Pub Date : 2025-04-22DOI: 10.1021/acs.inorgchem.5c00321
Carlos Martínez-Ceberio, Francisco José Fernández-de-Córdova, Pablo Ríos, Orestes Rivada-Wheelaghan
Herein, we report the synthesis, characterization, and binding properties of a new ligand, N,N′-di-tert-butyl-3,7-diaza-1,5(2,7)-1,8-naphthyridinacyclooctaphane (tBuN6), with copper (I), CuI, centers. We demonstrate the flexibility and the ability of tBuN6 to adopt various conformations in solution and when coordinated to CuIcenters. NMR studies exhibit the labile coordination nature of CuI. However, the lability of the complexes is blocked by counterion exchange, which enables the use of less coordinating solvents such as tetrahydrofuran (THF) and avoids using acetonitrile. Thus, the exchange of [BF4]− with tetrakis 3,5-bis(trifluoromethyl)phenyl borate, [B(ArF)4]−, in 1·BF4, [Cu2(MeCN)2(tBuN6)][BF4], generates 1·B(ArF)4, which is stable in THF and reacts under a CO atmosphere to generate a syn,syn bis(carbonyl) complex. This complex is sufficiently stable in solution under CO and Ar atmosphere to be characterized by NMR and IR spectroscopy, the latter revealing two stretching bands for the CO bound to the CuI–centers at 2102 and 2088 cm–1.
{"title":"Synthesis and Characterization of Bimetallic Copper(I) Complexes Supported by a Hexadentate Naphthyridine-Based Macrocycle Ligand","authors":"Carlos Martínez-Ceberio, Francisco José Fernández-de-Córdova, Pablo Ríos, Orestes Rivada-Wheelaghan","doi":"10.1021/acs.inorgchem.5c00321","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00321","url":null,"abstract":"Herein, we report the synthesis, characterization, and binding properties of a new ligand, <i>N</i>,<i>N</i>′-di-<i>tert</i>-butyl-3,7-diaza-1,5(2,7)-1,8-naphthyridinacyclooctaphane (<sup><b>tBu</b></sup><b>N6</b>), with copper (I), Cu<sup>I</sup>, centers. We demonstrate the flexibility and the ability of <sup><b>tBu</b></sup><b>N6</b> to adopt various conformations in solution and when coordinated to Cu<sup>I</sup>centers. NMR studies exhibit the labile coordination nature of Cu<sup>I</sup>. However, the lability of the complexes is blocked by counterion exchange, which enables the use of less coordinating solvents such as tetrahydrofuran (THF) and avoids using acetonitrile. Thus, the exchange of [BF<sub>4</sub>]<sup>−</sup> with tetrakis 3,5-bis(trifluoromethyl)phenyl borate, [B(Ar<sup>F</sup>)<sub>4</sub>]<sup>−</sup>, in <b>1·BF</b><sub><b>4</b></sub>, [Cu<sub>2</sub>(MeCN)<sub>2</sub>(<sup>tBu</sup>N6)][BF<sub>4</sub>], generates <b>1·B(Ar</b><sup><b>F</b></sup><b>)</b><sub><b>4</b></sub>, which is stable in THF and reacts under a CO atmosphere to generate a <i>syn,syn</i> bis(carbonyl) complex. This complex is sufficiently stable in solution under CO and Ar atmosphere to be characterized by NMR and IR spectroscopy, the latter revealing two stretching bands for the CO bound to the Cu<sup>I</sup>–centers at 2102 and 2088 cm<sup>–1</sup>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"49 3 Pt 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.4c05443
Lorena Maria Borges Pereira, Diego França de Oliveira, Marco Antonio Tiburcio, Gabriel H. Ribeiro, Carlos André Ferreira Moraes, Flávio Olimpio Sanches Neto, Ademir João Camargo, Leonardo De Boni, Otaciro Rangel Nascimento, Manoel G. P. Homem, Rose Maria Carlos
This study explores the dynamics of charge separation (CS) and recombination in the photoinduced electron transfer of the [Ru(phen)2(pNDIp)]2+ dyad, focusing on the thermal equilibrium between rapid charge separation (CS) and the slower charge-separated state (CSS). The pNDIp component is a naphthalene diimide linked to one of the phen ligands, providing nearly unrestricted orthogonal freedom between the {[Ru(phen)3]2+} and {pNDIp} units. The investigation employs steady-state and time-resolved spectroscopic techniques, electrochemical methods, and DFT/TD-DFT computational calculations. The results show that selective excitation of the {[Ru(phen)3]2+} at 450 nm partially quenches the 3MLCT emission due to thermal equilibrium with the 3CSS state, 3{Ru3+(phen•–)2(pNDIp)} ⇌ 3{Ru3+(phen)2(pNDIp•–)}. This equilibrium is attributed to a combination of nonradiative forward (τCT = 10 ps) and reverse (τ–CT = 140 ps) time decays, driven by the intramolecular charge transfer. The long-lived 3MLCT state, the reduced distance between the donor and acceptor, and the vibrational structure of the dyad provide sufficient time for 3CS⇌3CSS equilibrium. These findings support Marcus theory and highlight key parameters such as −ΔGCS = 0.279 eV, λ = 0.49 eV, and HDA = 0.28 eV. Additionally, the dyad’s ability to generate singlet oxygen under 450 nm light suggests potential applications in photodynamic therapy and oxidative processes. Its ability to form radical anion RupNDIp•– upon 350 nm light exposure further demonstrates its versatility in photocatalytic applications.
