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Structure and Redox Behaviour of a Paramagnetic Rh–Pt–Cu–Pt–Rh Heterometallic- Extended Metal -Atom Chain 顺磁 Rh-Pt-Cu-Pt-Rh 异金属-扩展金属-原子链的结构和氧化还原行为
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt01134a
Kazuhiro Uemura, Yuya Ikeda
A paramagnetic, pentanuclear, metal–metal bonded complex comprising three metals is isolated. The Cu dx2y2 orbital of the Rh–Pt–Cu–Pt–Rh chain contains an unpaired electron. The close energetic levels and symmetric overlap of the Cu dx2y2 and Rh–Pt δ* induces a charge-transfer reaction to achieve the diamagnetic Rh–Pt–Cu–Pt–Rh complex.
分离出一种由三种金属组成的顺磁五核金属-金属键复合物。Rh-Pt-Cu-Pt-Rh 链的 Cu dx2-y2 轨道含有一个未成对电子。由于 Cu dx2-y2 和 Rh-Pt δ* 的能级接近且对称重叠,因此发生了电荷转移反应,形成了二磁性的 Rh-Pt-Cu-Pt-Rh 复合物。
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引用次数: 0
Photosubstitution and photoreduction of a diazido platinum(IV) anticancer complex. 重氮铂(IV)抗癌复合物的光取代和光还原。
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt01587h
Huayun Shi, Christian Ward-Deitrich, Fortuna Ponte, Emilia Sicilia, Heidi Goenaga-Infante, Peter J Sadler

The hyphenation of HPLC with its high separation ability and ICP-MS with its excellent sensitivity, allows the analysis of Pt drugs in biological samples at the low nanomolar concentration levels. On the other hand, LC-MS provides molecular structural confirmation for each species. Using a combination of these methods, we have investigated the speciation of the photoactive anticancer complex diazido Pt(IV) complex trans, trans, trans-[Pt(N3)2(OH)2(py)2] (FM-190) in aqueous solution and biofluids at single-digit nanomolar concentrations before and after irradiation. FM-190 displays high stability in human blood plasma in the dark at 37 °C. Interestingly, the polyhydroxido species [{PtIV(py)2(OH)4} + Na]+ and [{PtIV(py)2(N3)(OH)3} + Na]+ resulting from the replacement of azido ligands, as determined by LC-MS, were the major products after photoirradiation of FM-190 with blue light (463 nm). This finding suggests that such photosubstituted Pt(IV) tri- and tetra-hydroxido species could play important roles in the biological activity of this anticancer complex. Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations show that these Pt(IV) species arising from FM-190 in aqueous media can be formed directly from a singlet excited state. The results highlight how speciation analysis (metallomics) can shed light on photoactivation pathways for FM-190 and formation of potential excited-state pharmacophores. The ability to detect and identify photoproducts at physiologically-relevant concentrations in cells and tissues will be important for preclinical development studies of this class of photoactivatable platinum drugs.

