Inorganic Chemistry最新文献

{"title":"Thermal Jahn-Teller Distortion Changes and Slow Relaxation of Magnetization in Mn(III) Schiff Base Complexes.","authors":"Chantalaksana Chantarangkul, Apinya Patigo, John C McMurtrie, Rodolphe Clérac, Mathieu Rouzières, Silvia Gómez-Coca, Eliseo Ruiz, Phimphaka Harding, David J Harding","doi":"10.1021/acs.inorgchem.4c01317","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01317","url":null,"abstract":"<p><p>The impact that the anion and alkyl group has on the electronic structures and magnetic properties of four mononuclear Mn(III) complexes is explored in [Mn(salEen-Br)₂]Y (salEen-Br = 2-{[2-(ethylamino)ethylimino]methyl}-4-Br-phenol; Y = ClO₄^- <b>1</b> and BF₄^-·1/3CH₂Cl₂ <b>2</b>) and [Mn(salBzen-Br)₂]Y (salBzen-Br = 2-{[2-(benzylamino)ethylimino]methyl}-4-Br-phenol; Y = ClO₄^- <b>3</b> and BF₄^- <b>4</b>). X-ray structures of [Mn(salEen-Br)₂]ClO₄·0.45C₆H₁₄ <b>1-hexane</b>, [Mn(salEen-Br)₂]BF₄·0.33CH₂Cl₂·0.15C₆H₁₄ <b>2-dcm-hexane</b>, and <b>3</b>-<b>4</b> reveal that they crystallize in ambient conditions in the monoclinic <i>P</i>2₁/<i>c</i> space group. Lowering the temperature, <b>2-dcm-hexane</b> uniquely exhibits a structural phase transition toward a monoclinic <i>P</i>2₁/<i>n</i> crystal structure determined at 100 K with the unit cell trebling in size. Remarkably, at room temperature, the axially elongated Jahn-Teller axis in <b>2-dcm-hexane</b> is poorly defined but becomes clearer at low temperature after the phase transition. Magnetic susceptibility measurements of <b>1</b>-<b>4</b> reveal that only <b>3</b> and <b>4</b> show slow relaxation of magnetization with Δ_eff/<i>k</i>_B = 27.9 and 20.7 K, implying that the benzyl group is important for observing single-molecule magnet (SMM) properties. Theoretical calculations demonstrate that the alkyl group subtly influences the orbital levels and therefore very likely the observed SMM properties.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453726","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}

{"title":"pH-Driven Rotational Configuration of Keggin-Fe13 Clusters and Their Transformations","authors":"Man-Ting Chen, Qiao-Fei Xu, La-Sheng Long, Lan-Sun Zheng","doi":"10.1021/acs.inorgchem.4c01369","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01369","url":null,"abstract":"Keggin-Fe₁₃ clusters are considered foundational building blocks or prenucleation precursors of ferrihydrite. Understanding the factors that influence the rotational configuration of these clusters, and their transformations in water, is vital for comprehending the formation mechanism of ferrihydrite. Here, we report syntheses and crystal structures of four lanthanide-iron-oxo clusters, namely, [Dy₆Fe₁₃(Gly)₁₂(μ₂–OH)₆(μ₃–OH)₁₈(μ₄–O)₄(H₂O)₁₇]·13ClO₄·19H₂O (<b>1</b>), [Dy₆Fe₁₃(Gly)₁₂(μ₃–OH)₂₄(μ₄–O)₄(H₂O)₁₈]·13ClO₄·14H₂O (<b>2</b>), [Pr₈Fe₃₄(Gly)₂₄(μ₃–OH)₂₈(μ₃–O)₃₀(μ₄–O)₄(H₂O)₃₀]·6ClO₄·20H₂O (<b>3</b>), and [Pr₆Fe₁₃(Gly)₁₂(μ₃–OH)₂₄(μ₄–O)₄(H₂O)₁₈]·13ClO₄·22H₂O (<b>4</b>, Gly = glycine). Single-crystal analyses reveal that <b>1</b> has a β-Keggin-Fe₁₃ cluster, marking the first documented instance of such a cluster to date. Conversely, both <b>2</b> and <b>4</b> contain an α-Keggin-Fe₁₃ cluster, while <b>3</b> is characterized by four hexavacant ε-Keggin-Fe₁₃ clusters. Magnetic property investigations of <b>1</b> and <b>2</b> show that <b>2</b> exhibits ferromagnetic interactions, while <b>1</b> exhibits antiferromagnetic interactions. An exploration of the synthetic conditions for <b>1</b> and <b>2</b> indicates that a higher pH promotes the formation of α-Keggin-Fe₁₃ clusters, while a lower pH favors β-Keggin-Fe₁₃ clusters. A detailed analysis of the transition from <b>3</b> to <b>4</b> emphasizes that lacunary Keggin-Fe₁₃ clusters can morph into Keggin-Fe₁₃ clusters with a decrease in pH, accompanied by a significant change in their rotational configuration.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462084","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}