{"title":"Exploring the Reversible Equilibrium State between 3CS and 3CSS in a Ru(phen)–Naphthalene Diimide Dyad","authors":"Lorena Maria Borges Pereira, Diego França de Oliveira, Marco Antonio Tiburcio, Gabriel H. Ribeiro, Carlos André Ferreira Moraes, Flávio Olimpio Sanches Neto, Ademir João Camargo, Leonardo De Boni, Otaciro Rangel Nascimento, Manoel G. P. Homem, Rose Maria Carlos","doi":"10.1021/acs.inorgchem.4c05443","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05443","url":null,"abstract":"This study explores the dynamics of charge separation (CS) and recombination in the photoinduced electron transfer of the [Ru(phen)<sub>2</sub>(pNDIp)]<sup>2+</sup> dyad, focusing on the thermal equilibrium between rapid charge separation (CS) and the slower charge-separated state (CSS). The pNDIp component is a naphthalene diimide linked to one of the phen ligands, providing nearly unrestricted orthogonal freedom between the {[Ru(phen)<sub>3</sub>]<sup>2+</sup>} and {pNDIp} units. The investigation employs steady-state and time-resolved spectroscopic techniques, electrochemical methods, and DFT/TD-DFT computational calculations. The results show that selective excitation of the {[Ru(phen)<sub>3</sub>]<sup>2+</sup>} at 450 nm partially quenches the <sup>3</sup>MLCT emission due to thermal equilibrium with the <sup>3</sup>CSS state, <sup>3</sup>{Ru<sup>3+</sup>(phen<sup>•<sup>–</sup></sup>)<sub>2</sub>(pNDIp)} ⇌ <sup>3</sup>{Ru<sup>3+</sup>(phen)<sub>2</sub>(pNDIp<sup>•<sup>–</sup></sup>)}. This equilibrium is attributed to a combination of nonradiative forward (τ<sub>CT</sub> = 10 ps) and reverse (τ<sub>–CT</sub> = 140 ps) time decays, driven by the intramolecular charge transfer. The long-lived <sup>3</sup>MLCT state, the reduced distance between the donor and acceptor, and the vibrational structure of the dyad provide sufficient time for <sup>3</sup>CS⇌<sup>3</sup>CSS equilibrium. These findings support Marcus theory and highlight key parameters such as −Δ<i>G</i><sub>CS</sub> = 0.279 eV, λ = 0.49 eV, and H<sub>DA</sub> = 0.28 eV. Additionally, the dyad’s ability to generate singlet oxygen under 450 nm light suggests potential applications in photodynamic therapy and oxidative processes. Its ability to form radical anion RupNDIp<sup>•<sup>–</sup></sup> upon 350 nm light exposure further demonstrates its versatility in photocatalytic applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.5c00724
Katrin Beuthert, Nils Spang, Diana Carolina Alzate Millan, Lukas Guggolz, Stefanie Dehnen
Binary Zintl anions comprising atoms of two p-block elements, and ternary Zintl clusters, in which the latter are combined with d-/f-block metal ions, are being studied with great activity. However, although an impressive variety of elemental compositions have been realized, some combinations of the p-block (semi)metals are lacking in corresponding substructures. The In/Sb combination is extremely rare, and Tl/Sb has not yet been realized at all, although the existence of pseudo-tetrahedral species, for instance, was predicted by quantum chemical studies. Extraction of the novel ternary phase K6InSb3 and of K6Tl2Sb3 with ethane-1,2-diamine (en) yielded binary Zintl anions of these elemental combinations as salts comprising pseudo-tetrahedral anions (InSb3)2– and (TlSb3)2– or nine-vertex cages (In4Sb5)3– and (Tl4Sb5)3–, respectively. To establish efficient synthesis routes, the extractions were monitored using electrospray-ionization mass spectrometry and fractionated crystallization. We thereby isolated salts of two further anions that might represent intermediates on the way to larger species, namely, a novel salt of the Sb73– anion, and a salt of the new binary anion (TlSb7)2–. We describe the experimental approach, the process of its optimization, the geometric structures of the new compounds as well as their electronic structures that were established by DFT calculations.
