The present work descries the strategic design and synthesis of a dinuclear mixed-valence Co(III)/Co(II) complex, [(N3)CoIIILr(μ-O2CR1)CoII(N3)]·CH3OH, which has been synthesized using an N2O4 donor compartmental ligand, H2Lr {(2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)}, CoCl2·6H2O, benzoic acid (R1CO2H) and NaN3 in 1: 2: 1: 2 ratio. Single crystal X-ray diffraction structure confirms the presence of a Co2O2 core in the complex. Co(III) center is present in the inner N2O2 donor pocket and cobalt(II) center is trapped in the outer O2O′2 donor pocket, as confirmed by bond length consideration and BVS calculation. Experimental effective magnetic moment supports the presence of three unpaired electron in the complex. DFT calculation is performed to confirm th oxidation state of The high spin configuration is 28.2 kcal/mol more stable than the low spin configuration at the CAM-B3LYP/Lanl2DZ/6-31G(d) level of theory, thus supporting the quadruplet nature of the complex.
{"title":"Synthesis, structural characterization and DFT study of a cobalt(III)/cobalt(II) complex derived from N,O donor reduced Schiff base ligand","authors":"Rabi Sankar Sarkar , Snehasis Banerjee , Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.122618","DOIUrl":"10.1016/j.ica.2025.122618","url":null,"abstract":"<div><div>The present work descries the strategic design and synthesis of a dinuclear mixed-valence Co(III)/Co(II) complex, [(N<sub>3</sub>)Co<sup>III</sup>L<sup>r</sup>(<em>μ-O</em><sub><em>2</em></sub><em>CR</em><sup><em>1</em></sup>)Co<sup>II</sup>(N<sub>3</sub>)]·CH<sub>3</sub>OH<strong>,</strong> which has been synthesized using an N<sub>2</sub>O<sub>4</sub> donor compartmental ligand, H<sub>2</sub>L<sup>r</sup> {(2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)}, CoCl<sub>2</sub>·6H<sub>2</sub>O, benzoic acid (<em>R</em><sup><em>1</em></sup><em>CO</em><sub><em>2</em></sub><em>H</em>) and NaN<sub>3</sub> in 1: 2: 1: 2 ratio. Single crystal X-ray diffraction structure confirms the presence of a Co<sub>2</sub>O<sub>2</sub> core in the complex. Co(III) center is present in the inner N<sub>2</sub>O<sub>2</sub> donor pocket and cobalt(II) center is trapped in the outer O<sub>2</sub>O′<sub>2</sub> donor pocket, as confirmed by bond length consideration and BVS calculation. Experimental effective magnetic moment supports the presence of three unpaired electron in the complex. DFT calculation is performed to confirm th oxidation state of The high spin configuration is 28.2 kcal/mol more stable than the low spin configuration at the CAM-B3LYP/Lanl2DZ/6-31G(d) level of theory, thus supporting the quadruplet nature of the complex.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122618"},"PeriodicalIF":2.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563297","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}
Pub Date : 2025-03-03DOI: 10.1016/j.ica.2025.122626
Yonghua Zhang, Cancan Shi, Shuqi Wang, Yufang Wang
A new one-dimensional Co-based coordination polymer (CP), namely, [Co(Hbta2−)(L)] (Co-CP) (H3bta = 1,3,5-benzenetricarboxylic acid and L = 4̕ -(4-(1H-imidazol-1-yl)phenyl)-2,2′:6–2″-terpyridine) was successfully prepared through the simple one-step solvothermal method. Co(II) is five-coordinated with two carboxylate oxygen atoms from two different Hbta2− ligands and three nitrogen atoms from one L ligand. Hbta2− and L coordinate with cobalt to form a one-dimensional chain by carboxyl groups bridging, and the one-dimensional chains interconnected by strong hydrogen bonding interactions to generate a two-dimensional layer, which is further extended by π-π stacking interactions into a three-dimensional supramolecular architecture. N-rich L ligands enhance the electrochemical properties of coordination polymer. Cyclic voltammetry (CV) and amperometric investigation exhibited that the Co-CP showed excellent nonenzymatic electrochemical sensing performance toward glucose. The Co-CP modified electrode offered a wide linear range from 20 μM to 19.7 mM in three segments and a low detection limit of 5 μM (S/N = 3). The electrochemical glucose sensor also exhibited excellent stability.
