The design and synthesis of new mid-infrared functional crystals with novel structures and excellent properties is a hot topic in the material scientific research field. Different from the traditional mid-far infrared crystals system, such as chalcogenides and phosphides, a recently developed heavy metal oxyhalide system, with a wide bandgap and transmittance range, is a very promising mid-infrared crystal material research system. Herein, the first case of the salt-inclusion compound in lead oxyhalide, Cs2Pb24O21I8 (3Pb8O7I2·2CsI), has been synthesized by a high-temperature solution method. Cs2Pb24O21I8 features a “chain” like structure constructed by 1∞[O21Pb30] chain composed of [OPb4] tetrahedra and [OPb3] pyramid, then 1∞[CsI4] chain inserted in the tunnel. The results show that the salt-inclusion strategy significantly enriches the structure diversity of lead oxyhalides and provides a new research idea for exploring new infrared functional materials.
{"title":"3Pb8O7I2·2CsI: Salt-inclusion strategy enriches the structural chemistry in lead oxyhalides","authors":"Mayinuer Maimaiti, Yuchen Yan, Jinche Wu, Tingwen Han, Jing Xie, Min Zhang","doi":"10.1039/d4dt03212h","DOIUrl":"https://doi.org/10.1039/d4dt03212h","url":null,"abstract":"The design and synthesis of new mid-infrared functional crystals with novel structures and excellent properties is a hot topic in the material scientific research field. Different from the traditional mid-far infrared crystals system, such as chalcogenides and phosphides, a recently developed heavy metal oxyhalide system, with a wide bandgap and transmittance range, is a very promising mid-infrared crystal material research system. Herein, the first case of the salt-inclusion compound in lead oxyhalide, Cs2Pb24O21I8 (3Pb8O7I2·2CsI), has been synthesized by a high-temperature solution method. Cs2Pb24O21I8 features a “chain” like structure constructed by 1∞[O21Pb30] chain composed of [OPb4] tetrahedra and [OPb3] pyramid, then 1∞[CsI4] chain inserted in the tunnel. The results show that the salt-inclusion strategy significantly enriches the structure diversity of lead oxyhalides and provides a new research idea for exploring new infrared functional materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917608","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
W. W. Lukens, M. Speldrich, P. Yang, T. J. Duignan, J. Autschbach and P. Kögerler
Correction for ‘The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study’ by W. W. Lukens et al., Dalton Trans., 2016, 45, 11508–11521, https://doi.org/10.1039/C6DT00634E.
{"title":"Correction: The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study","authors":"W. W. Lukens, M. Speldrich, P. Yang, T. J. Duignan, J. Autschbach and P. Kögerler","doi":"10.1039/D4DT90222J","DOIUrl":"10.1039/D4DT90222J","url":null,"abstract":"<p >Correction for ‘The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study’ by W. W. Lukens <em>et al.</em>, <em>Dalton Trans.</em>, 2016, <strong>45</strong>, 11508–11521, https://doi.org/10.1039/C6DT00634E.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 3","pages":" 1276-1276"},"PeriodicalIF":3.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d4dt90222j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Juan Santo Domingo Peñaranda, Arpan Dhara, Aditya Chalishazar, Matthias Marcus Minjauw, Jolien Dendooven, Christophe Detavernier
Phosphorous-containing materials are used in a wide array of fields, from energy conversion and storage to heterogeneous catalysis and biomaterials. Among these materials, organic–inorganic metal phosphonate solids and thin films present an interesting option, due to their remarkable thermal and chemical stability. Yet, the synthesis of phosphonate hybrids by vapour phase thin film deposition techniques remains largely unexplored. In this work, we present successful deposition of phosphonate-containing films using dimethyl vinylphosphonate (DMVP) as a phosphonate precursor. Two processes have been studied, being a three-step MLD process comprising alternating exposure to trimethylaluminum (TMA), water (H2O) and DMVP (ABC process), and a four-step process with an extra O3 step following the DMVP pulse (ABCD process). The O3 treatment is employed for in situ functionalisation of the adsorbed phosphonate precursor, transforming the vinyl group into a carboxylic acid end group. For both processes, good precursor saturation was found, with the ABCD process exhibiting a more stable growth per cycle (0.54-0.38 Å/cycle) in the investigated temperature range (100-250○C). Phosphonate features were visible in FTIR spectra for both films, with the ABCD films also exhibiting a carboxylate signal. XPS showed a higher P incorporation in the ABCD films deposited at 250○C, although still moderate (P/Al = 0.27), consistent with an alumina structure with phosphonate inclusions. The film stability upon immersion in water was tested, showing a slow oxidation over the course of a week. Finally, annealing experiments in air demonstrated stable films up to 400○C.