{"title":"Photochromic Ln-MOFs: A Platform for Metal-Photoswitch Cooperativity.","authors":"Corey R Martin, Grace C Thaggard, Ingrid Lehman-Andino, Eduardo Mollinedo, Binod K Rai, Matthew A Page, Kathryn Taylor-Pashow, Natalia B Shustova","doi":"10.1021/acs.inorgchem.4c01283","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01283","url":null,"abstract":"<p><p>Optoelectronic devices based on lanthanide-containing materials are an emergent area of research due to imminent interest in a new generation of diode materials, optical and magnetic sensors, and ratiometric thermometers. Tailoring material properties through the employment of photo- or thermochromic moieties is a powerful approach that requires a deep fundamental understanding of possible cooperativity between lanthanide-based metal centers and integrated switchable units. In this work, we probe this concept through the synthesis, structural analysis, and spectroscopic characterization of novel photochromic lanthanide-based metal-organic materials containing noncoordinatively integrated photoresponsive 4,4'-azopyridine between lanthanide-based metal centers. As a result, a photophysical material response tailored on demand through the incorporation of photochromic compounds within a rigid matrix was investigated. The comprehensive analysis of photoresponsive metal-organic materials includes single-crystal X-ray diffraction and diffuse reflectance spectroscopic studies that provide guiding principles necessary for understanding photochromic unit-lanthanide-based metal-organic framework (MOF) cooperativity. Furthermore, steady-state and time-resolved diffuse reflectance spectroscopic studies revealed a rapid rate of photoresponsive moiety attenuation upon its integration within the rigid matrix of lanthanide-based MOFs in comparison with that in solution, highlighting a unique role and synergy that occurred between stimuli-responsive moieties and the lanthanide-based MOF platform, allowing for tunability and control of material photoisomerization kinetics.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453725","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}

{"title":"Using Iron L-Edge and Nitrogen K-Edge X-ray Absorption Spectroscopy to Improve the Understanding of the Electronic Structure of Iron Carbene Complexes.","authors":"Meiyuan Guo, Robert Temperton, Giulio D'Acunto, Niclas Johansson, Rosemary Jones, Karsten Handrup, Sven Ringelband, Om Prakash, Hao Fan, Lisa H M de Groot, Valtýr Freyr Hlynsson, Simon Kaufhold, Olga Gordivska, Nicolás Velásquez González, Kenneth Wärnmark, Joachim Schnadt, Petter Persson, Jens Uhlig","doi":"10.1021/acs.inorgchem.4c01026","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01026","url":null,"abstract":"<p><p>Iron-centered N-heterocyclic carbene compounds have attracted much attention in recent years due to their long-lived excited states with charge transfer (CT) character. Understanding the orbital interactions between the metal and ligand orbitals is of great importance for the rational tuning of the transition metal compound properties, e.g., for future photovoltaic and photocatalytic applications. Here, we investigate a series of iron-centered N-heterocyclic carbene complexes with +2, + 3, and +4 oxidation states of the central iron ion using iron L-edge and nitrogen K-edge X-ray absorption spectroscopy (XAS). The experimental Fe L-edge XAS data were simulated and interpreted through restricted-active space (RAS) and multiplet calculations. The experimental N K-edge XAS is simulated and compared with time-dependent density functional theory (TDDFT) calculations. Through the combination of the complementary Fe L-edge and N K-edge XAS, direct probing of the complex interplay of the metal and ligand character orbitals was possible. The σ-donating and π-accepting capabilities of different ligands are compared, evaluated, and discussed. The results show how X-ray spectroscopy, together with advanced modeling, can be a powerful tool for understanding the complex interplay of metal and ligand.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453727","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}