{"title":"A one-dimensional co-based coordination polymer: Synthesis, crystal structure and nonenzymatic electrochemical sensing for glucose","authors":"Yonghua Zhang, Cancan Shi, Shuqi Wang, Yufang Wang","doi":"10.1016/j.ica.2025.122626","DOIUrl":"10.1016/j.ica.2025.122626","url":null,"abstract":"<div><div>A new one-dimensional <em>Co</em>-based coordination polymer (CP), namely, [Co(Hbta<sup>2−</sup>)(L)] (Co-CP) (H<sub>3</sub>bta = 1,3,5-benzenetricarboxylic acid and L = 4̕ -(4-(1H-imidazol-1-yl)phenyl)-2,2′:6–2″-terpyridine) was successfully prepared through the simple one-step solvothermal method. Co(II) is five-coordinated with two carboxylate oxygen atoms from two different Hbta<sup>2−</sup> ligands and three nitrogen atoms from one L ligand. Hbta<sup>2−</sup> and L coordinate with cobalt to form a one-dimensional chain by carboxyl groups bridging, and the one-dimensional chains interconnected by strong hydrogen bonding interactions to generate a two-dimensional layer, which is further extended by π-π stacking interactions into a three-dimensional supramolecular architecture. N-rich L ligands enhance the electrochemical properties of coordination polymer. Cyclic voltammetry (CV) and amperometric investigation exhibited that the Co-CP showed excellent nonenzymatic electrochemical sensing performance toward glucose. The Co-CP modified electrode offered a wide linear range from 20 μM to 19.7 mM in three segments and a low detection limit of 5 μM (S/N = 3). The electrochemical glucose sensor also exhibited excellent stability.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122626"},"PeriodicalIF":2.7,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551756","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}
Pub Date : 2025-03-02DOI: 10.1016/j.ica.2025.122619
Hao-Yu Zhu , Suo Peng , Li-Jun Xue , Yi Zhang , Wei-Min Chen , Lu Xue , Fang-Ming Wang , Li-Li Wen
Herein, we report a new blue emission metal-organic framework [(CH3)2NH2+]In (C28H12N2O8) (MOF) (In-BCTC) with high porosity and internal quantum yield (IQY) at 6.97 % based on the ligand [9,9′-bicarbazole]-3,3′,6,6′-tetracarboxylic acid (H4BCTC) by solvothermal method. When encapsulating trace amounts (0.003 wt%) of an orange-emitting dye Rhodamine 6G (Rho6G), there obtains bright pure white light emitting material Rho6G@In-BCTC with an ideal CIE coordinate of (0.33, 0.33) and increases its IQY up to 23.65 %, with the moderate correlated color temperature (CCT: 5566 K). It is an interesting development in a MOF-based white-light-emitting phosphors.
