Inorganic Chemistry最新文献_第6页

Second Harmonic Generation in β-K2TeW3O12: An Acentric Crystal Designed from Centric Phase via Pressure Modulation β-K2TeW3O12中的二次谐波生成：通过压力调制从中心相位设计的同心晶体

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-28 DOI: 10.1021/acs.inorgchem.4c01427

Min Chen, Zhengli Liang, Yi Shui, Bingxuan Li, Xingxing Jiang, Zheshuai Lin, Hongming Liu

The latent value of nonlinear optical (NLO) crystals applied in solid-state laser equipment necessitates the development of applicable strategies for constructing noncentrosymmetric (NCS) crystals. By modulating the synthetic temperature and pressure to achieve the rearrangement of [TeO₃]^2– groups, a new NCS tellurium tungstate, β-K₂TeW₃O₁₂ (β-KTW), with a strong second harmonic generation (SHG) response was synthesized based on its centrosymmetric polymorphic phase α-K₂TeW₃O₁₂ (α-KTW). Computational calculation reveals that the large SHG response of β-KTW (15 × KH₂PO₄@1064 and 1.5 × KTiOPO₄@1950 nm) could be attributed to the uniform arrangement of the NLO-active [TeO₃]^2– and [WO₆]^6– groups. β-KTW also exhibits enlarged birefringence (0.196@1064 nm) and a high laser damage threshold (42.3 MW cm^–2), showing great potential as a nonlinear crystalline material. This work also provides a new route for the construction of NLO crystals based on centric structure, i.e., reverse pressure regulation.

由于非线性光学（NLO）晶体在固态激光设备中的应用具有潜在价值，因此有必要开发适用于构建非中心对称（NCS）晶体的策略。通过调节合成温度和压力实现[TeO3]2-基团的重排，在其中心对称多晶相α-K2TeW3O12 (α-KTW)的基础上合成了具有强二次谐波发生（SHG）响应的新型非对称碲钨酸盐β-K2TeW3O12 (β-KTW)。计算显示，β-KTW（15 × KH2PO4@1064 和 1.5 × KTiOPO4@1950 nm）的巨大 SHG 响应可归因于 NLO 活性[TeO3]2- 和[WO6]6- 基团的均匀排列。β-KTW 还表现出更大的双折射（0.196@1064 nm）和更高的激光损伤阈值（42.3 MW cm-2），显示出作为非线性晶体材料的巨大潜力。这项工作还为基于中心结构（即反向压力调节）构建 NLO 晶体提供了一条新途径。

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引用次数: 0

Weak Exchange Interactions in Multispin Systems: EPR Studies of Metalloporphyrins Decorated with {Cr7Ni} Rings 多卟啉体系中的弱交换相互作用：用 {Cr7Ni} 环装饰的金属卟啉的 EPR 研究环

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-28 DOI: 10.1021/acs.inorgchem.4c01248

Fabio Santanni, Edmund Little, Selena J. Lockyer, George F. S. Whitehead, Eric J. L. McInnes, Grigore A. Timco, Alice M. Bowen, Roberta Sessoli, Richard E. P. Winpenny

Both metalloporphyrins and heterometallic {Cr₇Ni} rings are of significant research interest due to their proposed roles in quantum information processing devices. In this study, we present a series of complexes in which [Cr₇NiF₃(Etglu)(O₂C^tBu)₁₅] (N-EtgluH₅ = N-ethyl-d-glucamine) heterometallic rings are coordinated to metalloporphyrin linkers: the symmetric [M(TPyP)] for M = Cu²⁺, VO²⁺, and H₂TPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin; and the asymmetric [{VO}(TrPPyP)] for H₂(TrPPyP) = 5,10,15-(triphenyl)-20-(4-pyridyl)porphyrin. The magnetic interactions present in these complexes are unraveled using the continuous wave (CW) electron paramagnetic resonance (EPR) technique. The nature of the coupling between the {Cr₇Ni} rings and the central metalloporphyrin is assessed by numerical simulations of CW EPR spectra and determined to be on the order of 0.01 cm^–1, larger than the dipolar ones and suitable for individual spin addressability in multiqubit architectures.