{"title":"Expanding the Toolbox: Synthesis of Zintl Salts Containing Anions of the In/Sb and Tl/Sb Elemental Combinations","authors":"Katrin Beuthert, Nils Spang, Diana Carolina Alzate Millan, Lukas Guggolz, Stefanie Dehnen","doi":"10.1021/acs.inorgchem.5c00724","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00724","url":null,"abstract":"Binary Zintl anions comprising atoms of two p-block elements, and ternary Zintl clusters, in which the latter are combined with d-/f-block metal ions, are being studied with great activity. However, although an impressive variety of elemental compositions have been realized, some combinations of the p-block (semi)metals are lacking in corresponding substructures. The In/Sb combination is extremely rare, and Tl/Sb has not yet been realized at all, although the existence of <i>pseudo</i>-tetrahedral species, for instance, was predicted by quantum chemical studies. Extraction of the novel ternary phase K<sub>6</sub>InSb<sub>3</sub> and of K<sub>6</sub>Tl<sub>2</sub>Sb<sub>3</sub> with ethane-1,2-diamine (en) yielded binary Zintl anions of these elemental combinations as salts comprising <i>pseudo</i>-tetrahedral anions (InSb<sub>3</sub>)<sup>2–</sup> and (TlSb<sub>3</sub>)<sup>2–</sup> or nine-vertex cages (In<sub>4</sub>Sb<sub>5</sub>)<sup>3–</sup> and (Tl<sub>4</sub>Sb<sub>5</sub>)<sup>3–</sup>, respectively. To establish efficient synthesis routes, the extractions were monitored using electrospray-ionization mass spectrometry and fractionated crystallization. We thereby isolated salts of two further anions that might represent intermediates on the way to larger species, namely, a novel salt of the Sb<sub>7</sub><sup>3–</sup> anion, and a salt of the new binary anion (TlSb<sub>7</sub>)<sup>2–</sup>. We describe the experimental approach, the process of its optimization, the geometric structures of the new compounds as well as their electronic structures that were established by DFT calculations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.5c00998
Gen Li, Wei Zeng, Gangji Yi, Xuan Zou, Xize Zhan, Hongmei Zeng, Zhien Lin, Guohong Zou
Oxyhalides are promising candidates for nonlinear optical (NLO) applications due to their unique structural and optical properties. In this study, we report the synthesis of two tellurium-based oxyhalides, Te8O15Cl2 and Te6O11Cl2, which exhibit distinct structural features and exceptional optical performance. Te8O15Cl2 crystallizes in a noncentrosymmetric 2D layered structure, while Te6O11Cl2 adopts a centrosymmetric 1D chain arrangement. Both compounds display wide optical transmission windows (0.30/0.31–25 μm), with Te8O15Cl2 achieving a large second-harmonic generation (SHG) efficiency surpassing conventional materials and a significant birefringence (Δn = 0.185 at 546 nm). The SHG response of Te8O15Cl2 is attributed to the alignment of nonlinear-active units driven by the [TeO3Cl] disphenoid and the stereochemically active lone pairs (SCALPs), facilitated by halogen-mediated structural distortion. These results highlight the potential of halogen modification for the design of advanced NLO materials with enhanced performance.
