Correction for ‘Silver(I)–iodine cluster with efficient thermally activated delayed fluorescence and suppressed concentration quenching’ by Xiao Li et al., Dalton Trans., 2025, https://doi.org/10.1039/d4dt02855d.
对 Xiao Li 等人的 "具有高效热激活延迟荧光和抑制浓度淬灭的银（I）-碘簇（Silver(I)-iodine cluster with efficient thermally activated delayed fluorescence and suppressed concentration quenching）"的更正，Dalton Trans.，2025, https://doi.org/10.1039/d4dt02855d.
{"title":"Correction: Silver(I)–iodine cluster with efficient thermally activated delayed fluorescence and suppressed concentration quenching","authors":"Xiao Li, Shan-Yue Wei, Dong-Hai Zhang, Jia-Xuan Hu, Chen-Lu Hou, Ting-Ting Lin, Xu-Lin Chen, Can-Zhong Lu","doi":"10.1039/d5dt90008e","DOIUrl":"https://doi.org/10.1039/d5dt90008e","url":null,"abstract":"Correction for ‘Silver(<small>I</small>)–iodine cluster with efficient thermally activated delayed fluorescence and suppressed concentration quenching’ by Xiao Li <em>et al.</em>, <em>Dalton Trans.</em>, 2025, https://doi.org/10.1039/d4dt02855d.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"43 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968558","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}
Bone is one of the most common target organs for distant metastases of solid tumors, which imposes a heavy burden on society. Early diagnosis of bone metastases is of great significance and positron emission tomography (PET) imaging plays an important role in the diagnosis of bone metastases. PET tracers applied for diagnosing bone metastases are constantly being updated, but they all have certain limitations like a relatively low bone/kidney ratio or no capacity to label therapeutic radionuclides. Alendronate, a representative bisphosphonate (BP), has been usually considered the standard clinical treatment for bone related diseases. In this study, alendronate was strategically modified with different linkers in an attempt to improve target/non-target ratios and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was used as the chelator. Finally, three 68Ga-labeled tracers were successfully developed. The results showed that [68Ga]Ga-AABP1/2/3 all exhibited high radiochemical purity, biosafety, and excellent stability. In the biodistribution study of normal BALB/c mice, [68Ga]Ga-AABP3, when modified with phenylalanine and β-alanine as the linker, showed the highest bone/non-bone ratio at 1.5 h. In micro-PET/CT imaging of normal BALB/c mice, [68Ga]Ga-AABP3 showed the highest SUVmax value at the bones (2.24 ± 0.16 at 1.5 h). In micro-PET/CT imaging of the mouse model of bone metastases, compared with [68Ga]Ga-AABP1 and [68Ga]Ga-AABP2, the SUVmax in the foci after injection of [68Ga]Ga-AABP3 was the highest (2.64 ± 0.08 at 0.5 h and 2.67 ± 0.10 at 1.5 h), significantly higher than that of the contralateral normal bone. Besides, [68Ga]Ga-AABP3 showed the highest tumor/non-tumor ratio at 1.5 h. The results suggest that [68Ga]Ga-AABP3 has the potential for diagnosis of bone metastases. Furthermore, AABP3 with the chelator DOTA could also be labeled with 177Lu or 225Ac, providing possibility for further application in radioligand therapy.