高效液相色谱(HPLC)具有高分离能力,而 ICP-MS 具有出色的灵敏度,两者的结合使生物样品中铂类药物的分析达到了纳摩尔级的低浓度水平。另一方面,LC-MS 还能对每种药物进行分子结构确认。我们综合使用了这些方法,研究了光活性抗癌复合物重氮铂(IV)复合物反式、反式、反式-[Pt(N3)2(OH)2(py)2](FM-190)在照射前后水溶液和生物液体中个位数纳摩尔浓度的分型。FM-190 在 37 °C、黑暗环境下的人体血浆中显示出很高的稳定性。有趣的是,经 LC-MS 测定,FM-190 在接受蓝光(463 纳米)光照射后,因取代叠氮配体而产生的多羟基物种 [{PtIV(py)2(OH)4} + Na]+ 和 [{PtIV(py)2(N3)(OH)3} + Na]+ 是主要产物。这一发现表明,这种光取代的铂(IV)三羟基和四羟基物种可能在该抗癌复合物的生物活性中发挥重要作用。密度泛函理论(DFT)和时间相关 DFT(TDDFT)计算表明,FM-190 在水介质中产生的这些铂(IV)物种可以直接从单线激发态形成。这些结果突显了规格分析(金属组学)如何揭示 FM-190 的光活化途径以及潜在激发态药剂的形成。检测和鉴定细胞和组织中生理相关浓度的光产物的能力对于这类光活化铂类药物的临床前开发研究非常重要。
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引用次数: 0
Facile hydrothermal synthesis of a tri-metallic Cu-Mn-Ni oxide-based electrochemical pseudo capacitor. 铜-锰-镍三金属氧化物电化学伪电容器的简便水热合成。
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt00142g
Komal Ali Rao, Muhammad Ehsan Mazhar, Javed Ahmad

Transition metal oxide nanocomposites with heterostructures have gained a lot of attention for use in supercapacitors owing to their low cost, high surface area, fast transport of ions and electrons and high specific capacitance due to efficacious interplay between the electrode and the electrolytes. In this study, we fabricated tri-metallic Cu, Mn, Ni(CMNO), bi-metallic Mn, Ni(MNO) and mono-metallic Ni(NO) oxides through a facile hydrothermal route. All the fabricated materials were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDX), and their electrochemical properties were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge (GCD). The CMNO material showed remarkable electrochemical performance with a specific capacitance of 790.63 F g-1 at a current density of 1 A g-1, surpassing the performance of MNO (438.4 F g-1) and NO (290.82 F g-1). Furthermore, CMNO showed high cycling stability with a retention of 96.7% specific capacitance after 8000 cycles. Based on remarkable and unique properties, the CMNO material is regarded as a promising material for new-generation pseudo-capacitor applications.

具有异质结构的过渡金属氧化物纳米复合材料因其低成本、高比表面积、离子和电子的快速传输以及电极和电解质之间的高效相互作用所产生的高比电容而在超级电容器中的应用获得了广泛关注。在本研究中,我们通过简便的水热法制备了铜、锰、镍三金属(CMNO)、锰、镍双金属(MNO)和镍单金属(NO)氧化物。利用扫描电子显微镜(SEM)、X 射线衍射(XRD)、X 射线光电子能谱(XPS)和能量色散光谱(EDX)对所有制备材料进行了表征,并利用循环伏安法(CV)、电化学阻抗能谱(EIS)和电静态充放电法(GCD)研究了它们的电化学特性。CMNO 材料表现出卓越的电化学性能,在电流密度为 1 A g-1 时,比电容为 790.63 F g-1,超过了 MNO(438.4 F g-1)和 NO(290.82 F g-1)。此外,CMNO 还具有很高的循环稳定性,在 8000 次循环后仍能保持 96.7% 的比电容。CMNO 材料具有显著而独特的特性,被认为是新一代伪电容器应用的理想材料。
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引用次数: 0
Exploring the effect of the axial ligands on the anticancer activity of [C,N,N'] Pt(IV) cyclometallated compounds. 探索轴向配体对 [C,N,N'] Pt(IV) 环金属化合物抗癌活性的影响。
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt01225a
Ariadna Lázaro, Ramón Bosque, Silvia Marín, Raúl Pérez-León, Josefa Badia, Laura Baldomà, Laura Rodríguez, Margarita Crespo, Marta Cascante

The synthesis of three novel [C,N,N'] Pt(IV) cyclometallated compounds containing hydroxo, dichloroacetato or trifluoroacetato axial ligands is reported. Compound [PtCl(OH)2{(CH3)2N(CH2)2NCH(4-FC6H3)}] (3) was prepared by the oxidative addition of hydrogen peroxide to [C,N,N'] Pt(II) cyclometallated compound [PtCl{(CH3)2N(CH2)2NCH(4-FC6H3)}] (1) and further the reaction of compound 3 with dichloroacetate or trifluoroacetate anhydrides led to the formation of the corresponding compounds [PtCl(CHCl2COO)2{(CH3)2N(CH2)2NCH(4-FC6H3)}] (4) and [PtCl(CF3COO)2{(CH3)2N(CH2)2NCH(4-FC6H3)}] (5). The properties of the new compounds along with those of the compound [PtCl3{(CH3)2N(CH2)2NCH(4-FC6H3)}] (2), including