{"title":"Vapour Phase Deposition of Phosphonate-containing Alumina Thin Films using Dimethyl Vinylphosphonate as Precursor","authors":"Juan Santo Domingo Peñaranda, Arpan Dhara, Aditya Chalishazar, Matthias Marcus Minjauw, Jolien Dendooven, Christophe Detavernier","doi":"10.1039/d4dt02851a","DOIUrl":"https://doi.org/10.1039/d4dt02851a","url":null,"abstract":"Phosphorous-containing materials are used in a wide array of fields, from energy conversion and storage to heterogeneous catalysis and biomaterials. Among these materials, organic–inorganic metal phosphonate solids and thin films present an interesting option, due to their remarkable thermal and chemical stability. Yet, the synthesis of phosphonate hybrids by vapour phase thin film deposition techniques remains largely unexplored. In this work, we present successful deposition of phosphonate-containing films using dimethyl vinylphosphonate (DMVP) as a phosphonate precursor. Two processes have been studied, being a three-step MLD process comprising alternating exposure to trimethylaluminum (TMA), water (H<small><sub>2</sub></small>O) and DMVP (ABC process), and a four-step process with an extra O<small><sub>3</sub></small> step following the DMVP pulse (ABCD process). The O<small><sub>3</sub></small> treatment is employed for in situ functionalisation of the adsorbed phosphonate precursor, transforming the vinyl group into a carboxylic acid end group. For both processes, good precursor saturation was found, with the ABCD process exhibiting a more stable growth per cycle (0.54-0.38 Å/cycle) in the investigated temperature range (100-250<small><sup>○</sup></small>C). Phosphonate features were visible in FTIR spectra for both films, with the ABCD films also exhibiting a carboxylate signal. XPS showed a higher P incorporation in the ABCD films deposited at 250<small><sup>○</sup></small>C, although still moderate (P/Al = 0.27), consistent with an alumina structure with phosphonate inclusions. The film stability upon immersion in water was tested, showing a slow oxidation over the course of a week. Finally, annealing experiments in air demonstrated stable films up to 400<small><sup>○</sup></small>C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
During the oxygen evolution reaction (OER), Metal-organic frameworks (MOFs) catalysts undergo structural reorganization, a phenomenon that is still not fully comprehended. Additionally, designing MOFs that undergo structural reconstruction to produce highly active OER catalysts continues to pose significant challenges. Herein, bimetallic MOF (CoNi-MOF) with carboxylate oxygen and pyridine nitrogen coordination has been synthesized and its reconstruction behavior has been analyzed. The CoNi-MOF electrocatalyst attains a current density of 10 mA cm−2 with a minimal overpotential of just 250 mV, along with a Tafel slope of 91.57 mV dec−1, which is relatively low. After undergoing CV cycling tests, changes were observed in its catalytic activity, as well as in the microstructure and electrochemically active surface area, which are related to its activity. Importantly, in-situ Raman analysis indicates that during the electrocatalytic process, the MOFs undergo a transition to MOOH, signifying the occurrence of reconstruction. Notably, compared to monometallic MOF, bimetallic MOF undergoes reconstruction at lower voltage and with a faster reconstruction rate. Further analysis has revealed that the electrochemical reconstruction rate of the Co-N/O coordination mode at the active center is higher than that of Ni-N/O, playing a crucial role in enhancing OER activity. This study underscores the significance of the reconstruction strategy in enhancing the activity of MOF catalysts, providing new insights for the development of high-activity materials.