金属卟啉和杂金属{Cr7Ni}环因其在量子信息处理设备中的作用而备受研究关注。在本研究中，我们提出了一系列[Cr7NiF3(Etglu)(O2CtBu)15]（N-EtgluH5 = N-乙基-d-葡萄糖胺）杂金属环与金属卟啉连接体配位的配合物：M = Cu2+、VO2+ 和 H2TPyP = 5,10,15,20-四（4-吡啶基）卟啉的对称[M(TPyP)]；以及 H2(TrPPyP) = 5,10,15-（三苯基）-20-（4-吡啶基）卟啉的不对称[{VO}(TrPPyP)]。利用连续波（CW）电子顺磁共振（EPR）技术揭示了这些复合物中存在的磁性相互作用。通过对连续波电子顺磁共振光谱进行数值模拟，评估了{Cr7Ni}环和中心金属卟啉之间耦合的性质，并确定其耦合度为 0.01 cm-1，大于偶极耦合度，适用于多量子位架构中的单个自旋寻址。

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引用次数: 0

An NIR Type I Photosensitizer Based on a Cyclometalated Ir(III)-Rhodamine Complex for a Photodynamic Antibacterial Effect toward Both Gram-Positive and Gram-Negative Bacteria 一种基于环甲基化 Ir(III)-Rhodamine 复合物的近红外 I 型光敏剂，可对革兰氏阳性和革兰氏阴性细菌产生光动力抗菌效果

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01914

Chuangjun Liu, Qihang Ding, Youju Liu, Zepeng Wang, Yinling Xu, Qiang Lu, Xinyu Chen, Junhang Liu, Yuanyuan Sun, Rongqiang Li, Yang Yang, Yao Sun, Siqiang Li, Pengfei Wang, Jong Seung Kim

Type I photosensitizers offer an advantage in photodynamic therapy (PDT) due to their diminished reliance on oxygen levels, thus circumventing the challenge of hypoxia commonly encountered in PDT. In this study, we present the synthesis and comprehensive characterization of a novel type I photosensitizer derived from a cyclometalated Ir(III)-rhodamine complex. Remarkably, the complex exhibits a shift in absorption and fluorescence, transitioning from “off” to “on” states in aprotic and protic solvents, respectively, contrary to initial expectations. Upon exposure to light, the complex demonstrates the effective generation of O₂^– and ·OH radicals via the type I mechanism. Additionally, it exhibits notable photodynamic antibacterial activity against both Gram-positive and Gram-negative bacteria, demonstrated through in vitro and in vivo experiments. This research offers valuable insights for the development of novel type I photosensitizers.

I 型光敏剂在光动力疗法（PDT）中具有优势，因为它们对氧气水平的依赖性较低，从而规避了光动力疗法中常见的缺氧挑战。在这项研究中，我们合成并全面表征了一种新型 I 型光敏剂，它来自环甲基化的 Ir(III)-rhodamine 复合物。值得注意的是，该复合物的吸收和荧光发生了转变，在非质子和质子溶剂中分别从 "关 "态过渡到 "开 "态，这与最初的预期相反。在光照下，该复合物通过 I 型机制有效地生成了 O2- 和 -OH 自由基。此外，通过体外和体内实验，它还对革兰氏阳性和革兰氏阴性细菌表现出显著的光动力抗菌活性。这项研究为开发新型 I 型光敏剂提供了宝贵的启示。

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引用次数: 0

Twisted and Disconnected Chains: Flexible Linear Tetracuprous Arrays and a Decanuclear CuI Cluster as Blue- and Green/Yellow-Light Emitters 扭曲和断开的链条：灵活的线性四核阵列和十核 CuI 簇作为蓝光和绿/黄光发射器