stability in aqueous media, reduction potential using cyclic voltammetry, cytotoxic activity against the HCT116 CRC cell line, DNA interaction, topoisomerase I and cathepsin inhibition, and computational studies involving reduction of the Pt(IV) compounds and molecular docking studies, are presented. Interestingly, the antiproliferative activity of these compounds against the HCT116 CRC cell line, which is in all cases higher than that of cisplatin, follows the same trend as the reduction potentials so that the most easily reduced compound 2 is the most potent. In contrast, according to the electrophoretic mobility and molecular docking studies, the efficacy of these compounds in binding to DNA is not related to their cytotoxicity. The most active compound 2 does not modify the DNA electrophoretic mobility while the less potent compound 3 is the most efficient in binding to DNA. Although compounds 2 and 3 have only a slight effect on cell cycle distribution and apoptosis induction, generation of ROS to a higher extent for the most easily reduced compound 2 was observed.

报告了三种新型[C,N,N'] Pt(IV)环金属化合物的合成,这些化合物含有羟基、二氯乙酰基或三氟乙酰基轴向配体。化合物[PtCl(OH)2{(CH3)2N(CH2)2NCH(4-FC6H3)}] (3) 是通过过氧化氢与[C,N、N']铂(II)环金属化合物[PtCl{(CH3)2N(CH2)2NCH(4-FC6H3)}](1)的氧化加成制备了化合物 3,进一步将化合物 3 与二氯乙酸或三氟乙酸酐反应生成了相应的化合物[PtCl(CHCl2COO)2{(CH3)2N(CH2)2NCH(4-FC6H3)}](2)。FC6H3)}] (4) 和 [PtCl(CF3COO)2{(CH3)2N(CH2)2NCH(4-FC6H3)}] (5)。本文介绍了这些新化合物以及化合物[PtCl3{(CH3)2N(CH2)2NCH(4-FC6H3)}](2)的特性,包括在水介质中的稳定性、利用循环伏安法测定的还原电位、对 HCT116 CRC 细胞系的细胞毒性活性、DNA 相互作用、拓扑异构酶 I 和 cathepsin 抑制作用,以及涉及还原铂(IV)化合物和分子对接研究的计算研究。有趣的是,这些化合物对 HCT116 CRC 细胞系的抗增殖活性在所有情况下都高于顺铂,其趋势与还原电位相同,因此最容易还原的化合物 2 的活性最强。相反,根据电泳迁移率和分子对接研究,这些化合物与 DNA 结合的功效与其细胞毒性无关。活性最强的化合物 2 不会改变 DNA 的电泳迁移率,而活性较弱的化合物 3 与 DNA 的结合效率最高。虽然化合物 2 和 3 只对细胞周期分布和细胞凋亡诱导有轻微影响,但观察到最易还原的化合物 2 产生的 ROS 更多。
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引用次数: 0
Orthogonal magnetic orbit-als in high spin Cu-VO units: structure, mag-netism and EPR study of aniso-tropic hetero-metallic com-plexes 高自旋 Cu-VO 单元中的正交磁轨道:各向异性杂金属复合物的结构、磁网和 EPR 研究
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt01346h
Qing-Song Deng, Yu-Shuang Zhang, Ye-Xin Wang, Yi Xie, Pengxiang Fu, Song Gao, Zheng Liu, ShangDa Jiang
Molecular-based magnetic materials are expected to serve as building blocks for quantum bits. To realize high-dimensional Hilbert space and addressability, we constructed anisotropic multi-level systems based on CuII and VIV with orthogonal magnetic orbitals. The crystal structures and intramolecular magnetic cou-plings of four CuIIVOII com-plexes [{CuVO(appen)2}2], [{CuVO(fhma)2EDA}2], [{Cu-VO(hfca)2EDA}2] and [Cu-VO(hfca)2DPEDA]n are charac-terized. Due to the orthogonal magnetic orbitals of CuII and VIV, the Cu-V pairs in the four complexes have strong ferro-magnetic couplings, and the coupling strength is linearly related to the dihedral angle between the two equatorial planes of the two coordination polyhedra. Because of the triplet ground state, the sys-tem can be described by an effective Hamiltonian model consisting of two S = 1 spins coupled, the anisotropy pa-rameters of [{Cu-VO(hfca)2EDA}2] and [Cu-VO(hfca)2DPEDA]n were ob-tained by the simulation of X-band continuous wave elec-tron paramagnetic resonance (cw-EPR) spectra, confirming that both complexes have zero-field splitting addressable on the relative energy scale. The results indicate that con-structing multi-centre com-plexes based on orthogonal magnetic orbitals makes a promising strategy for design-ing multidimensional quantum bits.