{"title":"Encapsulating Rhodamine 6G in a new anionic in-based metal-organic framework to realize pure white light emission","authors":"Hao-Yu Zhu , Suo Peng , Li-Jun Xue , Yi Zhang , Wei-Min Chen , Lu Xue , Fang-Ming Wang , Li-Li Wen","doi":"10.1016/j.ica.2025.122619","DOIUrl":"10.1016/j.ica.2025.122619","url":null,"abstract":"<div><div>Herein, we report a new blue emission metal-organic framework [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub><sup>+</sup>]In (C<sub>28</sub>H<sub>12</sub>N<sub>2</sub>O<sub>8</sub>) (MOF) (<strong>In-BCTC</strong>) with high porosity and internal quantum yield (IQY) at 6.97 % based on the ligand [9,9′-bicarbazole]-3,3′,6,6′-tetracarboxylic acid (H<sub>4</sub>BCTC) by solvothermal method. When encapsulating trace amounts (0.003 wt%) of an orange-emitting dye Rhodamine 6G (Rho6G), there obtains bright pure white light emitting material Rho6G@<strong>In-BCTC</strong> with an ideal CIE coordinate of (0.33, 0.33) and increases its IQY up to 23.65 %, with the moderate correlated color temperature (CCT: 5566 K). It is an interesting development in a MOF-based white-light-emitting phosphors.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122619"},"PeriodicalIF":2.7,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551677","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}
Pub Date : 2025-03-01DOI: 10.1016/j.ica.2025.122621
Hao-Yi Huang , Hong Li , Xingwei Cai , Shuyang Chen , Shaojun Zheng , Lulu Li , Peipei Cen , Lei Chen
Two new heterometallic coordination polymers, [Dy(TPA)Fe(CN6)(H2O)2]·4H2O (1-Dy) and [Gd2(TPA)2Fe2(CN6)2(CH3OH)2]·8.5H2O (2-Gd) were synthesized by reacting DyCl3·6H2O with K3[Fe(CN)6] and tri[(2-pyridyl)methyl]amine (TPA). The structures of both complexes were established by single crystal X-ray diffraction. Polymer 1-Dy exhibits a one-dimensional (1D) chain structure formed by [Fe(CN)6]3− bridging the [Dy(TPA)(H2O)2]3+ units. For polymer 2-Gd, each [Fe(CN)6]3− unit is connected to three [Gd(TPA)(CH3OH)]3+ units through three nearly coplanar CN groups, forming a near-rectangular grid Gd2Fe2. These Gd2Fe2 extend to generate a 2-dimensional (2D) monolayered topology, which represents a cyclic formation of a novel grid structure. Hydrogen bonding interactions via water molecules stabilize both structures. Magnetic susceptibility measurements indicate weak antiferromagnetic interactions between Ln(III) and Fe(III) ions, with Fe(III) and Ln(III) centers behaving as nearly isolated magnetic entities.
{"title":"Syntheses, crystal structures, and magnetic properties of cyanido-bridged one- and two-dimensional Ln(III)-Fe(III) coordination polymers","authors":"Hao-Yi Huang , Hong Li , Xingwei Cai , Shuyang Chen , Shaojun Zheng , Lulu Li , Peipei Cen , Lei Chen","doi":"10.1016/j.ica.2025.122621","DOIUrl":"10.1016/j.ica.2025.122621","url":null,"abstract":"<div><div>Two new heterometallic coordination polymers, [Dy(<em>TPA</em>)Fe(CN<sub>6</sub>)(H<sub>2</sub>O)<sub>2</sub>]·4H<sub>2</sub>O (<strong>1-Dy</strong>) and [Gd<sub>2</sub>(TPA)<sub>2</sub>Fe<sub>2</sub>(CN<sub>6</sub>)<sub>2</sub>(CH<sub>3</sub>OH)<sub>2</sub>]·8.5H<sub>2</sub>O (<strong>2-Gd</strong>) were synthesized by reacting DyCl<sub>3</sub>·6H<sub>2</sub>O with K<sub>3</sub>[Fe(CN)<sub>6</sub>] and tri[(2-pyridyl)methyl]amine (TPA). The structures of both complexes were established by single crystal X-ray diffraction. Polymer <strong>1-Dy</strong> exhibits a one-dimensional (1D) chain structure formed by [Fe(CN)<sub>6</sub>]<sup>3−</sup> bridging the [Dy(TPA)(H<sub>2</sub>O)<sub>2</sub>]<sup>3+</sup> units. For polymer <strong>2-Gd</strong>, each [Fe(CN)<sub>6</sub>]<sup>3−</sup> unit is connected to three [Gd(TPA)(CH<sub>3</sub>OH)]<sup>3+</sup> units through three nearly coplanar CN groups, forming a near-rectangular grid Gd<sub>2</sub>Fe<sub>2</sub>. These Gd<sub>2</sub>Fe<sub>2</sub> extend to generate a 2-dimensional (2D) monolayered topology, which represents a cyclic formation of a novel grid structure. Hydrogen bonding interactions via water molecules stabilize both structures. Magnetic susceptibility measurements indicate weak antiferromagnetic interactions between Ln(III) and Fe(III) ions, with Fe(III) and Ln(III) centers behaving as nearly isolated magnetic entities.