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01646

Janet Arras, Alvaro Calderón-Díaz, Sergei Lebedkin, Samer Gozem, Colin D. McMillen, Nattamai Bhuvanesh, Michael Stollenz

Defined arrays of transition metal ions embedded in tailored polydentate ligand scaffolds allow for a systematic design of their physical properties. Such molecular strings of closed-shell transition metal centers are particularly interesting for Group 11 metal ions in the oxidation state +1 if they undergo metallophilic d¹⁰···d¹⁰ contact interactions since these clusters are oftentimes efficient photoluminescence (PL) emitters. Copper is particularly attractive as a sustainable earth-abundant coinage metal source and because of the ability of several Cu^I complexes to serve as powerful thermally activated delayed fluorescence (TADF) emitters in molecular/organic light-emitting devices (OLEDs). Our combined synthetic, crystallographic, photophysical, and computational study describes a straight tetracuprous array possessing a centrally disconnected Cu^I₂···Cu^I₂ chain and a continuous helically bent Cu^I₄ complex. This molecular helix undergoes a facile rearrangement in diethyl ether solution, yielding an unprecedented nanosized Cu^I₁₀ cluster (2.9 × 2.0 nm) upon crystallization. All three clusters show either bright blue phosphorescence, TADF, or green/yellow multiband phosphorescence with quantum yields between 6.5 and 67%, which is persistent under hydrostatic pressure up to 30 kbar. Temperature-dependent PL investigations in combination with time-dependent density-functional theory (TD-DFT) calculations and void space analyses of the crystal packings complement a comprehensive correlation between the molecular structures and photoluminescence properties.

嵌入定制的多齿配体支架中的过渡金属离子的定义阵列可以对其物理性质进行系统设计。对于氧化态+1的第11族金属离子（如果它们发生亲金属的d10--d10接触相互作用）来说，这种闭壳过渡金属中心的分子串特别有趣，因为这些簇通常是高效的光致发光（PL）发光体。铜作为一种可持续的地球富集金属源特别具有吸引力，因为几种 CuI 复合物能够在分子/有机发光器件（OLED）中用作强大的热激活延迟荧光（TADF）发射器。我们的综合合成、晶体学、光物理和计算研究描述了一种直四面体阵列，它拥有一个中心断开的 CuI2-CuI2 链和一个连续螺旋弯曲的 CuI4 复合物。这种分子螺旋在二乙醚溶液中发生了简单的重排，结晶后产生了前所未有的纳米级 CuI10 簇（2.9 × 2.0 nm）。所有三个簇都显示出明亮的蓝色磷光、TADF 或绿色/黄色多波段磷光，量子产率介于 6.5% 和 67% 之间，在高达 30 千巴的静水压力下持续存在。与温度相关的磷光研究结合了与时间相关的密度泛函理论（TD-DFT）计算和晶体堆积的空隙分析，补充了分子结构与光致发光特性之间的全面关联。

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引用次数: 0

Mechanical, Thermal Properties, and Extreme Phase Stability of High-Entropy Diborides (V0.2Nb0.2Ta0.2Cr0.2W0.2)B2 高熵二硼化物（V0.2Nb0.2Ta0.2Cr0.2W0.2）B2 的力学、热学特性和极端相稳定性

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c00016

Haidong Long, Shixue Guan, Zhengang Zhang, Yipeng Wang, Wenjia Liang, Jie Chen, Ruike Zhang, Peihong He, Ling Ran, Peng Yang, Fang Peng