分子磁性材料有望成为量子比特的构件。为了实现高维希尔伯特空间和可寻址性,我们构建了基于具有正交磁轨道的 CuII 和 VIV 的各向异性多级系统。我们研究了四种 CuIIVOII 组合[{CuVO(appen)2}2]、[{CuVO(fhma)2EDA}2]、[{Cu-VO(hfca)2EDA}2]和[Cu-VO(hfca)2DPEDA]n 的晶体结构和分子内磁耦合。由于 CuII 和 VIV 的正交磁轨道,四个配合物中的 Cu-V 对具有很强的铁磁耦合,耦合强度与两个配位多面体的两个赤道平面之间的二面角成线性关系。通过模拟 X 波段连续波电子顺磁共振(cw-EPR)光谱,得到了[{Cu-VO(hfca)2EDA}2]和[Cu-VO(hfca)2DPEDA]n 的各向异性参数,证实这两种配合物在相对能量尺度上具有零场分裂。结果表明,基于正交磁轨道构建多中心复合物是设计多维量子比特的一种有前途的策略。
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引用次数: 0
A Green Approach to Encapsulate Proteins and Enzymes Within Crystalline Lanthanide-Based Tb and Gd MOFs 在晶体镧系元素铽和钆 MOFs 中封装蛋白质和酶的绿色方法
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-19 DOI: 10.1039/d4dt01667j
Davide Tocco, Madhura Joshi, Rosangela Mastrangelo, Emiliano Fratini, Andrea Salis, Martin Hartmann
In this work, bovine serum albumin (BSA) and Aspergillus sp. laccase (LC) were encapsulated in-situ within two lanthanide-based MOFs (TbBTC and GdBTC) through a green one-pot synthesis (almost neutral aqueous solution, T = 25 °C, and atmospheric pressure) in about 1 h. Pristine MOFs and protein-encapsulated MOFs were characterized through wide angle X-ray scattering, scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared and Raman spectroscopies. The location of immobilized BSA molecules, used as a model protein, was investigated through small angle X-ray scattering. BSA occurs both on the inner and on the outer surface of the MOFs. LC@TbBTC, and LC@GdBTC samples were also characterized in terms of specific activity, kinetic parameters, and storage stability both in water and acetate buffer. The specific activity of LC@TbBTC was almost twice that of LC@GdBTC (10.8 µmol min-1 mg-1 vs 6.6 µmol min-1 mg-1). Both biocatalysts showed similar storage stabilities retaining  60 % of their initial activity after 7 days and  20% after 21 days. LC@TbBTC dispersed in acetate buffer exhibited a higher storage stability than LC@GdBTC. Additionally, terbium-based MOFs showed interesting luminescent properties. Together, these findings suggest that TbBTC and GdBTC are promising supports for the in-situ immobilization of proteins and enzymes.