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122621"},"PeriodicalIF":2.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563296","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}
Pub Date : 2025-03-01DOI: 10.1016/j.ica.2025.122623
Kai Zheng , Kaikai Zhao , Weibiao Guo , Xuquan Liu , Yu Liang , Kuan Liang , Qianjun Deng , Hongxia Xi , Pengfei Yang , Xuejiao Sun , Chongxiong Duan
With the increasing reliance on nuclear energy and the potential environmental release of uranium radionuclides, public concern regarding uranium pollution has steadily grown. Metal-organic frameworks (MOFs), known for their abundant active sites and unique porous structures, exhibit significant promise in addressing uranium-related challenges. In this study, a nano-hierarchical porous structure of Cu-BTC (NH-Cu-BTC) was synthesized at room temperature and atmospheric pressure, utilizing N,N-dimethylethylenediamine as a templating agent in the aqueous phase. The impact of activation on the porosity characteristics of NH-Cu-BTC was investigated. The as-synthesized NH-Cu-BTC possessed micropores, mesopores, and macropores, with crystal sizes approximately 150 nm. Through simulation calculations, the electrostatic potential and orbital energies of the templating agent molecule were analyzed to elucidate the synthesis mechanism. Various factors influencing the adsorption of uranium (VI) by NH-Cu-BTC, including pH, contact time, and temperature, were explored, and the underlying adsorption mechanisms were elaborated. Compared to C-Cu-BTC, NH-Cu-BTC exhibited a 32.8 % enhancement in its adsorption capacity for uranium (VI). This investigation furnishes precious comprehension regarding the fabrication and utilization of porous substances, proffering a novel tactic for proficiently eliminating uranium (VI) from aqueous mediums.
{"title":"Water-phase synthesis of nano-hierarchical porous metal–organic frameworks for removal of uranium (VI) from aqueous solution","authors":"Kai Zheng , Kaikai Zhao , Weibiao Guo , Xuquan Liu , Yu Liang , Kuan Liang , Qianjun Deng , Hongxia Xi , Pengfei Yang , Xuejiao Sun , Chongxiong Duan","doi":"10.1016/j.ica.2025.122623","DOIUrl":"10.1016/j.ica.2025.122623","url":null,"abstract":"<div><div>With the increasing reliance on nuclear energy and the potential environmental release of uranium radionuclides, public concern regarding uranium pollution has steadily grown. Metal-organic frameworks (MOFs), known for their abundant active sites and unique porous structures, exhibit significant promise in addressing uranium-related challenges. In this study, a nano-hierarchical porous structure of Cu-BTC (NH-Cu-BTC) was synthesized at room temperature and atmospheric pressure, utilizing <em>N,N</em>-dimethylethylenediamine as a templating agent in the aqueous phase. The impact of activation on the porosity characteristics of NH-Cu-BTC was investigated. The as-synthesized NH-Cu-BTC possessed micropores, mesopores, and macropores, with crystal sizes approximately 150 nm. Through simulation calculations, the electrostatic potential and orbital energies of the templating agent molecule were analyzed to elucidate the synthesis mechanism. Various factors influencing the adsorption of uranium (VI) by NH-Cu-BTC, including pH, contact time, and temperature, were explored, and the underlying adsorption mechanisms were elaborated. Compared to C-Cu-BTC, NH-Cu-BTC exhibited a 32.8 % enhancement in its adsorption capacity for uranium (VI). This investigation furnishes precious comprehension regarding the fabrication and utilization of porous substances, proffering a novel tactic for proficiently eliminating uranium (VI) from aqueous mediums.