High-entropy diborides (HEDBs) have gained significant attention in industrial applications due to their vast composition space and tunable properties. We propose a solid solution reaction at high temperatures and pressures that successfully synthesized and sintered a novel, dense, and phase-pure HEDB (V_0.2Nb_0.2Ta_0.2Cr_0.2W_0.2)B₂. A high asymptotic Vickers hardness of 26.3 ± 0.6 GPa and a bulk modulus of 320.5 ± 10.6 GPa were obtained. Additionally, we investigated the thermal oxidation process using TG-DSC from room temperature to 1500 °C and explored the phase stability of HEDBs under high-pressure conditions through in situ high-pressure synchrotron radiation X-ray diffraction. We analyzed the formation of lattice distortion, chemical bonding, and band structure in (V_0.2Nb_0.2Ta_0.2Cr_0.2W_0.2)B₂ using first-principles calculations. Surprisingly, we found that the predominant distortion in diborides occurs in the boron layer, supported by ELF. This may be due to uneven electron transfer rather than a straightforward correlation with the atomic radius. These results provide a novel synthesis process and additional experimental data on the mechanical and thermal properties and high-pressure phase stability of HEDBs. Our study offers further insights into the microscopic structure of lattice distortion in HEDBs, which could prove crucial for the selection and design of engineering advanced HEDBs.

高熵二硼化物（HEDBs）因其广阔的组成空间和可调整的特性而在工业应用中备受关注。我们提出了一种高温高压下的固溶反应，成功合成并烧结了一种新型、致密、相纯的 HEDB (V0.2Nb0.2Ta0.2Cr0.2W0.2)B2。该材料的渐近维氏硬度为 26.3 ± 0.6 GPa，体积模量为 320.5 ± 10.6 GPa。此外，我们还利用 TG-DSC 研究了从室温到 1500 ℃ 的热氧化过程，并通过原位高压同步辐射 X 射线衍射探索了 HEDB 在高压条件下的相稳定性。我们利用第一原理计算分析了（V0.2Nb0.2Ta0.2Cr0.2W0.2）B2 中晶格畸变的形成、化学键和能带结构。令人惊讶的是，我们发现二硼化物的主要畸变发生在硼层，并得到了 ELF 的支持。这可能是由于电子转移不均匀造成的，而不是与原子半径直接相关。这些结果提供了一种新的合成工艺，以及有关 HEDBs 的机械和热性能以及高压相稳定性的更多实验数据。我们的研究进一步揭示了 HEDB 中晶格畸变的微观结构，这对工程先进 HEDB 的选择和设计至关重要。

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引用次数: 0

Asymmetrically Coordinated Calcium Single Atom for High-Performance Oxygen Reduction Reaction 用于高性能氧还原反应的不对称配位钙单原子

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c02178

Yan Yang, Gang Wang, Changwei Liu, Yutao Lin, Chi Jiao, Qingqing Chen, Zhiwen Zhuo, Junjie Mao, Yan Liu

S-block single atoms represent an ideal catalyst for the oxygen reduction reaction (ORR) as they can suppress the Fenton reaction. However, the symmetry of the s/p orbitals tends to generate either an excessively strong or weak interaction with intermediates. Herein, Ca single atoms coordinated with -S, -OP, and three N atoms (Ca/NPS-HC) were fabricated to modulate the adsorption of intermediates and promote the efficiency of s-block ORR catalysts. The experimental results from ORR demonstrated that the Ca/NPS-HC catalyst exhibited outstanding catalytic capability with a half-wave potential of 0.89 V, a kinetic current density of 56.6 mA cm^–2 at 0.85 V, and a Tafel slope of 42 mV dec^–1, outperforming commercial Pt/C. The detailed mechanistic studies revealed that the asymmetric coordination of Ca single atoms led to the symmetry-breaking of electron distribution in Ca single atoms, attenuating the s-p hybridization from the intermediate adsorption process, and thereby minimizing the energy barrier of the whole ORR.