{"title":"Controlled Reconstruction of Metal-Organic Frameworks via Coordination Environment Tuning as Oxygen Evolution Electrocatalysts","authors":"Jiangli Gong, Qianglong Qi, Zhiyuan Wang, Guangxin Zhao, Jianliang Yuan, Chengxu Zhang, Jue Hu","doi":"10.1039/d4dt03348e","DOIUrl":"https://doi.org/10.1039/d4dt03348e","url":null,"abstract":"During the oxygen evolution reaction (OER), Metal-organic frameworks (MOFs) catalysts undergo structural reorganization, a phenomenon that is still not fully comprehended. Additionally, designing MOFs that undergo structural reconstruction to produce highly active OER catalysts continues to pose significant challenges. Herein, bimetallic MOF (CoNi-MOF) with carboxylate oxygen and pyridine nitrogen coordination has been synthesized and its reconstruction behavior has been analyzed. The CoNi-MOF electrocatalyst attains a current density of 10 mA cm−2 with a minimal overpotential of just 250 mV, along with a Tafel slope of 91.57 mV dec−1, which is relatively low. After undergoing CV cycling tests, changes were observed in its catalytic activity, as well as in the microstructure and electrochemically active surface area, which are related to its activity. Importantly, in-situ Raman analysis indicates that during the electrocatalytic process, the MOFs undergo a transition to MOOH, signifying the occurrence of reconstruction. Notably, compared to monometallic MOF, bimetallic MOF undergoes reconstruction at lower voltage and with a faster reconstruction rate. Further analysis has revealed that the electrochemical reconstruction rate of the Co-N/O coordination mode at the active center is higher than that of Ni-N/O, playing a crucial role in enhancing OER activity. This study underscores the significance of the reconstruction strategy in enhancing the activity of MOF catalysts, providing new insights for the development of high-activity materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Energy crisis and environmental pollution are two central themes of contemporary research towards achievement of Sustainable Development Goals (SDGs). Material chemistry is the chief discipline to serve such glitches through the appropriate design of chemical compounds those could have multifunctional properties. In this regard, two stable coordination polymers (CPs) are synthesised by using Zn(II) (3d10) and Cd(II) (d10) metal nodes with 1,4-benzenedicarboxylate (bdc2-) as bridging ligand and monodentate pyridyl-N coordination by 9H-Fluoren-2-yl-pyridin-4-ylmethylene-amine (flpy) as fluorogenic partner. The structures of the polymers, [Zn2(bdc)4(flpy)2]n (CP1) and [Cd(bdc)2(flpy)2(H2O)]n.(flpy) (CP2) have been established by the Single Crystal X-Ray diffraction measurements. In CP1, [Zn2(bdc)4], a paddle-wheel coordination unit, propagates to constitute the 2D polymer while in CP2, CdN2O5, a capped octahedron motif generates the 1D chain. The CP1 and CP2 are strongly emissive and the emission has been quenched selectively by Pd2+ in aqueous solution in presence of as many as twenty other metal ions. Pd(II) is most toxic out of three oxidation states (0,II,IV) and the limit of detection of Pd2+(aq) is 79.1 nM (CP1) and 89.2 nM (CP2) and much below the toxicity limit of Pd2+ as recommended by WHO (Tolerance boundary of Pd2+ in water is 3.97 - 46.98 µM). The Tauc’s plot of thin film ITO/(CP1 or CP2)/Al, determines the band gap 3.63 eV (theoretical, 3.28 eV) (CP1) and 3.55 eV (theoretical, 3.21 eV) (CP2) and has insisted to fabricate the Schottky semiconducting device which has measured the electrical conductivity at ambient condition as 1.285×10-4 (CP1) and 2.399×10-4 S m-1 (CP2). Therefore, two important applications of these CPs can be highly accomplished towards sustainability for the future generation.