{"title":"Halogen-Driven Structural Engineering in Tellurium Oxyhalides: Enhanced SHG Response and Broad Optical Transparency","authors":"Gen Li, Wei Zeng, Gangji Yi, Xuan Zou, Xize Zhan, Hongmei Zeng, Zhien Lin, Guohong Zou","doi":"10.1021/acs.inorgchem.5c00998","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00998","url":null,"abstract":"Oxyhalides are promising candidates for nonlinear optical (NLO) applications due to their unique structural and optical properties. In this study, we report the synthesis of two tellurium-based oxyhalides, Te<sub>8</sub>O<sub>15</sub>Cl<sub>2</sub> and Te<sub>6</sub>O<sub>11</sub>Cl<sub>2</sub>, which exhibit distinct structural features and exceptional optical performance. Te<sub>8</sub>O<sub>15</sub>Cl<sub>2</sub> crystallizes in a noncentrosymmetric 2D layered structure, while Te<sub>6</sub>O<sub>11</sub>Cl<sub>2</sub> adopts a centrosymmetric 1D chain arrangement. Both compounds display wide optical transmission windows (0.30/0.31–25 μm), with Te<sub>8</sub>O<sub>15</sub>Cl<sub>2</sub> achieving a large second-harmonic generation (SHG) efficiency surpassing conventional materials and a significant birefringence (Δ<i>n</i> = 0.185 at 546 nm). The SHG response of Te<sub>8</sub>O<sub>15</sub>Cl<sub>2</sub> is attributed to the alignment of nonlinear-active units driven by the [TeO<sub>3</sub>Cl] disphenoid and the stereochemically active lone pairs (SCALPs), facilitated by halogen-mediated structural distortion. These results highlight the potential of halogen modification for the design of advanced NLO materials with enhanced performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.5c00883
Xian-Yu Shen, Ya-Nan Wang, Ya-Ting Zheng, Ye Wang, Wen-Wen Dong, Jun Zhao, Dong-Sheng Li
Formaldehyde (HCHO), a crucial industrial chemical, finds extensive applications across diverse sectors, including household products, commercial materials, aviation, and medical supplies. Methane (CH4), as an abundant C1 resource, presents a promising feedstock for HCHO synthesis. However, the direct conversion of CH4 to HCHO remains challenging due to its inherent chemical inertness, characterized by low polarizability and high C–H bond dissociation energy (439 kJ mol–1), coupled with the high reactivity of intermediate products. The development of efficient strategies for selective CH4 oxidation to high-value HCHO under mild conditions is therefore of significant practical importance. In this study, we developed a series of MIL-125-NH2@FeOOH-x heterostructured photocatalysts (FM-x) through the controlled deposition of FeOOH nanoparticles on MIL-125-NH2 surfaces. Comprehensive characterization and photocatalytic evaluations reveal that the optimized FM-1 catalyst facilitates in situ H2O2 generation and subsequent decomposition into hydroxyl radicals (•OH), enabling efficient CH4 photooxidation. Remarkably, the FM-1 catalyst achieves an exceptional HCHO production rate of 197.79 μmol·gcat–1 with >99.99% selectivity in water vapor, significantly outperforming both pristine FeOOH and MIL-125-NH2 components. This work presents a promising photocatalytic system for selective CH4 conversion, offering new insights into the design of efficient catalysts for C1 chemistry.
{"title":"Core–Shell MIL-125-NH2@FeOOH Nanocomposites for Highly Selective Photocatalytic Oxidation of Methane to Formaldehyde in Water Vapor","authors":"Xian-Yu Shen, Ya-Nan Wang, Ya-Ting Zheng, Ye Wang, Wen-Wen Dong, Jun Zhao, Dong-Sheng Li","doi":"10.1021/acs.inorgchem.5c00883","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00883","url":null,"abstract":"Formaldehyde (HCHO), a crucial industrial chemical, finds extensive applications across diverse sectors, including household products, commercial materials, aviation, and medical supplies. Methane (CH<sub>4</sub>), as an abundant C1 resource, presents a promising feedstock for HCHO synthesis. However, the direct conversion of CH<sub>4</sub> to HCHO remains challenging due to its inherent chemical inertness, characterized by low polarizability and high C–H bond dissociation energy (439 kJ mol<sup>–1</sup>), coupled with the high reactivity of intermediate products. The development of efficient strategies for selective CH<sub>4</sub> oxidation to high-value HCHO under mild conditions is therefore of significant practical importance. In this study, we developed a series of MIL-125-NH<sub>2</sub>@FeOOH-<i>x</i> heterostructured photocatalysts (FM-<i>x</i>) through the controlled deposition of FeOOH nanoparticles on MIL-125-NH<sub>2</sub> surfaces. Comprehensive characterization and photocatalytic evaluations reveal that the optimized FM-1 catalyst facilitates in situ H<sub>2</sub>O<sub>2</sub> generation and subsequent decomposition into hydroxyl radicals (<sup>•</sup>OH), enabling efficient CH<sub>4</sub> photooxidation. Remarkably, the FM-1 catalyst achieves an exceptional HCHO production rate of 197.79 μmol·g<sub>cat</sub><sup>–1</sup> with >99.99% selectivity in water vapor, significantly outperforming both pristine FeOOH and MIL-125-NH<sub>2</sub> components. This work presents a promising photocatalytic system for selective CH<sub>4</sub> conversion, offering new insights into the design of efficient catalysts for C1 chemistry.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.4c05525
Dmitry Snetkov, Maksim Luginin, Tatiana Gerasimova, Aleksandra Paderina, Elena Grachova
Four bis-alkynyl Pt(II) complexes [Pt(dtbpy)(C2–L–P(O)Ph2)2] with dtbpy = 4,4′-ditertbutyl-2,2′-bipyridine and alkynylphosphine oxide ligands (L = no linker, Pt0; phenyl, Pt1; biphenyl, Pt2; naphthyl, Pt3) have been synthesized and fully characterized by spectroscopic methods and single crystal XRD analysis. It has been found that the nature of the π-conjugated linker is a key factor in fine-tuning the emission energy of the complexes in solution and in achieving the aggregation-induced phosphorescence enhancement (AIPE) effect for complex Pt0 with the most compact linker. Phosphine oxide fragment, which can be involved in weak intermolecular interactions, promotes the existence of two solid forms with different luminescence properties. These two forms can be switched from one to another upon grinding, thus featuring distinct mechanochromic luminescence properties. TDDFT calculations are consistent with the experimental results and assign mixed 3MLCT and 3LL′CT solution emission character and 3MMLCT and 3LL′CT emission nature in supramolecular dimeric structures.