在这项工作中,通过绿色一锅合成(近中性水溶液,T = 25 °C,常压),在约 1 小时内将牛血清白蛋白(BSA)和曲霉菌漆酶(LC)原位封装在两种镧系 MOFs(TbBTC 和 GdBTC)中。通过广角 X 射线散射、扫描电子显微镜、热重分析、傅立叶变换红外光谱和拉曼光谱对原始 MOFs 和蛋白质包封 MOFs 进行了表征。通过小角 X 射线散射研究了作为模型蛋白质的固定 BSA 分子的位置。BSA 同时出现在 MOFs 的内表面和外表面。LC@TbBTC 和 LC@GdBTC 样品在水和醋酸盐缓冲液中的比活度、动力学参数和储存稳定性也得到了表征。LC@TbBTC 的比活性几乎是 LC@GdBTC 的两倍(10.8 µmol min-1 mg-1 vs 6.6 µmol min-1 mg-1)。这两种生物催化剂显示出相似的储存稳定性,在 7 天后仍能保持  60% 的初始活性,在 21 天后仍能保持  20% 的初始活性。分散在醋酸盐缓冲液中的 LC@TbBTC 比 LC@GdBTC 具有更高的储存稳定性。此外,铽基 MOFs 还显示出有趣的发光特性。这些研究结果表明,TbBTC 和 GdBTC 是蛋白质和酶原位固定的理想支持物。
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引用次数: 0
An organic-organometallic CO-releasing material comprising 4,4'-bipyridine and molybdenum subcarbonyl building blocks. 一种由 4,4'-联吡啶和钼亚羰基结构单元组成的有机-有机金属二氧化碳释放材料。
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1039/d4dt01303d
Isabel B Calhau, Ana C Gomes, Ricardo F Mendes, Filipe A Almeida Paz, Isabel S Gonçalves, Martyn Pillinger

Over the past two decades, following the discovery of the important biological roles of carbon monoxide (CO), metal carbonyl complexes have been intensively studied as CO-releasing molecules (CORMs) for therapeutic applications. To improve the properties of "bare" low molecular weight CORMs, attention has been drawn to conjugating CORMs with macromolecular and inorganic scaffolds to produce CO-releasing materials (CORMAs) capable of storing and delivering large payloads of the gasotransmitter. A significant obstacle is to obtain CORMAs that retain the beneficial features of the parent CORMs. In the present work, a crystalline metal-organic framework (MOF) formulated as Mo(CO)3(4,4'-bipyridine)3/2 (Mobpy), with a structure based on Mo(CO)3 metallic nodes and bipyridine linkers, has been prepared in near quantitative yield by a straightforward reflux method, and found to exhibit CO-release properties that mimic those typically observed for molybdenum carbonyl CORMs. Mobpy was characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR, FT-Raman and diffuse reflectance (DR) UV-vis spectroscopies, and 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR. The release of CO from Mobpy was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. Mobpy liberates CO upon contact with a physiological buffer in the dark, leading to a maximum released amount of 1.3-1.5 mmol g-1, after 1.5 h at 37 °C, with half-lives of 0.5-1.0 h (time to transfer 0.5 equiv. of CO to Mb). In the solid-state and under open air, Mobpy undergoes complete decarbonylation over a period of 42 days, corresponding to a theoretical CO-release of 7.25 mmol g-1.