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122623"},"PeriodicalIF":2.7,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551757","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}
Pub Date : 2025-02-26DOI: 10.1016/j.ica.2025.122613
Badri Z. Momeni , Nastaran Fathi , Abbas Biglari , Reza Fallahpour , Jan Janczak , Richard J. Puddephatt
In situ reaction of SnMe2Cl2 with NaN3 or KOCN in methanol or a mixture of acetone/H2O solution has resulted in the formation of SnMe2(N3)2 (1a) and SnMe2(NCO)2 (1b) complexes, respectively. The reaction of dimethylplatinum(II) complexes [PtMe2(NN)], NN = bpy (bpy = 2,2′-bipyridine) or 4,4′-Me2bpy (4,4′-Me2bpy = 4,4′-dimethyl-2,2′-dipyridine), with 1a or 1b occurs initially by oxidative addition but the initial platinum(IV) products [PtXMe2(SnMe2X)(NN)], decompose during attempted isolation to give new organoplatinum(II)/(IV) complexes that contain Pt-N3 or Pt-NCO bonds, several of which were characterized crystallographically. The reaction of electron-rich complex [PtMe2(bpy)] (bpy = 2,2′-bipyridine) with 1a resulted in the formation of the new Pt(IV) complex fac-[PtMe3(N3)(bpy)] (2). However, the similar reaction of 1a or 1b with [PtMe2(4,4′-Me2bpy)] (4,4′-Me2bpy = 4,4′-dimethyl-2,2′-dipyridine) gave the corresponding Pt(II) complexes [PtMe(N3)(4,4′-Me2bpy)] (3), or [PtMe(NCO)(4,4′-Me2bpy)] (4), respectively. The reaction of [PtMe2(4,4′-Me2bpy)] or [PtMe2(bpy)] with SnMe2Cl2, followed by addition of KOCN, gave [PtCl2(4,4′-Me2bpy)] (5) or fac-[PtMe3Cl(bpy)] (6), respectively. The crystal architecture in compounds 2–4 and 6 is stabilized by weak hydrogen bonds and π···π interactions. Further insight was obtained by monitoring the reactions in situ using multinuclear (1H, 13C, 119Sn, 195Pt) NMR spectroscopy in different solvents and by DFT calculations.
{"title":"Structure and reactivity in reactions of dimethyltin(IV) di(azide) and di(isocyanate) with dimethylplatinum(II) complexes","authors":"Badri Z. Momeni , Nastaran Fathi , Abbas Biglari , Reza Fallahpour , Jan Janczak , Richard J. Puddephatt","doi":"10.1016/j.ica.2025.122613","DOIUrl":"10.1016/j.ica.2025.122613","url":null,"abstract":"<div><div><em>In situ</em> reaction of SnMe<sub>2</sub>Cl<sub>2</sub> with NaN<sub>3</sub> or KOCN in methanol or a mixture of acetone/H<sub>2</sub>O solution has resulted in the formation of SnMe<sub>2</sub>(N<sub>3</sub>)<sub>2</sub> (<strong>1a</strong>) and SnMe<sub>2</sub>(NCO)<sub>2</sub> (<strong>1b</strong>) complexes, respectively. The reaction of dimethylplatinum(II) complexes [PtMe<sub>2</sub>(NN)], NN = bpy (bpy = 2,2′-bipyridine) or 4,4′-Me<sub>2</sub>bpy (4,4′-Me<sub>2</sub>bpy <strong>=</strong> 4,4′-dimethyl-2,2′-dipyridine), with <strong>1a</strong> or <strong>1b</strong> occurs initially by oxidative addition but the initial platinum(IV) products [PtXMe<sub>2</sub>(SnMe<sub>2</sub>X)(NN)], decompose during attempted isolation to give new organoplatinum(II)/(IV) complexes that contain Pt-N<sub>3</sub> or Pt-NCO bonds, several of which were characterized crystallographically. The reaction of electron-rich complex [PtMe<sub>2</sub>(bpy)] (bpy = 2,2′-bipyridine) with <strong>1a</strong> resulted in the formation of the new Pt(IV) complex <em>fac</em>-[PtMe<sub>3</sub>(N<sub>3</sub>)(bpy)] (<strong>2</strong>). However, the