{"title":"Bis-alkynylphosphine Oxide Pt(II) Complexes: Aggregation-Induced Phosphorescence Enhancement and Mechanochromic Luminescence Properties","authors":"Dmitry Snetkov, Maksim Luginin, Tatiana Gerasimova, Aleksandra Paderina, Elena Grachova","doi":"10.1021/acs.inorgchem.4c05525","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05525","url":null,"abstract":"Four bis-alkynyl Pt(II) complexes [Pt(dtbpy)(C<sub>2</sub>–L–P(O)Ph<sub>2</sub>)<sub>2</sub>] with <b>dtbpy</b> = 4,4′-ditertbutyl-2,2′-bipyridine and alkynylphosphine oxide ligands (L = no linker, <b>Pt0</b>; phenyl, <b>Pt1</b>; biphenyl, <b>Pt2</b>; naphthyl, <b>Pt3</b>) have been synthesized and fully characterized by spectroscopic methods and single crystal XRD analysis. It has been found that the nature of the π-conjugated linker is a key factor in fine-tuning the emission energy of the complexes in solution and in achieving the aggregation-induced phosphorescence enhancement (AIPE) effect for complex <b>Pt0</b> with the most compact linker. Phosphine oxide fragment, which can be involved in weak intermolecular interactions, promotes the existence of two solid forms with different luminescence properties. These two forms can be switched from one to another upon grinding, thus featuring distinct mechanochromic luminescence properties. TDDFT calculations are consistent with the experimental results and assign mixed <sup>3</sup>MLCT and <sup>3</sup>LL′CT solution emission character and <sup>3</sup>MMLCT and <sup>3</sup>LL′CT emission nature in supramolecular dimeric structures.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"26 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853795","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Trivalent metal cation engineering in vacancy-ordered layered double perovskites (LDP) is a useful strategy to tune photocatalytic activity. However, the regulatory mechanism of cation composition on photocatalytic performance still lacks in-depth understanding. This study explores vacancy-ordered LDP with the formula Cs4CdX2Cl12 (X = Bi, Sb) for photocatalytic CO2 reduction. The catalytic performance is fine-tuned by regulating the composition of M(III)-site metal ions. The yields of CO and CH4 from Cs4CdSb2Cl12 MCs were measured at 23.81 and 2.68 μmol g–1, resulting in a CO selectivity of 89.9%. Cs4CdBi2Cl12 demonstrated higher yields, with CO and CH4 produced at 90.77 and 2.53 μmol g–1, achieving a CO selectivity of 97.2%. In addition, in situ diffuse reflectance infrared Fourier transform spectra reveal that the modulation of metal ions at the M(III)-position can enhance the photocatalytic activity of Cs4CdX2Cl12 (X = Bi, Sb) MCs. Density functional theory (DFT) analysis suggests that Bi displays a lower energy barrier than Sb for the rate-determining step, thus facilitating the effective photocatalytic reduction of CO2 to CO. These findings highlight the influence of metal cation selection on structural properties and catalytic performance.