{"title":"Structure-directing effect of Terephthalate bridging Zn(II)- and Cd(II)-based coordination polymers towards application for the detection of trace quantity of Pd2+ in aqueous medium and their electrical conductivities","authors":"Koushik Saha, Basudeb Dutta, Pubali Das, Angeera Chandra, Arnab Samanta, Sudeep Ranjan Jana, Sudip Naskar, Rajat Saha, Partha Pratim Ray, Chittaranjan Sinha","doi":"10.1039/d4dt03075c","DOIUrl":"https://doi.org/10.1039/d4dt03075c","url":null,"abstract":"Energy crisis and environmental pollution are two central themes of contemporary research towards achievement of Sustainable Development Goals (SDGs). Material chemistry is the chief discipline to serve such glitches through the appropriate design of chemical compounds those could have multifunctional properties. In this regard, two stable coordination polymers (CPs) are synthesised by using Zn(II) (3d10) and Cd(II) (d10) metal nodes with 1,4-benzenedicarboxylate (bdc2-) as bridging ligand and monodentate pyridyl-N coordination by 9H-Fluoren-2-yl-pyridin-4-ylmethylene-amine (flpy) as fluorogenic partner. The structures of the polymers, [Zn2(bdc)4(flpy)2]n (CP1) and [Cd(bdc)2(flpy)2(H2O)]n.(flpy) (CP2) have been established by the Single Crystal X-Ray diffraction measurements. In CP1, [Zn2(bdc)4], a paddle-wheel coordination unit, propagates to constitute the 2D polymer while in CP2, CdN2O5, a capped octahedron motif generates the 1D chain. The CP1 and CP2 are strongly emissive and the emission has been quenched selectively by Pd2+ in aqueous solution in presence of as many as twenty other metal ions. Pd(II) is most toxic out of three oxidation states (0,II,IV) and the limit of detection of Pd2+(aq) is 79.1 nM (CP1) and 89.2 nM (CP2) and much below the toxicity limit of Pd2+ as recommended by WHO (Tolerance boundary of Pd2+ in water is 3.97 - 46.98 µM). The Tauc’s plot of thin film ITO/(CP1 or CP2)/Al, determines the band gap 3.63 eV (theoretical, 3.28 eV) (CP1) and 3.55 eV (theoretical, 3.21 eV) (CP2) and has insisted to fabricate the Schottky semiconducting device which has measured the electrical conductivity at ambient condition as 1.285×10-4 (CP1) and 2.399×10-4 S m-1 (CP2). Therefore, two important applications of these CPs can be highly accomplished towards sustainability for the future generation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917613","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rabaa M. Khaled, Mahmoud T. Abo-Elfadl, Krzysztof Radacki, Mona A. M. Abo Zeid, Ola R. Shehab, Nora S. Abdel-Kader, Gamal A. E. Mostafa, Essam A. Ali, Shaikha S. Al Neyadi, Ahmed M. Mansour
The photo-induced CO-releasing properties of the dark-stable complex [RuCl2(CO)2L] (L = 2-(pyridin-2-yl)quinoxaline) were investigated under 468 nm light exposure in the presence and absence of biomolecules such as histidine, calf thymus DNA and hen egg white lysozyme. The CO release kinetics were consistent regardless of the presence of these biomolecules, suggesting that they did not influence the CO release mechanism. The quinoxaline ligand demonstrated exceptional cytotoxicity against human acute monocytic leukemia cells (THP-1), with evidence of potential DNA damage ascertained by comet assay, while it remained non-toxic to normal kidney epithelial cells derived from African green monkey (Vero) cell lines. In contrast, upon light activation, the Ru(II) complex showed no toxicity against THP-1 cells but was detrimental to Vero cells. In human colorectal carcinoma (HCT-116) cells, the ligand and the Ru(II) complex produced ROS under light and dark conditions. However, HCT-116 cells retained their ability to consume oxygen and produce ATP following CO treatment, suggesting that the ROS levels were insufficient to cause significant cellular damage. Morphological features of apoptosis, including apoptotic bodies, chromatin condensation, cell shrinkage, and membrane leakage, were observed in the presence of both the ligand and its complex, irrespective of light exposure.