S 块单原子是氧还原反应（ORR）的理想催化剂，因为它们可以抑制芬顿反应。然而，s/p 轨道的对称性往往会与中间产物产生过强或过弱的相互作用。在此，我们制作了与 -S、-OP 和三个 N 原子配位的 Ca 单原子（Ca/NPS-HC），以调节中间产物的吸附，提高 s-block ORR 催化剂的效率。ORR 实验结果表明，Ca/NPS-HC 催化剂的半波电位为 0.89 V，0.85 V 时的动力学电流密度为 56.6 mA cm-2，Tafel 斜率为 42 mV dec-1，催化能力优于商用 Pt/C。详细的机理研究表明，钙单质原子的不对称配位打破了钙单质原子电子分布的对称性，减弱了中间吸附过程的s-p杂化，从而最大限度地降低了整个ORR的能垒。

引用次数: 0

Studies on the Coordination Patterns of Diamine-Bridged Tetraphenoxy Ligands with Group 3 and 4 Metals 二胺桥接四苯氧基配体与第 3 和第 4 族金属的配位模式研究

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01111

Yongjie Chen, Liye Qu, Thierry Roisnel, Marie Cordier, Dan Yuan, Yingming Yao, Evgueni Kirillov

Alkane elimination reactions between the diamino- and dianilino-bridged tetrakis(phenolate) proligands 1a,b-H₄ and precursors M(CH₂SiMe₃)₃(THF)₂, M(CH₂C₆H₄-o-NMe₂)₃ (M = Sc and Y), and Hf(CH₂Ph)₄ were investigated. The diamino-bridged 1a-H₄ afforded nonsymmetric complex 2a-Y₂ incorporating two metal centers in different coordination environments. This one and other dinuclear compounds 2b-Sc₂, 2a-Hf₂, and 2b-Hf₂ were characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction study (for 2a-Y₂ and 2b-Sc₂) and turned out to be symmetric in solution. Compound 2a-Y₂, upon treatment with 2 equiv of 2-phenylpyridine, afforded symmetric bis(aryl) product 3a-Y₂, which was authenticated by NMR spectroscopy and X-ray crystallography. The mechanism of its formation was studied by DFT computations and presumably involves a cooperative reorganization process within the nonsymmetric parent 2a-Y₂ to afford a symmetric isomer prior to its reaction with 2-phenylpyridine.

研究了二氨基和二苯胺桥接四(苯酚)原基 1a,b-H4 与前体 M(CH2SiMe3)3(THF)2、M(CH2C6H4-o-NMe2)3 (M = Sc 和 Y) 和 Hf(CH2Ph)4 之间的烷消除反应。二氨基桥接的 1a-H4 生成了非对称配合物 2a-Y2，在不同的配位环境中含有两个金属中心。通过核磁共振光谱、元素分析和 X 射线衍射研究（2a-Y2 和 2b-Sc2）对该化合物和其他双核化合物 2b-Sc2、2a-Hf2 和 2b-Hf2 进行了表征，结果表明它们在溶液中是对称的。化合物 2a-Y2 用 2 等量的 2-苯基吡啶处理后，可得到对称的双（芳基）产物 3a-Y2，并通过核磁共振光谱和 X 射线晶体学进行了鉴定。通过 DFT 计算研究了其形成机理，推测其中涉及非对称母体 2a-Y2 在与 2-苯基吡啶反应之前的合作重组过程，以产生对称异构体。

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引用次数: 0

Computational Insights into the Intramolecular Aromatic C–C Coupling Catalyzed by the Cytochrome P450 Enzyme CYP121 from Mycobacterium tuberculosis 结核分枝杆菌细胞色素 P450 酶 CYP121 催化的分子内芳香族 C-C 偶联的计算启示

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01943

Xue Zhang, Qian Zhao, Yongjun Liu

CYP121 is a P450 enzyme that catalyzes the intramolecular C–C coupling of its native substrate, dicyclotyrosine (cYY). According to previous suggestions, when the cosubstrate peracetic acid was used to generate Cpd I, the substrate cYY was suggested to participate in the cleavage of the O–O bond; however, whether cYY is involved in the formation of Cpd I and how two distant aromatic carbon atoms are activated are still unclear. Here, we constructed computational models and performed QM/MM calculations to clarify the reaction mechanism. On the basis of our calculation results, cYY is not involved in the formation of Cpd I, and the C–C coupling reaction starts from hydrogen abstraction. In the second stage, the substrate should first undergo a complex conformational change, leading to two phenolic hydroxyls of cYY close to each other. In the subsequent reaction, the resultant Cpd II again abstracts a hydrogen atom from the proximal tyrosine to generate the diradical intermediate. In addition, the C–C coupling occurs in the active site, but the final aromatization may be a nonenzymatic reaction. In general, the intramolecular C–C coupling requires two basic conditions, including the active site having good flexibility and the substrate itself having a suitable and rotatable skeleton.