{"title":"Ir(I)-Bi(III) Donor-Acceptor Adducts Stabilized by Dispersion Interactions between the Metal Pincer Ligands and Their Possible Self-Assembly Forming Molecular 1D Semiconductors.","authors":"Zdeněk Chval","doi":"10.1021/acs.inorgchem.4c00364","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c00364","url":null,"abstract":"<p><p>Structure, stability, and electronic properties of the bimetallic {[Ir^I(terpy)(Me)]-[Bi^IIINNN]}_<i>n</i> monomeric, oligomeric, and polymeric structures (<i>n</i> = 1-3 and ∞; terpy = terpyridine; Me = methyl; BiNNN = bismuth triamide) and their derivatives (designated as (Bi·Ir)_<i>n</i> structures) were studied theoretically by DFT cluster and periodic calculations. Stable Bi·Ir adducts (monomers) were formed with short Bi-Ir bonds (<2.7 Å) and Gibbs free binding energies larger than 20 kcal/mol for all systems. The substitution of the pincer ligands of Ir(I) and Bi(III) complexes by the electron-donating (NH₂) and electron-withdrawing (NO₂, F, CF₃) groups, respectively, enhanced the Ir → Bi charge transfer, substantially stabilizing the Bi·Ir monomers. The monomers from the unsubstituted complexes can be considered as dispersion stabilized adducts, and they may form spontaneously (Bi·Ir)_<i>n</i> layered oligomers/polymers with semiconducting properties. The self-assembly of monomers into oligomers/polymers is hindered by bulkier protecting groups on the Bi(III) complex, such as tBu and SiMe₃.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453723","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}

{"title":"Open Active Sites in Ni-Based MOF with High Oxidation States for Electrooxidation of Benzyl Alcohol.","authors":"Wenli Su, Xingzi Zheng, Wei Xiong, Ying Ouyang, Zhe Zhang, Weijie Zeng, Haotian Duan, Xingyu Chen, Peiyuan Su, Zemin Sun, Mengwei Yuan","doi":"10.1021/acs.inorgchem.4c01507","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01507","url":null,"abstract":"<p><p>The kinetics of electrocatalytic reactions are closely related to the number and intrinsic activity of the active sites. Open active sites offer easy access to the substrate and allow for efficient desorption and diffusion of reaction products without significant hindrance. Metal-organic frameworks (MOFs) with open active sites show great potential in this context. To increase the density of active sites, trimesic acid was utilized as a ligand to anchor more Ni sites and in situ construct the nickel foam-loaded Ni-based trimesic MOF electrocatalyst (Ni-TMA-MOF/NF). When tested as an electrocatalyst for benzyl alcohol oxidation, Ni-TMA-MOF/NF exhibited lower overpotential and superior durability compared to Ni foam-loaded Ni-based terephthalic MOF electrocatalyst (Ni-PTA-MOF/NF) and Ni(OH)₂ nanosheet array (Ni(OH)₂/NF). Ni-TMA-MOF/NF required only a low potential of 1.65 V to achieve a high current density of 400 mA cm^-2. Even after 40000 s of electrocatalytic oxidation at 1.5 V, Ni-TMA-MOF/NF maintained a current density of 175 mA cm^-2 with ∼68% retention, showing its potential for benzyl alcohol oxidation. Through a combination of experimental and theoretical investigations, it was found that Ni-TMA-MOF/NF displayed superior electrocatalytic activity due to an optimized electron structure with high-valence Ni species and a high density of active sites, enabling long-term stable operation at high current densities. This study provides a new perspective on the design of electrocatalysts for benzyl alcohol oxidation.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453724","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}

{"title":"Attaching Metal-Containing Moieties to β-Lactam Antibiotics: The Case of Penicillin and Cephalosporin.","authors":"María Moreno-Latorre, María C de la Torre, Javier A Cabeza, Pablo García-Álvarez, Miguel A Sierra","doi":"10.1021/acs.inorgchem.4c01548","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01548","url":null,"abstract":"<p><p>Procedures for the preparation of transition metal complexes having intact bicyclic cepham or penam systems as ligands have been developed. Starting from readily available 4-azido-2-azetidinones, a synthetic approach has been tuned using a copper-catalyzed azide-alkyne cycloaddition between 3-azido-2-azetinones and alkynes, followed by methylation and transmetalation to Au(I) and Ir(III) complexes from the mesoionic carbene Ag(I) complexes. This methodology was applied to 6-azido penam and 7-azido cepham derivatives to build 6-(1,2,3-triazolyl)penam and 7-(1,2,3-triazolyl)cepham proligands, which upon methylation and metalation with Au(I) and Ir(III) complexes yielded products derived from the coordination of the metal to the penam C⁶ and cepham C⁷ positions, preserving intact the bicyclic structure of the penicillin and cephalosporin scaffolds. The crystal structure of complex <b>28b</b>, which has an Ir atom directly bonded to the intact penicillin bicycle, was determined by X-ray diffraction. This is the first structural report of a penicillin-transition-metal complex having the bicyclic system of these antibiotics intact. The selectivity of the coordination processes was interpreted using DFT calculations.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453660","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}