{"title":"Effect of Trivalent Metal Cations in Layered Double Perovskites on Highly Selective CO2 Photoreduction to CO","authors":"Wei Chen, Yanyi Huang, Daofu Wu, Hongmei Ran, Yichen Liu, Liqin Gao, Wenxia Zhang, Qiang Huang, Xiaosheng Tang","doi":"10.1021/acs.inorgchem.4c05292","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05292","url":null,"abstract":"Trivalent metal cation engineering in vacancy-ordered layered double perovskites (LDP) is a useful strategy to tune photocatalytic activity. However, the regulatory mechanism of cation composition on photocatalytic performance still lacks in-depth understanding. This study explores vacancy-ordered LDP with the formula Cs<sub>4</sub>CdX<sub>2</sub>Cl<sub>12</sub> (X = Bi, Sb) for photocatalytic CO<sub>2</sub> reduction. The catalytic performance is fine-tuned by regulating the composition of M<sup>(III)</sup>-site metal ions. The yields of CO and CH<sub>4</sub> from Cs<sub>4</sub>CdSb<sub>2</sub>Cl<sub>12</sub> MCs were measured at 23.81 and 2.68 μmol g<sup>–1</sup>, resulting in a CO selectivity of 89.9%. Cs<sub>4</sub>CdBi<sub>2</sub>Cl<sub>12</sub> demonstrated higher yields, with CO and CH<sub>4</sub> produced at 90.77 and 2.53 μmol g<sup>–1</sup>, achieving a CO selectivity of 97.2%. In addition, <i>in situ</i> diffuse reflectance infrared Fourier transform spectra reveal that the modulation of metal ions at the M<sup>(III)</sup>-position can enhance the photocatalytic activity of Cs<sub>4</sub>CdX<sub>2</sub>Cl<sub>12</sub> (X = Bi, Sb) MCs. Density functional theory (DFT) analysis suggests that Bi displays a lower energy barrier than Sb for the rate-determining step, thus facilitating the effective photocatalytic reduction of CO<sub>2</sub> to CO. These findings highlight the influence of metal cation selection on structural properties and catalytic performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"258 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853793","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.inorgchem.5c00525
Zhuo Wang, Yundi Huang, Bo Song, Yuanyuan Shi, Jingli Yuan
We proposed a strategy for developing a mitochondria-targeting lanthanide complex-based probe, Mito-ANMTTTA-Eu3+, designed for hypochlorous acid (HClO) detection using time-gated luminescence intensity and lifetime modes. The probe consists of a terpyridine polyacid-Eu3+ complex as the luminophore, a 4-amino-3-nitrophenyl group for HClO recognition, and a triphenylphosphonium (TPP) group as the mitochondrial-targeting moiety. The probe initially exists in a “dark state,” characterized by a relatively short luminescence lifetime. Upon reaction with HClO, the time-gated luminescence (TGL) intensity and the average luminescence lifetime of Mito-ANMTTTA-Eu3+ increased by approximately 20-fold and 15-fold, respectively. These features enable sensitive and accurate detection of HClO by utilizing TGL and luminescence lifetime as complementary detection strategies. Cell imaging studies revealed that the probe was predominantly localized in the mitochondria after coculture with live cells, and it could effectively image both endogenous and exogenous HClO in mitochondria under background-free TGL mode. Furthermore, the probe was effectively implemented for the imaging of HClO in zebrafish and the livers of drug-induced liver injury (DILI) mice, revealing a positive correlation between HClO levels and the degree of DILI. Consequently, this study paves a new way for designing lanthanide complex-based dual-made luminescent probes for biosensing and bioimaging.
{"title":"A Mitochondria-Targetable Europium(III) Complex-Based Probe for Time-Gated Luminescence and Lifetime Detection of Hypochlorous Acid In Vitro and In Vivo","authors":"Zhuo Wang, Yundi Huang, Bo Song, Yuanyuan Shi, Jingli Yuan","doi":"10.1021/acs.inorgchem.5c00525","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00525","url":null,"abstract":"We proposed a strategy for developing a mitochondria-targeting lanthanide complex-based probe, Mito-ANMTTTA-Eu<sup>3+</sup>, designed for hypochlorous acid (HClO) detection using time-gated luminescence intensity and lifetime modes. The probe consists of a terpyridine polyacid-Eu<sup>3+</sup> complex as the luminophore, a 4-amino-3-nitrophenyl group for HClO recognition, and a triphenylphosphonium (TPP) group as the mitochondrial-targeting moiety. The probe initially exists in a “dark state,” characterized by a relatively short luminescence lifetime. Upon reaction with HClO, the time-gated luminescence (TGL) intensity and the average luminescence lifetime of Mito-ANMTTTA-Eu<sup>3+</sup> increased by approximately 20-fold and 15-fold, respectively. These features enable sensitive and accurate detection of HClO by utilizing TGL and luminescence lifetime as complementary detection strategies. Cell imaging studies revealed that the probe was predominantly localized in the mitochondria after coculture with live cells, and it could effectively image both endogenous and exogenous HClO in mitochondria under background-free TGL mode. Furthermore, the probe was effectively implemented for the imaging of HClO in zebrafish and the livers of drug-induced liver injury (DILI) mice, revealing a positive correlation between HClO levels and the degree of DILI. Consequently, this study paves a new way for designing lanthanide complex-based dual-made luminescent probes for biosensing and bioimaging.