similar reaction of <strong>1a</strong> or <strong>1b</strong> with [PtMe<sub>2</sub>(4,4′-Me<sub>2</sub>bpy)] (4,4′-Me<sub>2</sub>bpy <strong>=</strong> 4,4′-dimethyl-2,2′-dipyridine) gave the corresponding Pt(II) complexes [PtMe(N<sub>3</sub>)(4,4′-Me<sub>2</sub>bpy)] (<strong>3</strong>), or [PtMe(NCO)(4,4′-Me<sub>2</sub>bpy)] (<strong>4</strong>), respectively. The reaction of [PtMe<sub>2</sub>(4,4′-Me<sub>2</sub>bpy)] or [PtMe<sub>2</sub>(bpy)] with SnMe<sub>2</sub>Cl<sub>2</sub>, followed by addition of KOCN, gave [PtCl<sub>2</sub>(4,4′-Me<sub>2</sub>bpy)] (<strong>5</strong>) or <em>fac</em>-[PtMe<sub>3</sub>Cl(bpy)] (<strong>6</strong>), respectively. The crystal architecture in compounds <strong>2</strong>–<strong>4</strong> and <strong>6</strong> is stabilized by weak hydrogen bonds and π···π interactions. Further insight was obtained by monitoring the reactions <em>in situ</em> using multinuclear (<sup>1</sup>H, <sup>13</sup>C, <sup>119</sup>Sn, <sup>195</sup>Pt) NMR spectroscopy in different solvents and by DFT calculations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122613"},"PeriodicalIF":2.7,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551676","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}
Pub Date : 2025-02-24DOI: 10.1016/j.ica.2025.122598
Angelo Lembo, Miriam Demingo, Marilena Carbone, Pietro Tagliatesta
Porphyrins are peculiar molecules with very interesting photochemical properties, generally their absorption spectrum typically spans from 350 nm to 650 or 590 nm for the free-base or metal-complex porphyrins, respectively. This wide absorption window makes them suitable candidates for many different applications dealing with light interaction, as need in the new emerging solar cells technologies, in the non-linear optics field and in medical applications such as bioimaging and photodynamic therapy (PDT). By introducing substituents at the meso- or beta-pyrrole position, the porphyrin absorption spectrum can be modified according to the requirements of the different application fields. One of the most effective way to deep affect the UV–vis spectrum of porphyrins is to extend the π-electron system of the tetrapyrrole ring. This can be achieved by introducing triple or double CC bonds directly connected at meso- or beta-position. However, while the introduction of a simple triple bond and, more in general, alkynes exploiting Sonogashira reaction is widely used in porphyrin chemistry affording very high yields, the introduction of a double bond or alkenyl compounds with a well-defined stereochemistry through classical reactions or palladium-catalyzed cross-coupling reactions still remains problematic in terms of hard reaction conditions, excess of alkene reagents, by-products formation. In this review we want to report the synthetic methods described in the literature for obtaining meso- and beta-functionalized porphyrins by means of coupling alkenyl derivatives with porphyrins and metalloporphyrins, thorough the use of the Heck cross-coupling reaction that, if on one hand, is well consolidated with canonical reagents (e.g. with simple aryl-halides, either bromo- or iodo-, or even aryltriflates) on the other side it can be very tricky when meso- or- beta-brominated porphyrin are used. Nevertheless the Heck cross-coupling reaction still remains one of the most versatile synthetic methodology to modify the porphyrin core and, consequently, the optical properties of the tetrapyrrole macrocycle. We will briefly discuss which results can be obtained when bromoporphyins are used as starting aryl-halide and show the last achievements of such coupling by the use of the modern palladium transmetallation reactions.