{"title":"Preparation and preclinical evaluation of 68Ga-labeled alendronate analogs for diagnosis of bone metastases","authors":"Yixiang Lin, Yuan Pan, Jinglin Zhang, Bo Zhou, Guihua Hou, Feng Gao","doi":"10.1039/d4dt03159h","DOIUrl":"https://doi.org/10.1039/d4dt03159h","url":null,"abstract":"Bone is one of the most common target organs for distant metastases of solid tumors, which imposes a heavy burden on society. Early diagnosis of bone metastases is of great significance and positron emission tomography (PET) imaging plays an important role in the diagnosis of bone metastases. PET tracers applied for diagnosing bone metastases are constantly being updated, but they all have certain limitations like a relatively low bone/kidney ratio or no capacity to label therapeutic radionuclides. Alendronate, a representative bisphosphonate (BP), has been usually considered the standard clinical treatment for bone related diseases. In this study, alendronate was strategically modified with different linkers in an attempt to improve target/non-target ratios and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was used as the chelator. Finally, three <small><sup>68</sup></small>Ga-labeled tracers were successfully developed. The results showed that [<small><sup>68</sup></small>Ga]Ga-AABP<strong>1</strong>/<strong>2</strong>/<strong>3</strong> all exhibited high radiochemical purity, biosafety, and excellent stability. In the biodistribution study of normal BALB/c mice, [<small><sup>68</sup></small>Ga]Ga-AABP<strong>3</strong>, when modified with phenylalanine and β-alanine as the linker, showed the highest bone/non-bone ratio at 1.5 h. In micro-PET/CT imaging of normal BALB/c mice, [<small><sup>68</sup></small>Ga]Ga-AABP<strong>3</strong> showed the highest SUV<small><sub>max</sub></small> value at the bones (2.24 ± 0.16 at 1.5 h). In micro-PET/CT imaging of the mouse model of bone metastases, compared with [<small><sup>68</sup></small>Ga]Ga-AABP<strong>1</strong> and [<small><sup>68</sup></small>Ga]Ga-AABP<strong>2</strong>, the SUV<small><sub>max</sub></small> in the foci after injection of [<small><sup>68</sup></small>Ga]Ga-AABP<strong>3</strong> was the highest (2.64 ± 0.08 at 0.5 h and 2.67 ± 0.10 at 1.5 h), significantly higher than that of the contralateral normal bone. Besides, [<small><sup>68</sup></small>Ga]Ga-AABP<strong>3</strong> showed the highest tumor/non-tumor ratio at 1.5 h. The results suggest that [<small><sup>68</sup></small>Ga]Ga-AABP<strong>3</strong> has the potential for diagnosis of bone metastases. Furthermore, AABP<strong>3</strong> with the chelator DOTA could also be labeled with <small><sup>177</sup></small>Lu or <small><sup>225</sup></small>Ac, providing possibility for further application in radioligand therapy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"36 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968562","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}
Light-emitting Electrochemical Cells (LECs) are an attractive technology in the field of Solid State Light Devices (SSLD) as their simple architectures allow the preparation of cost-effective lighting devices. Consequently, low-cost and sustainable emitters are highly desired. The transition metal complexes are attractive in this field as they proved to possess compatible optoelectronic properties. Nowadays, the best emitters are based on platinum and iridium class metals which is a limitation for industrial production. For this concern, researchers have turned their attention to Earth-abundant metal complexes. But, are we aware that the cost consideration for these emitters should not be blinded by the abundance of the metal? Herein,the photophysical properties of the most interesting Earth-abundant metal complexes and their performance in LECs are put into context with respect to their real cost based on their metal precursors, bringing some surprises.
{"title":"Earth Abundant Transition Metals Complexes in Light-emitting Electrochemical Cells: Successes, Challenges and Perspectives","authors":"Ginevra Giobbio, Rubén D. Costa, Sylvain Gaillard","doi":"10.1039/d4dt03210a","DOIUrl":"https://doi.org/10.1039/d4dt03210a","url":null,"abstract":"Light-emitting Electrochemical Cells (LECs) are an attractive technology in the field of Solid State Light Devices (SSLD) as their simple architectures allow the preparation of cost-effective lighting devices. Consequently, low-cost and sustainable emitters are highly desired. The transition metal complexes are attractive in this field as they proved to possess compatible optoelectronic properties. Nowadays, the best emitters are based on platinum and iridium class metals which is a limitation for industrial production. For this concern, researchers have turned their attention to Earth-abundant metal complexes. But, are we aware that the cost consideration for these emitters should not be blinded by the abundance of the metal? Herein,the photophysical properties of the most interesting Earth-abundant metal complexes and their performance in LECs are put into context with respect to their real cost based on their metal precursors, bringing some surprises.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"122 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968557","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}
Molecules featuring a metal centre in a positive valance surrounded by 1,3-dialkyltrianzenide ligands, Mx+(R–N=N–N–R’)x, were shown to have both high thermal stability and volatility, making them interesting as precursors in chemical vapour deposition (CVD) and atomic layer deposition (ALD). So far, metals from groups 11-14 and lanthanoids form stable triazenides and the In and Ga triazenides have proven to be excellent precursors for InN, In2O3, GaN and InGaN. We believe the exploration of the triazenides as CVD and ALD precursors has only begun and hope to inspire further research with this perspective.