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Homogeneous catalysts using a mononuclear molybdenum nitride (Mo≡N) complex bearing PCP-type pincer ligands allow nitrogen fixation under very mild conditions. The catalytic cycle involves three hydrogenation processes yielding an Mo-ammine complex [MoI(NH3)(PCP)] from the Mo-nitride complex [MoI(N)(PCP)]. We primarily focused on the first hydrogenation step, forming an Mo-imide complex [MoI(NH)(PCP)] since previous experimental and theoretical studies suggest that imide formation is the rate-limiting step in the catalytic cycle. The choice of protonating agent and reductant strongly influences the catalytic reactivity in imide formation. In this computational quantum chemical study, 2,4,6-collidinium (ColH+) was employed as the protonation agent, while metallocenes Cp2MII and decamethylmetallocenes Cp*2MII (M = V, Cr, Mn, Fe, Co, and Ni) were employed as reductants. The reaction of ColH+ with the metallocenes yields protonated metallocenes, where a cyclopentadienyl ring of the metallocenes is protonated. Protonated Cp*2CrII and Cp*2CoII are potential proton-coupled electron transfer (PCET) mediators to facilitate the imide formation of [MoI(N)(PCP)] with low activation free energies. The concerted reaction mechanism was compared with the stepwise reaction, where ColH+ directly protonates [MoI(N)(PCP)], followed by reduction with the decamethylmetallocenes. Furthermore, we analyzed how proton transfer and electron transfer are concerted in the reaction of the PCET mediators with [MoI(N)(PCP)] by tracing electronic states along the reaction coordinates.
{"title":"Theoretical Study of Imide Formation in Nitrogen Fixation Catalyzed by Molybdenum Complex Bearing PCP-Type Pincer Ligand with Metallocenes","authors":"Taiji Nakamura, Yusuke Tsuruta, Akihito Egi, Hiromasa Tanaka, Yoshiaki Nishibayashi, Kazunari Yoshizawa","doi":"10.1021/acs.inorgchem.5c00695","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00695","url":null,"abstract":"Homogeneous catalysts using a mononuclear molybdenum nitride (Mo≡N) complex bearing PCP-type pincer ligands allow nitrogen fixation under very mild conditions. The catalytic cycle involves three hydrogenation processes yielding an Mo-ammine complex [MoI(NH<sub>3</sub>)(PCP)] from the Mo-nitride complex [MoI(N)(PCP)]. We primarily focused on the first hydrogenation step, forming an Mo-imide complex [MoI(NH)(PCP)] since previous experimental and theoretical studies suggest that imide formation is the rate-limiting step in the catalytic cycle. The choice of protonating agent and reductant strongly influences the catalytic reactivity in imide formation. In this computational quantum chemical study, 2,4,6-collidinium (ColH<sup>+</sup>) was employed as the protonation agent, while metallocenes Cp<sub>2</sub>M<sup>II</sup> and decamethylmetallocenes Cp*<sub>2</sub>M<sup>II</sup> (M = V, Cr, Mn, Fe, Co, and Ni) were employed as reductants. The reaction of ColH<sup>+</sup> with the metallocenes yields protonated metallocenes, where a cyclopentadienyl ring of the metallocenes is protonated. Protonated Cp*<sub>2</sub>Cr<sup>II</sup> and Cp*<sub>2</sub>Co<sup>II</sup> are potential proton-coupled electron transfer (PCET) mediators to facilitate the imide formation of [MoI(N)(PCP)] with low activation free energies. The concerted reaction mechanism was compared with the stepwise reaction, where ColH<sup>+</sup> directly protonates [MoI(N)(PCP)], followed by reduction with the decamethylmetallocenes. Furthermore, we analyzed how proton transfer and electron transfer are concerted in the reaction of the PCET mediators with [MoI(N)(PCP)] by tracing electronic states along the reaction coordinates.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photocatalytic conversion of CO2 into chemical fuels has emerged as a research hotspot, aiming to mitigate the rapid depletion of fossil fuels and alleviate global warming. However, the inherent low carrier separation efficiency and limited solar light utilization of photocatalysts lead to unsatisfactory CO2 conversion efficiency. In this study, an appealing CuCo2S4/g-C3N4–x S-scheme heterostructure is successfully fabricated by a simple polyol reflux method. Notably, nitrogen vacancies enhance the Fermi level difference between CuCo2S4 and g-C3N4–x, resulting in a stronger interfacial built-in electric field. The full-spectrum strong optical absorption capability endows the synthesized catalysts with superior light-harvesting property. The photothermal effect-induced temperature increase accelerates the cyclic process of CO2 adsorption and CO desorption on the catalyst surface. Most importantly, the S-scheme charge transfer pathway ensures the efficient separation of photogenerated carriers. Thanks to these synergistic benefits, CuCo2S4/g-C3N4–x exhibits exceptional photothermal-assisted photocatalytic CO2 reduction performance. Under simulated sunlight, the average CO production rate of CuCo2S4/g-C3N4–x reaches 24.64 μmol g–1 h–1, which is 12.1 and 27.1 times higher than that of g-C3N4 and CuCo2S4, respectively. This study offers a novel strategy for designing photocatalysts with outstanding CO2 conversion performance.
