and turning EMFs into applicable materials. In this review, we present exhaustive progress on the functionalization of EMFs since 2019. Classic functionalization reactions include Prato reactions, Bingel–Hirsch reactions, radical addition reactions, carbene addition reactions, and so on are summarized. And new complicated multi-component reactions and other creative reactions are presented as well. We also discuss the structural features of derivatives of EMFs and the corresponding reaction mechanisms to understand the reactivity and regioselectivity of EMFs. In the end, we make conclusions and put forward an outlook on the prospect of the functionalization of EMFs.
{"title":"Recent Progress on the Functionalization of Endohedral Metallofullerenes","authors":"Song Wang, Xianming Zhang, Xi Tan, Hongzhen Li, Songxin Dai, B. Yao, Xingyan Liu, Youzhou He, Fei Jin","doi":"10.3390/inorganics11080346","DOIUrl":"https://doi.org/10.3390/inorganics11080346","url":null,"abstract":"Functionalization of endohedral metallofullerenes (EMFs) plays an important role in exploring the reactivity of EMFs and stabilizing missing EMFs, thus conferring tunable properties and turning EMFs into applicable materials. In this review, we present exhaustive progress on the functionalization of EMFs since 2019. Classic functionalization reactions include Prato reactions, Bingel–Hirsch reactions, radical addition reactions, carbene addition reactions, and so on are summarized. And new complicated multi-component reactions and other creative reactions are presented as well. We also discuss the structural features of derivatives of EMFs and the corresponding reaction mechanisms to understand the reactivity and regioselectivity of EMFs. In the end, we make conclusions and put forward an outlook on the prospect of the functionalization of EMFs.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2023-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41736231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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