在过去的二十年里,人们发现了一氧化碳(CO)的重要生物学作用,并将金属羰基复合物作为用于治疗的一氧化碳释放分子(CORMs)进行了深入研究。为了改善 "裸 "低分子量 CORMs 的特性,人们开始关注将 CORMs 与大分子和无机支架共轭,生产出能够储存和输送大量有效载荷的一氧化碳释放材料(CORMAs)。一个重要的障碍是如何获得能够保留母 CORMs 的有益特性的 CORMAs。本研究采用直接回流法制备了一种结晶金属有机框架 (MOF),名为 Mo(CO)3(4,4'-联吡啶)3/2(Mobpy),其结构基于 Mo(CO)3 金属节点和联吡啶连接体,产量接近定量。通过粉末 X 射线衍射 (PXRD)、热重分析 (TGA)、傅立叶变换红外光谱 (FT-IR)、傅立叶变换拉曼光谱 (FT-Raman)、漫反射 (DR) 紫外可见光谱以及 13C{1H} 交叉偏振 (CP) 魔角旋转 (MAS) NMR 对 Mobpy 进行了表征。通过脱氧-肌红蛋白(deoxy-Mb)/碳单氧-肌红蛋白(MbCO)紫外-可见检测法研究了 Mobpy 释放 CO 的情况。Mobpy 在黑暗中与生理缓冲液接触时会释放出 CO,在 37 °C 下 1.5 小时后,最大释放量为 1.3-1.5 mmol g-1,半衰期为 0.5-1.0 小时(将 0.5 等量 CO 转移到 Mb 的时间)。在固态和露天条件下,Mobpy 会在 42 天内完全脱碳,理论上释放出 7.25 mmol g-1。
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引用次数: 0
Creation of spin-switching in graphene oxide-based hybrid film materials with anionic Fe(III) 5Cl-salicyaldehyde-thiosemicarbazone complex 用阴离子 Fe(III) 5Cl 水杨醛-硫代氨基脲络合物在氧化石墨烯基混合薄膜材料中创建自旋开关
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1039/d4dt01593b
Natalia Spitsyna, Anatoly S Lobach, Maxim Blagov, nadezhda N. Dremova, Alexey I. Dmitriev, Michael V. Zhidkov, Sergey Simonov
The present article describes the synthesis of hybrid composite film materials formed during the self-assembly process through non-covalent interactions of graphene oxide (GO) nanosheets with salt 1, represented by the anionic spin-crossover complex [FeIII(5Cl-thsa)2]- (5Cl-thsa – 5-chlorosalicylaldehyde thiosemicarbazone) and the organic tetraethylammonium cation [Et4N]+. The insertion of salt 1 molecule into the interlayer space of GO nanosheets with the subsequent formation of hybrid material GO-1 was observed. The film of the hybrid material GO-1 was characterized by scanning electron microscopy, energy dispersive analysis, IR, Raman, and 57Fe Mössbauer spectroscopy, dc magnetic measurements, powder X-ray diffraction. The comparison of the magnetic properties of salt 1 and the film of the hybrid material GO-1 demonstrated a significant influence of the GO nanosheets matrix on the completeness of the spin transition and showed a slight shift of the hysteresis loop by 1 K in the temperature range of 200-230 K.. DFT calculations showed an important role of the organic cation [Et4N]+ in the process of adsorption of the spin-crossover anion [FeIII(5Cl-thsa)2]- on the GO nanosheets surface.
本文介绍了在自组装过程中,通过氧化石墨烯(GO)纳米片与以阴离子自旋交叉复合物[FeIII(5Cl-thsa)2]-(5Cl-thsa - 5-氯代水杨醛硫代氨基脲)和有机四乙基铵阳离子[Et4N]+为代表的盐 1 的非共价相互作用而形成的混合复合薄膜材料的合成。观察到盐 1 分子插入 GO 纳米片的层间空间,随后形成了杂化材料 GO-1。通过扫描电子显微镜、能量色散分析、红外光谱、拉曼光谱、57Fe 莫斯鲍尔光谱、直流电磁测量、粉末 X 射线衍射等方法对混合材料 GO-1 的薄膜进行了表征。对盐 1 和混合材料 GO-1 薄膜的磁性能进行的比较表明,GO 纳米片基质对自旋转变的完整性有显著影响,在 200-230 K 的温度范围内,磁滞回线略微偏移了 1 K。DFT 计算表明,有机阳离子 [Et4N]+ 在 GO 纳米片表面吸附自旋转换阴离子 [FeIII(5Cl-thsa)2]- 的过程中发挥了重要作用。
{"title":"Creation of spin-switching in graphene oxide-based hybrid film materials with anionic Fe(III) 5Cl-salicyaldehyde-thiosemicarbazone complex","authors":"Natalia Spitsyna, Anatoly S Lobach, Maxim Blagov, nadezhda N. Dremova, Alexey I. Dmitriev, Michael V. Zhidkov, Sergey Simonov","doi":"10.1039/d4dt01593b","DOIUrl":"https://doi.org/10.1039/d4dt01593b","url":null,"abstract":"The present article describes the synthesis of hybrid composite film materials formed during the self-assembly process through non-covalent interactions of graphene oxide (GO) nanosheets with salt <strong>1</strong>, represented by the anionic spin-crossover complex [Fe<small><sup>III</sup></small>(5Cl-thsa)<small><sub>2</sub></small>]<small><sup>-</sup></small> (5Cl-thsa – 5-chlorosalicylaldehyde thiosemicarbazone) and the organic tetraethylammonium cation [Et<small><sub>4</sub></small>N]<small><sup>+</sup></small>. The insertion of salt <strong>1 </strong> molecule into the interlayer space of GO nanosheets with the subsequent formation of hybrid material GO-<strong>1</strong> was observed. The film of the hybrid material GO-<strong>1</strong> was characterized by scanning electron microscopy, energy dispersive analysis, IR, Raman, and <small><sup>57</sup></small>Fe Mössbauer spectroscopy, <em>dc </em>magnetic measurements, powder X-ray diffraction. The comparison of the magnetic properties of salt <strong>1 </strong>and the film of the hybrid material GO-<strong>1</strong> demonstrated a significant influence of the GO nanosheets matrix on the completeness of the spin transition and showed a slight shift of the hysteresis loop by 1 K in the temperature range of 200-230 K.. DFT calculations showed an important role of the organic cation [Et<small><sub>4</sub></small>N]<small><sup>+</sup></small> in the process of adsorption of the spin-crossover anion [Fe<small><sup>III</sup></small>(5Cl-thsa)<small><sub>2</sub></small>]<small><sup>-</sup></small> on the GO nanosheets surface.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141726284","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}
引用次数: 0
Synthesis of triphyrin(2.1.1)-triphyrin(2.1.1) homo dimers and bis-Re(I) triphyrin dimer complex. 三卟啉(2.1.1)-三卟啉(2.1.1)同源二聚体和双-Re(I)三卟啉二聚体复合物的合成。
IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1039/d4dt01448k
Gurpreet Kaur, Mangalampalli Ravikanth

First examples of covalently linked triphyrin(2.1.1)-triphyrin(2.1.1) homo dimers connected via flexible alkoxy linkers at β-pyrrole positions were synthesized in 28-30% yields by reacting 2-bromo triphyrin(2.1.1) with three different alkane diols such as 1,2-ethanediol, 1,4-butanediol and 1,6-hexanediol in toluene under Pd2(dba)3/DPEphos catalyzed conditions by refluxing for 12-20 h. One of the free base triphyrin-triphyrin homo dimers was metallated by treating the homo dimer with Re(CO)5Cl in toluene under reflux and afforded bis-Re(I) homo dimer complex in 53% yield. Three free base homo dimers and one bis-Re(I) homo dimer complex were thoroughly characterized and studied using HR-MS, 1D and 2D NMR, absorption spectroscopy, cyclic voltammetry and DFT calculations. Our attempts to obtain the X-ray structure of homo dimers were not successful. However, DFT studies revealed that homo dimers prefer to exist in anti-conformation rather than syn-conformation and both triphyrin macrocycles in homo dimers were similar in terms of the deviation of pyrrole rings from the mean plane defined by the four meso carbons of the respective triphyrin unit. Absorption spectra of homo dimers showed similar absorption features such as in triphyrin(2.1.1) with slight changes in their absorption peak maxima. Electrochemical studies revealed that the homo dimers were electron rich, whereas the bis-Re(I) complex was electron deficient in nature.