{"title":"Triazenide based metal precursors for vapour deposition","authors":"Nathan J. O'Brien, Henrik Pedersen","doi":"10.1039/d4dt02608j","DOIUrl":"https://doi.org/10.1039/d4dt02608j","url":null,"abstract":"Molecules featuring a metal centre in a positive valance surrounded by 1,3-dialkyltrianzenide ligands, M<small><sup>x+</sup></small>(R–N=N–N–R’)<small><sub>x</sub></small>, were shown to have both high thermal stability and volatility, making them interesting as precursors in chemical vapour deposition (CVD) and atomic layer deposition (ALD). So far, metals from groups 11-14 and lanthanoids form stable triazenides and the In and Ga triazenides have proven to be excellent precursors for InN, In<small><sub>2</sub></small>O<small><sub>3</sub></small>, GaN and InGaN. We believe the exploration of the triazenides as CVD and ALD precursors has only begun and hope to inspire further research with this perspective.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968559","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}
The design of acidic oxygen evolution reaction (OER) electrocatalysts with high activity and durability is the key to achieving efficient hydrogen production. Herein, we report a Cr-doped RuO2 (Ru0.9Cr0.1O2) catalyst that exhibits good OER activity in acidic electrolytes. The doping of Cr increases the valence state of Ru, which enhances the activity of the catalyst, and a current density of 10 mA cm−2 can be achieved at only 235 mV, which is superior to that of unmodified RuO2 of 299 mV. The Tafel slope of the catalyst was 63.9 mV dec−1, which is much better than that of unmodified RuO2 at 91.1 mV dec−1. In addition, this catalyst was able to maintain stable catalytic performance in 0.5 M H2SO4 for up to 30 hours. Density functional theory (DFT) calculations also showed that Cr doping optimized the adsorption of intermediates at Ru sites and significantly increased the catalytic activity of the Ru sites.
{"title":"Uncovering the role of the Cr dopant in RuO2 in highly efficient acid water oxidation","authors":"Hui Liu, Maolin Li, Zhizhao Zhang, Ying Li, Qiuyan Hao, Limin Liang, Wen Zhang","doi":"10.1039/d4dt03131h","DOIUrl":"https://doi.org/10.1039/d4dt03131h","url":null,"abstract":"The design of acidic oxygen evolution reaction (OER) electrocatalysts with high activity and durability is the key to achieving efficient hydrogen production. Herein, we report a Cr-doped RuO<small><sub>2</sub></small> (Ru<small><sub>0.9</sub></small>Cr<small><sub>0.1</sub></small>O<small><sub>2</sub></small>) catalyst that exhibits good OER activity in acidic electrolytes. The doping of Cr increases the valence state of Ru, which enhances the activity of the catalyst, and a current density of 10 mA cm<small><sup>−2</sup></small> can be achieved at only 235 mV, which is superior to that of unmodified RuO<small><sub>2</sub></small> of 299 mV. The Tafel slope of the catalyst was 63.9 mV dec<small><sup>−1</sup></small>, which is much better than that of unmodified RuO<small><sub>2</sub></small> at 91.1 mV dec<small><sup>−1</sup></small>. In addition, this catalyst was able to maintain stable catalytic performance in 0.5 M H<small><sub>2</sub></small>SO<small><sub>4</sub></small> for up to 30 hours. Density functional theory (DFT) calculations also showed that Cr doping optimized the adsorption of intermediates at Ru sites and significantly increased the catalytic activity of the Ru sites.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"87 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968560","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}
Jyotirmoy Dutta, Are Varshini, Sri Ganga Padaga, Arpan Bera, Tukki Sarkar, Swati Biswas, Akhtar Hussain
Photoactive complexes of bioessential 3d metals, activable within the phototherapeutic window (650–900 nm), have gained widespread interest due to their therapeutic potential. Herein, we report the synthesis, characterization, and light-enhanced anticancer and antibacterial properties of four new dinuclear Co(II) complexes: [Co(phen)(cat)]₂ (Co-1), [Co(dppz)(cat)]₂ (Co-2), [Co(phen)(esc)]₂ (Co-3), and [Co(dppz)(esc)]₂ (Co-4). In these complexes, phen (1,10-phenanthroline) and dppz (dipyrido[3,2-a:2’,3’-c]phenazine) act as neutral N, N-donor ligands, while cat2‒ and esc2‒ serve as O,O-donor catecholate ligands derived from catechol (1,2-dihydroxybenzene) and esculetin (6,7-dihydroxy coumarin). Their high-spin paramagnetic nature and dimeric identity in solution were confirmed by magnetic susceptibility, UV-visible, emission, and mass spectral data. Co-1–Co-4 exhibited an absorption band within the 600–850 nm range, originating from a charge transfer transition. The electrically neutral complexes demonstrated sufficient solution stability both in the dark and under irradiated conditions. The dppz complexes Co-2 and Co-4 exhibited notable toxicity towards A549 lung carcinoma cells, with potency increasing significantly under brief (5 min) exposure to 660 nm (red) and 808 nm (NIR) laser light (IC50 ~ 8.9 to 14.9 µM). Notably, their toxicity towards normal NIH-3T3 fibroblast cells was minimal. Cellular assays highlighted that the induced cell death followed an apoptotic pathway, primarily due to mitochondrial damage. Co-2 and Co-4 also demonstrated significant antibacterial potency against Gram-(+) S. aureus and Gram-(–) P. aeruginosa, with effectiveness significantly enhanced upon 808 nm laser irradiation (MIC ~ 15–142 µM). The increase in the anticancer and antibacterial efficacies was attributed to the generation of cytotoxic singlet oxygen (1O2) species upon red/NIR light exposure. Notably, 808 nm NIR irradiation produced more pronounced effects compared to 660 nm. This study is the first to report on cobalt complexes exhibiting red and NIR light-triggered enhancement of antibacterial and anticancer activities, illuminating the path for the development of long-wavelength absorbing cobalt complexes with enhanced therapeutic efficacy.