{"title":"Visible-light-induced CO-releasing properties and cytotoxicity of a Ru(II) carbonyl complex containing 2-(pyridin-2-yl)-quinoxaline","authors":"Rabaa M. Khaled, Mahmoud T. Abo-Elfadl, Krzysztof Radacki, Mona A. M. Abo Zeid, Ola R. Shehab, Nora S. Abdel-Kader, Gamal A. E. Mostafa, Essam A. Ali, Shaikha S. Al Neyadi, Ahmed M. Mansour","doi":"10.1039/d4dt03082f","DOIUrl":"https://doi.org/10.1039/d4dt03082f","url":null,"abstract":"The photo-induced CO-releasing properties of the dark-stable complex [RuCl<small><sub>2</sub></small>(CO)<small><sub>2</sub></small>L] (L = 2-(pyridin-2-yl)quinoxaline) were investigated under 468 nm light exposure in the presence and absence of biomolecules such as histidine, calf thymus DNA and hen egg white lysozyme. The CO release kinetics were consistent regardless of the presence of these biomolecules, suggesting that they did not influence the CO release mechanism. The quinoxaline ligand demonstrated exceptional cytotoxicity against human acute monocytic leukemia cells (THP-1), with evidence of potential DNA damage ascertained by comet assay, while it remained non-toxic to normal kidney epithelial cells derived from African green monkey (Vero) cell lines. In contrast, upon light activation, the Ru(<small>II</small>) complex showed no toxicity against THP-1 cells but was detrimental to Vero cells. In human colorectal carcinoma (HCT-116) cells, the ligand and the Ru(<small>II</small>) complex produced ROS under light and dark conditions. However, HCT-116 cells retained their ability to consume oxygen and produce ATP following CO treatment, suggesting that the ROS levels were insufficient to cause significant cellular damage. Morphological features of apoptosis, including apoptotic bodies, chromatin condensation, cell shrinkage, and membrane leakage, were observed in the presence of both the ligand and its complex, irrespective of light exposure.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
M. Trinidad Martín, Carlos J. Carrasco, Nazaret Santamaría, Celia Maya, Auxiliadora Prieto, Agustin Galindo, M. Carmen Nicasio
Preformed Ni(0) complexes are rarely used as precatalysts in cross-coupling reactions, although they can incorporate catalytically active nickel directly into the reaction. In this work, we focus on the preparation and the catalytic application of low-coordinate Ni(0) complexes supported by bulky monophosphine ligands in C-S cross-coupling reactions. We have prepared two families of Ni(0) complexes, bis-phosphine aducts of the type [Ni(PR2Ar’)2] (Ar’ = m-terphenyl group) and monophosphine derivatives of the type [Ni(PR2Ar’)(DVDS)] (DVDS = divinyltetramethyldisiloxane). DFT calculations were used to account for the atypical bent structures displayed by the bis-phosphine Ni(0) complexes. Monophosphine-Ni(0) complexes display catalytic activity superior to bis-phosphine Ni(0) adducts, which suggests that the former facilitate the generation of highly reactive monoligated PNi(0) species. Furthermore, the reactivity of monophosphine-Ni(0) precatalysts outperform that observed with Ni(II) precatalysts with the same phosphine ligands, supporting a more facile activation step to the same catalytic species. This enhanced reactivity allows for the use of lower catalyst loadings (1-5mol%) and for carrying out the challenging coupling between aryl chlorides and alkylthiols.
{"title":"Low-coordinate bis-phosphine and monophosphine Ni(0) complexes: synthesis and reactivity in C-S cross-coupling","authors":"M. Trinidad Martín, Carlos J. Carrasco, Nazaret Santamaría, Celia Maya, Auxiliadora Prieto, Agustin Galindo, M. Carmen Nicasio","doi":"10.1039/d4dt03375b","DOIUrl":"https://doi.org/10.1039/d4dt03375b","url":null,"abstract":"Preformed Ni(0) complexes are rarely used as precatalysts in cross-coupling reactions, although they can incorporate catalytically active nickel directly into the reaction. In this work, we focus on the preparation and the catalytic application of low-coordinate Ni(0) complexes supported by bulky monophosphine ligands in C-S cross-coupling reactions. We have prepared two families of Ni(0) complexes, bis-phosphine aducts of the type [Ni(PR2Ar’)2] (Ar’ = m-terphenyl group) and monophosphine derivatives of the type [Ni(PR2Ar’)(DVDS)] (DVDS = divinyltetramethyldisiloxane). DFT calculations were used to account for the atypical bent structures displayed by the bis-phosphine Ni(0) complexes. Monophosphine-Ni(0) complexes display catalytic activity superior to bis-phosphine Ni(0) adducts, which suggests that the former facilitate the generation of highly reactive monoligated PNi(0) species. Furthermore, the reactivity of monophosphine-Ni(0) precatalysts outperform that observed with Ni(II) precatalysts with the same phosphine ligands, supporting a more facile activation step to the same catalytic species. This enhanced reactivity allows for the use of lower catalyst loadings (1-5mol%) and for carrying out the challenging coupling between aryl chlorides and alkylthiols.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Antonio I Nicasio, Rosie Somerville, Pablo Sahagún, Enrique Soto, Joaquin Lopez-Serrano, Jesús Campos
Redox-active ligands provide alternative reaction pathways by facilitating redox events. Among those, tridentate bis(piridylimino)isoindole (BPI) fragments offer great potential, though its redox-active behaviour remains largely underdeveloped. We describe herein a family of BPI germanium(II) complexes and the study of their redox properties. Amido complexes (RBPI)Ge[N(SiMe3)2] 1-R (R = H, Me, Et) showing a κ2-Npy,Niso coordination to the germanium(II) centre were prepared. In contrast, chloride derivatives (RBPI)GeCl, 2-R, display dynamic κ3-Npy,Niso,Npy coordination to the metal centre. The addition of silver (bis)trifluoromethylsulfonimide to compound 1-H generates a dinuclear complex, 3, where the silver atoms are bound to the germanium and one of the imine nitrogen atoms of another BPI fragment. The reduction of 2-R with KC8 generates dinuclear complexes (4-R) characterized by the formation of new C–C bonds between the isoindoline five-membered rings of two different BPI ligands via a radical mechanism, a transformation that does not take place in the absence of germanium. Interestingly, computational and spectroscopic studies support that the reduction takes place exclusively over the RBPI ligand. Strikingly, the newly formed C‒C bond is also readily cleaved. Thus, subsequent reduction of 4-R (R = H, Me) using additional KC8 affords dinuclear species 5-R, with polymeric structures between potassium atoms and the corresponding dinuclear Ge2(RBPI2) fragments.