{"title":"Preparing Coordination Polymers with Acentric-Centric Structural Arrangements Related to SHG Response.","authors":"Lian Zhou, Yanfeng Cui, Han Zhao, QingHong Zhang, Qingchen Fan, Xiaomin He, Qi Wu, Jun Zhang","doi":"10.1021/acs.inorgchem.4c01927","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01927","url":null,"abstract":"<p><p>Three coordination polymers were successfully constructed in this work by applying biligands and were distinctly characterized through single crystal X-ray diffraction. The compounds crystallized in acentric and centric space groups under the direction of coordination bonds and adopted 1-dimensional link and 2-dimensional layer structures, as well as different coordination geometries for metal atoms. All compounds exhibited good thermal stability and luminescence properties, and compound <b>2</b> exhibited a good second harmonic generation (SHG) response. The method used in this work offers a feasible approach to using biligand and changing metal salt to obtain the microstructures of coordination materials with specific properties.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448960","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}

{"title":"Correction to \"Coordination Sphere of Lanthanide Aqua Ions Resolved with Ab Initio Molecular Dynamics and X-ray Absorption Spectroscopy\".","authors":"Richard C Shiery, John L Fulton, Mahalingam Balasubramanian, Manh-Thuong Nguyen, Jun-Bo Lu, Jun Li, Roger Rousseau, Vassiliki-Alexandra Glezakou, David C Cantu","doi":"10.1021/acs.inorgchem.4c02511","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c02511","url":null,"abstract":"","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141449007","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}

{"title":"Polyoxometalate Functionalized Cyclic Trinuclear Copper Compounds for Bifunctional Electrochemical Detection and Photocatalytic Reduction of Cr(VI).","authors":"Lin Yang, Zhou Yuan, Lufang He, Le Han, Bohan Li, Yan Xu","doi":"10.1021/acs.inorgchem.4c01508","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c01508","url":null,"abstract":"<p><p>The design and intentional construction of crystalline materials containing two clusters with redox properties in one framework still remains challenging. Linking oxidative polyoxometalate (POM) clusters and a reductive cyclic trinuclear copper complex (Cu-CTC) to prepare stable catalysts is rarely reported. Herein, we successfully obtained two new polyoxometalate-based metal-organic compounds (POMOCs) [Cu^II₃(PyCA)₃(μ₃-OH)(β-Mo₈O₂₆)_0.5(H₂O)₂]·5H₂O (<b>1</b>), [Cu^II₃(PyCA)₃(μ₃-OH)]₂(Cu^IIW₁₂O₄₀)[Cu^II(H₂O)₆] (<b>2</b>) (PyCA = 1H-pyrazole-4-carbaldehyde) by enabling precursors of Cu-CTC and POM cocrystallization in one pot via hydrothermal method. The [β-Mo₈O₂₆]^4- cluster in compound <b>1</b> combined with Cu-CTC units to form a 1D structure, and the [CuW₁₂O₄₀]^6- unit in compound <b>2</b> linked two Cu-CTC units to form a sandwich-like 0D structure. Also, Cu-CTC Cu^I₃(PyCA)₃·H₂O (<b>Cu3</b>) was synthesized for performance comparison. A series of characterizations indicate that compound <b>1</b> is more conducive to electron transfer than compound <b>2</b>. In addition, compounds <b>1</b> and <b>2</b> can act as bifunctional catalysts for the electrochemical detection and photocatalytic reduction of Cr(VI). Particularly, the photoreduction rates of Cr(VI) by compounds <b>1</b> and <b>2</b> are 96.7% and 96.3% for only 10 and 14 min under visible light, respectively, and it is better than that of <b>Cu3</b> and most other reported photocatalysts. Furthermore, the active sites and mechanisms for electrochemical detection and photocatalytic reduction of Cr(VI) were discussed.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448959","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}