在 Pd2(dba)条件下,在甲苯中将 2-溴三聚吡咯(2.1.1)与三种不同的烷二醇(如 1,2-乙二醇、1,4-丁二醇和 1,6-己二醇)反应,合成了首例共价连接的三聚吡咯(2.1.1)-三聚吡咯(2.1.1)均质二聚体,在 β-吡咯位置通过柔性烷氧基连接物连接,产率为 28-30%。1)与三种不同的烷二醇(如 1,2-乙二醇、1,4-丁二醇和 1,6-己二醇)在甲苯中在 Pd2(dba)3/DPEphos催化条件下反应,回流 12-20 小时。在回流条件下,用 Re(CO)5Cl 在甲苯中处理游离碱三氢萘-三氢萘同系二聚体,使其中一个游离碱三氢萘-三氢萘同系二聚体金属化,得到双-Re(I)同系二聚体络合物,收率为 53%。我们使用 HR-MS、1D 和 2D NMR、吸收光谱、循环伏安法和 DFT 计算对三种游离碱同源二聚体和一种双-Re(I) 同源二聚体复合物进行了全面的表征和研究。我们试图获得同源二聚体的 X 射线结构,但没有成功。不过,DFT 研究表明,同源二聚体更倾向于以反构象而非同构象的形式存在,而且同源二聚体中的两个三聚吡咯大环在吡咯环偏离由各自三聚吡咯单元的四个中碳定义的平均平面的程度上是相似的。同源二聚体的吸收光谱显示出与三聚吡咯(2.1.1)相似的吸收特征,但其吸收峰最大值略有变化。电化学研究表明,同源二聚体富电子,而双-Re(I) 复合物则缺电子。
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引用次数: 0
Group 11 Complexes of a Bulky Triazene Ligand 大体积三氮烯配体的第 11 组配合物
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-07-18 DOI: 10.1039/d4dt01561d
Tanner George, Tamika Grant, Isadora Schumann Munhoz, Thai Do, Jason Douglas Masuda
A new triazene ligand was prepared by the reaction of the bulky aryl azide, TerMesN3, (2,6-bis(2,4,6-trimethylphenyl)phenyl azide), with the bulky N-heterocyclic carbene (NHC), SIPr (N,N’-2,6-bis(diisopropylphenyl)-3,4-dihydroimidazol-2-ylidene). The steric bulk of these two groups leads to perpendicular bonding of the NHC-N3 plane and the aryl group which provides immense steric crowding around the triazene core. The corresponding π-conjugated triazene ligand was utilized as a neutral, monodentate ligand which results in monomeric Cu(I)Cl, Ag(I)OTf, and Au(I)Cl complexes. Instability of the π-conjugated triazene Au(I)Cl complex was observed, even under inert conditions. When dissolved and photolyzed in THF with workup in isopropanol, the compound decomposes forming [(SIPr=NH)2Au(I)][Au(I)Cl2] a relatively stable compound to light, moisture, and water – alongside the formation of gold nanoparticles which were characterized using scanning electron microscopy with energy dispersive spectroscopy.
通过大块芳基叠氮化物 TerMesN3(2,6-双(2,4,6-三甲基苯基)苯基叠氮化物)与大块 N-杂环碳(NHC)SIPr(N,N'-2,6-双(二异丙基苯基)-3,4-二氢咪唑-2-亚基)的反应,制备了一种新的三嗪配体。这两个基团的立体体积导致 NHC-N3 平面与芳基垂直结合,从而在三氮烯核心周围形成巨大的立体挤压。相应的π-共轭三嗪配体被用作中性单齿配体,从而产生了单体 Cu(I)Cl、Ag(I)OTf 和 Au(I)Cl 复合物。即使在惰性条件下,也能观察到 π 共轭三氮烯 Au(I)Cl 复合物的不稳定性。当在 THF 中溶解和光解,并在异丙醇中做功时,该化合物分解形成 [(SIPr=NH)2Au(I)][Au(I)Cl2] 一种对光、湿气和水相对稳定的化合物,同时形成金纳米颗粒,利用扫描电子显微镜和能量色散光谱对其进行表征。
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引用次数: 0
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Dalton Transactions
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