{"title":"Carbon‒Carbon Bond Formation and Cleavage at Redox Active Bis(piridylimino)isoindole (BPI) Germylene Compounds","authors":"Antonio I Nicasio, Rosie Somerville, Pablo Sahagún, Enrique Soto, Joaquin Lopez-Serrano, Jesús Campos","doi":"10.1039/d4dt03489a","DOIUrl":"https://doi.org/10.1039/d4dt03489a","url":null,"abstract":"Redox-active ligands provide alternative reaction pathways by facilitating redox events. Among those, tridentate bis(piridylimino)isoindole (BPI) fragments offer great potential, though its redox-active behaviour remains largely underdeveloped. We describe herein a family of BPI germanium(II) complexes and the study of their redox properties. Amido complexes (RBPI)Ge[N(SiMe3)2] 1-R (R = H, Me, Et) showing a κ2-Npy,Niso coordination to the germanium(II) centre were prepared. In contrast, chloride derivatives (RBPI)GeCl, 2-R, display dynamic κ3-Npy,Niso,Npy coordination to the metal centre. The addition of silver (bis)trifluoromethylsulfonimide to compound 1-H generates a dinuclear complex, 3, where the silver atoms are bound to the germanium and one of the imine nitrogen atoms of another BPI fragment. The reduction of 2-R with KC8 generates dinuclear complexes (4-R) characterized by the formation of new C–C bonds between the isoindoline five-membered rings of two different BPI ligands via a radical mechanism, a transformation that does not take place in the absence of germanium. Interestingly, computational and spectroscopic studies support that the reduction takes place exclusively over the RBPI ligand. Strikingly, the newly formed C‒C bond is also readily cleaved. Thus, subsequent reduction of 4-R (R = H, Me) using additional KC8 affords dinuclear species 5-R, with polymeric structures between potassium atoms and the corresponding dinuclear Ge2(RBPI2) fragments.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"18 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maksim Luginin, Dmitry Snetkov, Anastasia Sizova, Aleksandra V. Paderina, Vladimir Sizov, Elena V. Grachova
A series of cyclometalated Au(III) complexes [Au(C^N^C)(C2−L−P(O)Ph2)] with C^N^C = 2,6-diphenylpyridine and alkynylphosphine oxide ligands (L = no linker, Au1; phenyl, Au2; biphenyl, Au3; naphthyl, Au4; anthracenyl, Au5) were synthesized and fully characterized by spectroscopic methods and single crystal XRD analysis. The complexes obtained exhibit triplet (Au1−Au3) and dual (Au4, Au5) emission in solution, solid phase and in the PMMA film, whose characteristics depend on the linker’s nature of the alkynylphosphine oxide ligand. The description of electronic transitions responsible for energy absorption and emission in Au(III) complexes was made on the basis of a detailed analysis of the results of DFT calculations, and has shown to involve ILCT, LLCT and MLCT transitions of singlet and triplet nature. It was demonstrated that packing in the crystal affects the solid-state emission of Au(III) complexes, which differs from that in solution. Based on DFT calculations for the supramolecular dimer for Au1, it was shown that this phenomenon is result of packing of the complex molecules in the crystal.