{"title":"Porphyrins functionalization by alkenyl compounds using the Heck cross-coupling reaction. Insights on methodologies and reaction products","authors":"Angelo Lembo, Miriam Demingo, Marilena Carbone, Pietro Tagliatesta","doi":"10.1016/j.ica.2025.122598","DOIUrl":"10.1016/j.ica.2025.122598","url":null,"abstract":"<div><div>Porphyrins are peculiar molecules with very interesting photochemical properties, generally their absorption spectrum typically spans from 350 nm to 650 or 590 nm for the free-base or metal-complex porphyrins, respectively. This wide absorption window makes them suitable candidates for many different applications dealing with light interaction, as need in the new emerging solar cells technologies, in the non-linear optics field and in medical applications such as bioimaging and photodynamic therapy (PDT). By introducing substituents at the <em>meso</em>- or <em>beta</em>-pyrrole position, the porphyrin absorption spectrum can be modified according to the requirements of the different application fields. One of the most effective way to deep affect the UV–vis spectrum of porphyrins is to extend the π-electron system of the tetrapyrrole ring. This can be achieved by introducing triple or double C<img>C bonds directly connected at <em>meso</em>- or <em>beta</em>-position. However, while the introduction of a simple triple bond and, more in general, alkynes exploiting Sonogashira reaction is widely used in porphyrin chemistry affording very high yields, the introduction of a double bond or alkenyl compounds with a well-defined stereochemistry through classical reactions or palladium-catalyzed cross-coupling reactions still remains problematic in terms of hard reaction conditions, excess of alkene reagents, by-products formation. In this review we want to report the synthetic methods described in the literature for obtaining <em>meso</em>- and <em>beta</em>-functionalized porphyrins by means of coupling alkenyl derivatives with porphyrins and metalloporphyrins, thorough the use of the Heck cross-coupling reaction that, if on one hand, is well consolidated with canonical reagents (e.g. with simple aryl-halides, either bromo- or iodo-, or even aryltriflates) on the other side it can be very tricky when <em>meso-</em> or- <em>beta-</em>brominated porphyrin are used. Nevertheless the Heck cross-coupling reaction still remains one of the most versatile synthetic methodology to modify the porphyrin core and, consequently, the optical properties of the tetrapyrrole macrocycle. We will briefly discuss which results can be obtained when bromoporphyins are used as starting aryl-halide and show the last achievements of such coupling by the use of the modern palladium transmetallation reactions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122598"},"PeriodicalIF":2.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535405","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}
Pub Date : 2025-02-24DOI: 10.1016/j.ica.2025.122612
Arda Atakol , Beyhan Yiğit , Hasan Akdan , Enes Evren , Duygu Barut Celepci , Murat Yiğit , Muhittin Aygün , İsmail Özdemir
In this study, a series of amine-functionalized benzimidazolium salts and their PEPPSI-type N-heterocyclic carbene (NHC) palladium(II) complexes 3a-e were synthesized and characterized by FT-IR, 1H NMR and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. The molecular and crystal structure of 3c and 3d was confirmed by the single-crystal X-ray diffraction (SC-XRD) method. Structural analysis reveals that the geometries of the PdII centers of the complexes adopt slightly distorted square planar environment. The new palladium complexes were tested as catalysts in the direct C5 arylation of 2-acetylfuran and 2-acetylthiophene with aryl bromides at 120 °C in N,N-dimethylacetamide. The arylation reactions proceeded selectively at the C5 position of the heteroaromatic compounds, and the corresponding coupling products were obtained in moderate to good yields by using 1 mol% of the palladium complex. Also, solid computational validation of the experimental results was achieved by geometric optimizations, frontier molecular orbital and molecular electrostatic potential studies, as well as natural bonding orbital analysis utilizing density functional theory.