CYP121 是一种 P450 酶，可催化其原生底物双环酪氨酸（cYY）的分子内 C-C 偶联。然而，cYY 是否参与了 Cpd I 的形成，以及两个相距甚远的芳香碳原子是如何被激活的，目前仍不清楚。在此，我们构建了计算模型并进行了 QM/MM 计算，以阐明反应机理。根据我们的计算结果，cYY 不参与 Cpd I 的形成，C-C 偶联反应从氢的抽取开始。在第二阶段，底物应首先发生复杂的构象变化，导致 cYY 的两个酚羟基相互靠近。在随后的反应中，生成的 Cpd II 再次从近端酪氨酸中抽取一个氢原子，生成二叉中间体。此外，C-C 偶联发生在活性位点，但最终的芳香化可能是非酶促反应。一般来说，分子内 C-C 偶联需要两个基本条件，包括活性位点具有良好的柔韧性以及底物本身具有合适的可旋转骨架。

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引用次数: 0

Thermal Jahn-Teller Distortion Changes and Slow Relaxation of Magnetization in Mn(III) Schiff Base Complexes. 锰（III）希夫碱配合物中的热贾恩-泰勒畸变变化和磁化的缓慢弛豫。

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01317

Chantalaksana Chantarangkul, Apinya Patigo, John C McMurtrie, Rodolphe Clérac, Mathieu Rouzières, Silvia Gómez-Coca, Eliseo Ruiz, Phimphaka Harding, David J Harding

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^- 1 and BF₄^-·1/3CH₂Cl₂ 2) and [Mn(salBzen-Br)₂]Y (salBzen-Br = 2-{[2-(benzylamino)ethylimino]methyl}-4-Br-phenol; Y = ClO₄^- 3 and BF₄^- 4). X-ray structures of [Mn(salEen-Br)₂]ClO₄·0.45C₆H₁₄ 1-hexane, [Mn(salEen-Br)₂]BF₄·0.33CH₂Cl₂·0.15C₆H₁₄ 2-dcm-hexane, and 3-4 reveal that they crystallize in ambient conditions in the monoclinic P2₁/c space group. Lowering the temperature, 2-dcm-hexane uniquely exhibits a structural phase transition toward a monoclinic P2₁/n crystal structure determined at 100 K with the unit cell trebling in size. Remarkably, at room temperature, the axially elongated Jahn-Teller axis in 2-dcm-hexane is poorly defined but becomes clearer at low temperature after the phase transition. Magnetic susceptibility measurements of 1-4 reveal that only 3 and 4 show slow relaxation of magnetization with Δ_eff/k_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.

在 [Mn(salEen-Br)2]Y（salEen-Br = 2-{[2-（乙基氨基）乙基亚氨基]甲基}-4-Br-苯酚）中，我们探讨了阴离子和烷基对四种单核锰（III）配合物的电子结构和磁性能的影响；Y = ClO4- 1 和 BF4--1/3CH2Cl2 2）和 [Mn(salBzen-Br)2]Y（salBzen-Br = 2-{[2-（苄基氨基）乙基亚氨基]甲基}-4-Br-苯酚；Y = ClO4- 3 和 BF4- 4）。[Mn(salEen-Br)2]ClO4-0.45C6H14-1-己烷、[Mn(salEen-Br)2]BF4-0.33CH2Cl2-0.15C6H14-2-dcm-己烷和 3-4 的 X 射线结构显示，它们在环境条件下结晶为单斜 P21/c 空间群。降低温度后，2-dcm-己烷独特地向单斜 P21/n 晶体结构发生结构相变，该结构在 100 K 时确定，单胞尺寸增加了三倍。值得注意的是，在室温下，2-dcm-己烷中轴向拉长的 Jahn-Teller 轴并不清晰，但在相变后的低温下变得更加清晰。1-4 的磁感应强度测量显示，只有 3 和 4 显示出缓慢的磁化弛豫，Δeff/kB = 27.9 和 20.7 K，这意味着苄基对于观察单分子磁体（SMM）特性非常重要。理论计算表明，烷基对轨道水平有微妙的影响，因此很有可能影响观察到的单分子磁体特性。