{"title":"Red and NIR light-triggered enhancement of anticancer and antibacterial activities of dinuclear Co(II)-catecholate complexes","authors":"Jyotirmoy Dutta, Are Varshini, Sri Ganga Padaga, Arpan Bera, Tukki Sarkar, Swati Biswas, Akhtar Hussain","doi":"10.1039/d4dt03153a","DOIUrl":"https://doi.org/10.1039/d4dt03153a","url":null,"abstract":"Photoactive complexes of bioessential 3d metals, activable within the phototherapeutic window (650–900 nm), have gained widespread interest due to their therapeutic potential. Herein, we report the synthesis, characterization, and light-enhanced anticancer and antibacterial properties of four new dinuclear Co(II) complexes: [Co(phen)(cat)]₂ (Co-1), [Co(dppz)(cat)]₂ (Co-2), [Co(phen)(esc)]₂ (Co-3), and [Co(dppz)(esc)]₂ (Co-4). In these complexes, phen (1,10-phenanthroline) and dppz (dipyrido[3,2-a:2’,3’-c]phenazine) act as neutral N, N-donor ligands, while cat2‒ and esc2‒ serve as O,O-donor catecholate ligands derived from catechol (1,2-dihydroxybenzene) and esculetin (6,7-dihydroxy coumarin). Their high-spin paramagnetic nature and dimeric identity in solution were confirmed by magnetic susceptibility, UV-visible, emission, and mass spectral data. Co-1–Co-4 exhibited an absorption band within the 600–850 nm range, originating from a charge transfer transition. The electrically neutral complexes demonstrated sufficient solution stability both in the dark and under irradiated conditions. The dppz complexes Co-2 and Co-4 exhibited notable toxicity towards A549 lung carcinoma cells, with potency increasing significantly under brief (5 min) exposure to 660 nm (red) and 808 nm (NIR) laser light (IC50 ~ 8.9 to 14.9 µM). Notably, their toxicity towards normal NIH-3T3 fibroblast cells was minimal. Cellular assays highlighted that the induced cell death followed an apoptotic pathway, primarily due to mitochondrial damage. Co-2 and Co-4 also demonstrated significant antibacterial potency against Gram-(+) S. aureus and Gram-(–) P. aeruginosa, with effectiveness significantly enhanced upon 808 nm laser irradiation (MIC ~ 15–142 µM). The increase in the anticancer and antibacterial efficacies was attributed to the generation of cytotoxic singlet oxygen (1O2) species upon red/NIR light exposure. Notably, 808 nm NIR irradiation produced more pronounced effects compared to 660 nm. This study is the first to report on cobalt complexes exhibiting red and NIR light-triggered enhancement of antibacterial and anticancer activities, illuminating the path for the development of long-wavelength absorbing cobalt complexes with enhanced therapeutic efficacy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940083","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}
Expression of concern for ‘Synthesis and characterization of a novel copper carboxylate complex and a copper complex-coated polyether sulfone membrane for efficient degradation of methylene blue dye under UV irradiation: the single crystal X-ray structure of the copper carboxylate complex’ by Rupy Dhir et al., Dalton Trans., 2024, 53, 9441–9451, https://doi.org/10.1039/D4DT00871E.