{"title":"Cyclometalated Au(III) complexes with alkynylphosphine oxide ligands: synthesis and photophysical properties","authors":"Maksim Luginin, Dmitry Snetkov, Anastasia Sizova, Aleksandra V. Paderina, Vladimir Sizov, Elena V. Grachova","doi":"10.1039/d4dt03250k","DOIUrl":"https://doi.org/10.1039/d4dt03250k","url":null,"abstract":"A series of cyclometalated Au(III) complexes [Au(C^N^C)(C2−L−P(O)Ph2)] with C^N^C = 2,6-diphenylpyridine and alkynylphosphine oxide ligands (L = no linker, Au1; phenyl, Au2; biphenyl, Au3; naphthyl, Au4; anthracenyl, Au5) were synthesized and fully characterized by spectroscopic methods and single crystal XRD analysis. The complexes obtained exhibit triplet (Au1−Au3) and dual (Au4, Au5) emission in solution, solid phase and in the PMMA film, whose characteristics depend on the linker’s nature of the alkynylphosphine oxide ligand. The description of electronic transitions responsible for energy absorption and emission in Au(III) complexes was made on the basis of a detailed analysis of the results of DFT calculations, and has shown to involve ILCT, LLCT and MLCT transitions of singlet and triplet nature. It was demonstrated that packing in the crystal affects the solid-state emission of Au(III) complexes, which differs from that in solution. Based on DFT calculations for the supramolecular dimer for Au1, it was shown that this phenomenon is result of packing of the complex molecules in the crystal.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Silicon-based anode materials experience significant volume changes and low conductivity during the lithiation process, which severely hinders their successful application in lithium-ion batteries. Reducing the size of silicon particles and effectively combining them with carbon-based materials are considered the main strategies to enhance the lithium-ion storage performance of silicon-based anodes. In this study, we employed a “bottom-up” strategy to synthesize Si@C anode materials by cross-linking octa-aminopropyl polyhedral oligomeric silsesquioxane (NH2-POSS) with terephthalaldehyde and subsequent high-temperature treatment and low-temperature liquid reduction. The obtained nanospheres consist of ultra-thin silicon stripes embedded in a continuous carbon framework, forming a carbon-protected silicon-based anode material suitable for lithium-ion batteries. The Si@C nanospheres exhibit excellent lithium-ion storage performance. After 1000 cycles at a current density of 0.5 A g−1, it retains an impressive capacity of 1363 mA h g−1, which is more than three times the theoretical capacity of graphite and 182% of the first cycle capacity after activation (750 mA h g−1). This work not only provides new possibilities for the application of POSS but also broadens the design and application of advanced silicon-based anode materials in the energy storage field.
{"title":"Nano-confined Si@C Composites with Excellent Lithium-Ion Storage Performance Derived from POSS-based Covalent Framework and Low-Temperature Reduction Method","authors":"Yu Zhang, Yanan Xu, Shu-Peng Zhao, shiyue Zhang, Hao Li, Qing Hu, wenkai Wang, Hongbin Du","doi":"10.1039/d4dt03185g","DOIUrl":"https://doi.org/10.1039/d4dt03185g","url":null,"abstract":"Silicon-based anode materials experience significant volume changes and low conductivity during the lithiation process, which severely hinders their successful application in lithium-ion batteries. Reducing the size of silicon particles and effectively combining them with carbon-based materials are considered the main strategies to enhance the lithium-ion storage performance of silicon-based anodes. In this study, we employed a “bottom-up” strategy to synthesize Si@C anode materials by cross-linking octa-aminopropyl polyhedral oligomeric silsesquioxane (NH2-POSS) with terephthalaldehyde and subsequent high-temperature treatment and low-temperature liquid reduction. The obtained nanospheres consist of ultra-thin silicon stripes embedded in a continuous carbon framework, forming a carbon-protected silicon-based anode material suitable for lithium-ion batteries. The Si@C nanospheres exhibit excellent lithium-ion storage performance. After 1000 cycles at a current density of 0.5 A g−1, it retains an impressive capacity of 1363 mA h g−1, which is more than three times the theoretical capacity of graphite and 182% of the first cycle capacity after activation (750 mA h g−1). This work not only provides new possibilities for the application of POSS but also broadens the design and application of advanced silicon-based anode materials in the energy storage field.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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