光催化将二氧化碳转化为化学燃料已成为研究热点，其目的是缓解化石燃料的快速枯竭和全球变暖问题。然而，光催化剂固有的低载流子分离效率和有限的太阳光利用率导致二氧化碳转化效率不尽人意。本研究采用简单的多元醇回流法成功制备了一种极具吸引力的 CuCo2S4/g-C3N4-x S 型异质结构。值得注意的是，氮空位增强了 CuCo2S4 和 g-C3N4-x 之间的费米级差，从而产生了更强的界面内置电场。全谱强光吸收能力赋予了合成催化剂卓越的光收集特性。光热效应引起的温度升高加速了催化剂表面 CO2 吸附和 CO 解吸的循环过程。最重要的是，S 型电荷转移途径确保了光生载流子的有效分离。得益于这些协同优势，CuCo2S4/g-C3N4-x 表现出卓越的光热辅助光催化二氧化碳还原性能。在模拟阳光下，CuCo2S4/g-C3N4-x 的平均 CO 生成率达到 24.64 μmol g-1 h-1，分别是 g-C3N4 和 CuCo2S4 的 12.1 倍和 27.1 倍。这项研究为设计具有优异二氧化碳转化性能的光催化剂提供了一种新的策略。
{"title":"CuCo2S4/g-C3N4–x S-Scheme Heterojunction for Photothermal-Assisted Photocatalytic CO2 Reduction","authors":"Fangde Liu, Yanjie Song, Renzhi Xiong, Dongchen Duan, Xiao Xiao, Yanhe Xiao, Baochang Cheng, Shuijin Lei","doi":"10.1021/acs.inorgchem.5c00779","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00779","url":null,"abstract":"Photocatalytic conversion of CO<sub>2</sub> into chemical fuels has emerged as a research hotspot, aiming to mitigate the rapid depletion of fossil fuels and alleviate global warming. However, the inherent low carrier separation efficiency and limited solar light utilization of photocatalysts lead to unsatisfactory CO<sub>2</sub> conversion efficiency. In this study, an appealing CuCo<sub>2</sub>S<sub>4</sub>/g-C<sub>3</sub>N<sub>4–<i>x</i></sub> S-scheme heterostructure is successfully fabricated by a simple polyol reflux method. Notably, nitrogen vacancies enhance the Fermi level difference between CuCo<sub>2</sub>S<sub>4</sub> and g-C<sub>3</sub>N<sub>4–<i>x</i></sub>, resulting in a stronger interfacial built-in electric field. The full-spectrum strong optical absorption capability endows the synthesized catalysts with superior light-harvesting property. The photothermal effect-induced temperature increase accelerates the cyclic process of CO<sub>2</sub> adsorption and CO desorption on the catalyst surface. Most importantly, the S-scheme charge transfer pathway ensures the efficient separation of photogenerated carriers. Thanks to these synergistic benefits, CuCo<sub>2</sub>S<sub>4</sub>/g-C<sub>3</sub>N<sub>4–<i>x</i></sub> exhibits exceptional photothermal-assisted photocatalytic CO<sub>2</sub> reduction performance. Under simulated sunlight, the average CO production rate of CuCo<sub>2</sub>S<sub>4</sub>/g-C<sub>3</sub>N<sub>4–<i>x</i></sub> reaches 24.64 μmol g<sup>–1</sup> h<sup>–1</sup>, which is 12.1 and 27.1 times higher than that of g-C<sub>3</sub>N<sub>4</sub> and CuCo<sub>2</sub>S<sub>4</sub>, respectively. This study offers a novel strategy for designing photocatalysts with outstanding CO<sub>2</sub> conversion performance.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853816","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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