{"title":"Expression of concern: Synthesis and characterization of a novel copper carboxylate complex and a copper complex-coated polyether sulfone membrane for efficient degradation of methylene blue dye under UV irradiation: the single crystal X-ray structure of the copper carboxylate complex","authors":"Rupy Dhir, Bulle Shah, Narinder Singh","doi":"10.1039/d5dt90010g","DOIUrl":"https://doi.org/10.1039/d5dt90010g","url":null,"abstract":"Expression of concern for ‘Synthesis and characterization of a novel copper carboxylate complex and a copper complex-coated polyether sulfone membrane for efficient degradation of methylene blue dye under UV irradiation: the single crystal X-ray structure of the copper carboxylate complex’ by Rupy Dhir <em>et al.</em>, <em>Dalton Trans.</em>, 2024, <strong>53</strong>, 9441–9451, https://doi.org/10.1039/D4DT00871E.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"118 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940086","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}
Assembling chiral coordination polymers into nano/microflower structures may improve their performance such as chiral recognition and separation. In this study, we chose a chiral metal phosphonate system, i.e., In(NO3)3/R-, S-pempH2 [pempH2 = (1-phenylethylamino)methylphosphonic acid], and carried out a systematic work on the self-assembly of this system in different alcohol/H2O mixed solvents under solvothermal conditions. Enanotiomeric compounds R-, S-In₂(pempH)₂(μ₂-OH)₂(NO₃)₂(H₂O)₂ (R-, S-1) were obtained showing dense layered structures, but their morphologies varied with alcohol solvent. We obtained crystals of R-, S-1C in triethylene glycol (TEG)/H2O mixed solvent and spiral microflowers of R-, S-1MF in isopropanol (IPA)/H2O mixed solvent. Adsorption isotherms using enantiopure R-2-butanol and S-2-butanol as probe molecules revealed that compounds R-1MF and S-1MF had higher adsorption capacity compared to the crystalline sample and displayed enantioselective adsorption behaviour.
{"title":"Homochiral layered indium phosphonates: solvent modulation of morphology and chiral discrimination adsorption","authors":"Teng Qian, Song-Song Bao, Ran Gao, Li-Min Zheng","doi":"10.1039/d4dt03227f","DOIUrl":"https://doi.org/10.1039/d4dt03227f","url":null,"abstract":"Assembling chiral coordination polymers into nano/microflower structures may improve their performance such as chiral recognition and separation. In this study, we chose a chiral metal phosphonate system, i.e., In(NO3)3/R-, S-pempH2 [pempH2 = (1-phenylethylamino)methylphosphonic acid], and carried out a systematic work on the self-assembly of this system in different alcohol/H2O mixed solvents under solvothermal conditions. Enanotiomeric compounds R-, S-In₂(pempH)₂(μ₂-OH)₂(NO₃)₂(H₂O)₂ (R-, S-1) were obtained showing dense layered structures, but their morphologies varied with alcohol solvent. We obtained crystals of R-, S-1C in triethylene glycol (TEG)/H2O mixed solvent and spiral microflowers of R-, S-1MF in isopropanol (IPA)/H2O mixed solvent. Adsorption isotherms using enantiopure R-2-butanol and S-2-butanol as probe molecules revealed that compounds R-1MF and S-1MF had higher adsorption capacity compared to the crystalline sample and displayed enantioselective adsorption behaviour.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"98 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961545","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}
The development of viable, stable, and highly efficient molecular water oxidation catalysts under acidic aqueous conditions is challenging with earth-abundant metals in the field of renewable energy based on their low stability and catalytic activity. Herein, we discussed the effectiveness of transition metal complexes for electrocatalytic water oxidation under acidic conditions. We identified the scientific challenges that should be overcome for the future development and application of water oxidation electrochemical catalysts.