{"title":"PEPPSI-type N-heterocyclic carbene palladium(II) complexes as catalysts in the direct C5 arylation of furan and thiophene","authors":"Arda Atakol , Beyhan Yiğit , Hasan Akdan , Enes Evren , Duygu Barut Celepci , Murat Yiğit , Muhittin Aygün , İsmail Özdemir","doi":"10.1016/j.ica.2025.122612","DOIUrl":"10.1016/j.ica.2025.122612","url":null,"abstract":"<div><div>In this study, a series of amine-functionalized benzimidazolium salts and their PEPPSI-type N-heterocyclic carbene (NHC) palladium(II) complexes <strong>3a-e</strong> were synthesized and characterized by FT-IR, <sup>1</sup>H NMR and <sup>13</sup>C NMR spectroscopy, elemental analysis, and mass spectrometry. The molecular and crystal structure of <strong>3c</strong> and <strong>3d</strong> was confirmed by the single-crystal X-ray diffraction (SC-XRD) method. Structural analysis reveals that the geometries of the Pd<sup>II</sup> centers of the complexes adopt slightly distorted <em>square planar</em> environment. The new palladium complexes were tested as catalysts in the direct C5 arylation of 2-acetylfuran and 2-acetylthiophene with aryl bromides at 120 °C in <em>N,N</em>-dimethylacetamide. The arylation reactions proceeded selectively at the C5 position of the heteroaromatic compounds, and the corresponding coupling products were obtained in moderate to good yields by using 1 mol% of the palladium complex. Also, solid computational validation of the experimental results was achieved by geometric optimizations, frontier molecular orbital and molecular electrostatic potential studies, as well as natural bonding orbital analysis utilizing density functional theory.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"580 ","pages":"Article 122612"},"PeriodicalIF":2.7,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509539","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}
Pub Date : 2025-02-23DOI: 10.1016/j.ica.2025.122601
Jingyue Zhao , Xiangyu Dai , Mengdi Lv , Hanxue Liu, Meng Ren, Guojing Hu, Xuling Xue, Hong-Ke Liu
The clinical use of metal-based anticancer drugs is constrained by challenges like significant side effects and the development of drug resistance. In recent years, metal-based immunogenic cell death (ICD) inducers have attracted significant research interest for their potential in both chemotherapy and immunotherapy. Herein, we present a novel cyclometalated iridium(III) complex Ir-NPX with the COX-2 inhibitor naproxen (NPX) as a ligand, serving as an ICD inducer. Ir-NPX not only showed remarkable antitumor efficacy, notably in targeting cisplatin-resistant A549R cells, but also could inhibit the proliferation of 3D multicellular tumor spheroids. More importantly, Ir-NPX could induce severe mitochondrial injury and endoplasmic reticulum (ER) stress, lead to elevated intracellular free Ca2+ levels, and ultimately trigger the ICD effect in A549R cells. This approach of integrating bioactive molecules with metal species paved the way for the development of novel metal-based drugs for combined chemo-immunotherapy in cancer treatment.
{"title":"An efficient ICD inducer based on Ir(III) cyclometalated complex for anticancer and anti-migration effects towards cisplatin-resistant cancer cells","authors":"Jingyue Zhao , Xiangyu Dai , Mengdi Lv , Hanxue Liu, Meng Ren, Guojing Hu, Xuling Xue, Hong-Ke Liu","doi":"10.1016/j.ica.2025.122601","DOIUrl":"10.1016/j.ica.2025.122601","url":null,"abstract":"<div><div>The clinical use of metal-based anticancer drugs is constrained by challenges like significant side effects and the development of drug resistance. In recent years, metal-based immunogenic cell death (ICD) inducers have attracted significant research interest for their potential in both chemotherapy and immunotherapy. Herein, we present a novel cyclometalated iridium(III) complex <strong>Ir-NPX</strong> with the COX-2 inhibitor naproxen (NPX) as a ligand, serving as an ICD inducer. <strong>Ir-NPX</strong> not only showed remarkable antitumor efficacy, notably in targeting cisplatin-resistant A549R cells, but also could inhibit the proliferation of 3D multicellular tumor spheroids. More importantly, <strong>Ir-NPX</strong> could induce severe mitochondrial injury and endoplasmic reticulum (ER) stress, lead to elevated intracellular free Ca<sup>2+</sup> levels, and ultimately trigger the ICD effect in A549R cells. This approach of integrating bioactive molecules with metal species paved the way for the development of novel metal-based drugs for combined chemo-immunotherapy in cancer treatment.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"580 ","pages":"Article 122601"},"PeriodicalIF":2.7,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521039","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}
Pub Date : 2025-02-22DOI: 10.1016/j.ica.2025.122597
JunGang Deng , Gaoxing Su , Peng Chen , Yunpeng Du , Yi Gou , Yani Liu
{"title":"Correction to “Evaluation of DNA binding and DNA cleavage of nickel(II) complexes with tridentate α-N-heterocyclic thiosemicarbazones ligands” [Inorganica Chimica Acta 471 (2018) 194–202]","authors":"JunGang Deng , Gaoxing Su , Peng Chen , Yunpeng Du , Yi Gou , Yani Liu","doi":"10.1016/j.ica.2025.122597","DOIUrl":"10.1016/j.ica.2025.122597","url":null,"abstract":"","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"580 ","pages":"Article 122597"},"PeriodicalIF":2.7,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563642","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}
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