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引用次数: 0

pH-Driven Rotational Configuration of Keggin-Fe13 Clusters and Their Transformations pH 值驱动的 Keggin-Fe13 簇旋转构型及其转变

IF 4.6 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry

Pub Date : 2024-06-27 DOI: 10.1021/acs.inorgchem.4c01369

Man-Ting Chen, Qiao-Fei Xu, La-Sheng Long, Lan-Sun Zheng

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 (1), [Dy₆Fe₁₃(Gly)₁₂(μ₃–OH)₂₄(μ₄–O)₄(H₂O)₁₈]·13ClO₄·14H₂O (2), [Pr₈Fe₃₄(Gly)₂₄(μ₃–OH)₂₈(μ₃–O)₃₀(μ₄–O)₄(H₂O)₃₀]·6ClO₄·20H₂O (3), and [Pr₆Fe₁₃(Gly)₁₂(μ₃–OH)₂₄(μ₄–O)₄(H₂O)₁₈]·13ClO₄·22H₂O (4, Gly = glycine). Single-crystal analyses reveal that 1 has a β-Keggin-Fe₁₃ cluster, marking the first documented instance of such a cluster to date. Conversely, both 2 and 4 contain an α-Keggin-Fe₁₃ cluster, while 3 is characterized by four hexavacant ε-Keggin-Fe₁₃ clusters. Magnetic property investigations of 1 and 2 show that 2 exhibits ferromagnetic interactions, while 1 exhibits antiferromagnetic interactions. An exploration of the synthetic conditions for 1 and 2 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 3 to 4 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.

Keggin-Fe13团簇被认为是铁水物的基础构件或成核前体。了解影响这些团簇旋转构型的因素及其在水中的转化，对于理解铁水物的形成机制至关重要。在此，我们报告了四种镧铁氧簇的合成和晶体结构，即[Dy6Fe13(Gly)12(μ2-OH)6(μ3-OH)18(μ4-O)4(H2O)17]-13ClO4-19H2O (1)、[Dy6Fe13(Gly)12(μ3-OH)24(μ4-O)4(H2O)18]-13ClO4-14H2O（2）、[Pr8Fe34(Gly)24(μ3-OH)28(μ3-O)30(μ4-O)4(H2O)30]-6ClO4-20H2O（3）和[Pr6Fe13(Gly)12(μ3-OH)24(μ4-O)4(H2O)18]-13ClO4-22H2O（4，Gly = 甘氨酸）。单晶分析表明，1 具有一个 β-Keggin-Fe13 团簇，这是迄今为止首次记录到这种团簇。相反，2 和 4 都含有一个 α-Keggin-Fe13 团簇，而 3 则具有四个六价ε-Keggin-Fe13 团簇。对 1 和 2 的磁特性研究表明，2 表现出铁磁性相互作用，而 1 则表现出反铁磁性相互作用。对 1 和 2 的合成条件的研究表明，较高的 pH 值会促进 α-Keggin-Fe13 团簇的形成，而较低的 pH 值则有利于 β-Keggin-Fe13 团簇的形成。对从 3 到 4 的转变进行的详细分析强调，随着 pH 值的降低，裂隙型 Keggin-Fe13 团簇可以蜕变成 Keggin-Fe13 团簇，同时它们的旋转构型也会发生显著变化。

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引用次数: 0