{"title":"Chemical Design of Metal Complexes for Electrochemical Water Oxidation under Acidic Conditions","authors":"Zhentao Yu","doi":"10.1039/d4dt02874k","DOIUrl":"https://doi.org/10.1039/d4dt02874k","url":null,"abstract":"The development of viable, stable, and highly efficient molecular water oxidation catalysts under acidic aqueous conditions is challenging with earth-abundant metals in the field of renewable energy based on their low stability and catalytic activity. Herein, we discussed the effectiveness of transition metal complexes for electrocatalytic water oxidation under acidic conditions. We identified the scientific challenges that should be overcome for the future development and application of water oxidation electrochemical catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"14 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940139","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}
In a systematic study, six pseudopolymorphs coordination polymers containing ditopic 1,3-di(pyridin-4-yl)urea ligand (4bpu) and constructed with d10 metal cations; possessing the formula {[M(4bpu)I2]S}n [(M = Zn, Cd and Hg) , (S = MeOH or EtOH)], namely; Zn-MeOH, Zn-EtOH, Cd-MeOH, Cd-EtOH, Hg-MeOH and Hg-EtOH were obtained. The title compounds were characterized by single-crystal X-ray diffraction analysis (SC-XRD), elemental analysis (CHN), FT-IR spectroscopy, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). The diffraction studies show that these compounds are isostructural 1D zig-zag chain coordination polymers which is also confirmed using XPac 2.0.2 software and occurrence of three- and one-dimensional (3D and 1D) isostructurality was investigated in terms of their molecular assembly in solid state structures. These comparisons were performed by extracting the dissimilarity index and stretching parameter, providing quantitative insights into the structural similarity across the pseudopolymorphic coordination polymers, which exhibit robust 3D isostructurality. Additionally, the geometry of the zig-zag chain structures was thoroughly analyzed, highlighting the subtle variations and common features that contribute to isostructurality. The supramolecular architecture of these pseudopolymorphs is stabilized by robust and repetitive hydrogen bonding motifs involving N−H⋯O, O−H⋯I and C−H⋯I interactions between the framework and guest solvent molecules (MeOH or EtOH). These interactions replace the commonly observed bifurcated hydrogen bonds (α-tape motif) between urea moieties, emphasizing the pivotal role of solvent molecules in controlling of pseudopolymorphism and defining the final structural assembly. This detailed understanding of hydrogen bonding provides valuable insights into tailoring intermolecular interactions, enabling the design of materials with enhanced functionalities for diverse applications. A detailed investigation of urea−C=O⋯π interactions in urea-based compounds highlights the classification of these interactions as semilocalized (η2 – SL) based on geometric parameters and reveals their significance through crystallographic and database studies. Hirshfeld surface analysis has been performed for all compounds to determine the percentage contribution of intermolecular interactions.
{"title":"Controlling pseudopolymorphism via robust and repetitive solvent-containing supramolecular interactions in urea-based isostructural coordination polymers","authors":"Ghazaleh Khorshidi, Behrouz Notash","doi":"10.1039/d4dt03344b","DOIUrl":"https://doi.org/10.1039/d4dt03344b","url":null,"abstract":"In a systematic study, six pseudopolymorphs coordination polymers containing ditopic 1,3-di(pyridin-4-yl)urea ligand (4bpu) and constructed with d10 metal cations; possessing the formula {[M(4bpu)I2]S}n [(M = Zn, Cd and Hg) , (S = MeOH or EtOH)], namely; Zn-MeOH, Zn-EtOH, Cd-MeOH, Cd-EtOH, Hg-MeOH and Hg-EtOH were obtained. The title compounds were characterized by single-crystal X-ray diffraction analysis (SC-XRD), elemental analysis (CHN), FT-IR spectroscopy, thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD). The diffraction studies show that these compounds are isostructural 1D zig-zag chain coordination polymers which is also confirmed using XPac 2.0.2 software and occurrence of three- and one-dimensional (3D and 1D) isostructurality was investigated in terms of their molecular assembly in solid state structures. These comparisons were performed by extracting the dissimilarity index and stretching parameter, providing quantitative insights into the structural similarity across the pseudopolymorphic coordination polymers, which exhibit robust 3D isostructurality. Additionally, the geometry of the zig-zag chain structures was thoroughly analyzed, highlighting the subtle variations and common features that contribute to isostructurality. The supramolecular architecture of these pseudopolymorphs is stabilized by robust and repetitive hydrogen bonding motifs involving N−H⋯O, O−H⋯I and C−H⋯I interactions between the framework and guest solvent molecules (MeOH or EtOH). These interactions replace the commonly observed bifurcated hydrogen bonds (α-tape motif) between urea moieties, emphasizing the pivotal role of solvent molecules in controlling of pseudopolymorphism and defining the final structural assembly. This detailed understanding of hydrogen bonding provides valuable insights into tailoring intermolecular interactions, enabling the design of materials with enhanced functionalities for diverse applications. A detailed investigation of urea−C=O⋯π interactions in urea-based compounds highlights the classification of these interactions as semilocalized (η2 – SL) based on geometric parameters and reveals their significance through crystallographic and database studies. Hirshfeld surface analysis has been performed for all compounds to determine the percentage contribution of intermolecular interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940290","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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