Dalton Transactions最新文献_第3页

The influence of the coordination environment of cobalt(II) ions on the magnetic properties of heterometallic complexes with a {Co2Li2} metal core 钴离子配位环境对{Co2Li2}金属芯异质金属配合物磁性能的影响

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02560e

Irina K. Rubtsova, Dmitriy S. Yambulatov, Maxim A. Shmelev, Julia K. Voronina, Alexander S. Goloveshkin, Konstantin A. Babeshkin, Nikolay N. Efimov, Anna K. Matiukhina, Stanislav A. Nikolaevskii, Mikhail A. Kiskin, Igor L. Eremenko

Five new heterometallic carboxylate complexes of the composition [Co₂Li₂(A)₆(L)₂] (L = 4-phenylpyridine, A = 2-furoate anion (1); L = 2,2′-bipyridine, A = 2-furoate anion (2), 3,5-di-tert-butylbenzoate anion (3); L = quinoline, A = 3-cyanobenzoate anion (4), 4-cyanobenzoate anion (5)) were synthesized. The structures of all compounds were determined by single-crystal X-ray diffraction. When monodentate N-donor ligands are replaced by chelating 2,2′-bipyridine, the coordination polyhedron of cobalt ions changes from a distorted tetrahedron to a distorted octahedron. Complexes 1–4 are field induced single-molecule magnets. Mechanisms of slow magnetic relaxation are discussed taking into account both experimental data and quantum chemical calculations.

[Co2Li2(A)6(L)2] （L = 4-苯基吡啶，A = 2-糠酸阴离子）组成的五种新型杂金属羧酸配合物L = 2,2′-联吡啶，A = 2-糠酸阴离子(2),3,5-二叔丁基苯甲酸阴离子(3)；合成了L =喹啉，A = 3-三苯甲酸盐阴离子(4)，4-三苯甲酸盐阴离子(5)。所有化合物的结构均通过单晶x射线衍射测定。当单齿n给体被螯合的2,2 ' -联吡啶取代时，钴离子的配位多面体由畸变四面体变为畸变八面体。配合物1-4是场感应单分子磁体。结合实验数据和量子化学计算，讨论了慢磁弛豫的机理。

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引用次数: 0

Spectroscopic and electrochemical studies of tin(IV) complexes with noninnocent N₂S₂ and N₂O₂ ligands based on acenaphthene. 基于苊的非无害N2S2和N2O2配合物的光谱和电化学研究。

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02688a

Liliya D Labutskaya, Varvara A Klok, Irina V Krylova, Pavel G Shangin, Mikhail E Minyaev, Evgeny V Tretyakov, Mikhail A Syroeshkin, Mikhail P Egorov, Elena N Nikolaevskaya

New mononuclear tin(IV) complexes were obtained via condensation of tin oxides (Ph₂SnO and Et₂SnO) with acenaphthene-based bis(thiosemicarbazones). The structure of the complexes was confirmed using ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, as well as by X-ray diffraction analysis. The electronic and redox properties of complexes 1-5 were studied using UV spectroscopy and cyclic voltammetry (CV). It was shown that the electrochemical reduction of complexes 1-5 is quasi-reversible. Radical anion derivatives of complexes were described using CV and ESR spectroscopy. The second wave of electrochemical reduction of 1-4 is accompanied by further chemical transformations, while the electroreduction of complex 5 leads to the formation of persistent dianion species.

通过锡氧化物（Ph2SnO和Et2SnO）与苊基双硫代氨基脲缩合得到新的单核锡（IV）配合物。配合物的结构通过1H、13C和119Sn核磁共振波谱以及x射线衍射分析得到了证实。利用紫外光谱和循环伏安法（CV）研究了配合物1 ~ 5的电子和氧化还原性质。结果表明，配合物1 ~ 5的电化学还原是准可逆的。利用CV和ESR光谱对配合物的阴离子自由基衍生物进行了描述。1-4的第二波电化学还原伴随着进一步的化学转化，而配合物5的电还原导致了持久的dianion物种的形成。

引用次数: 0

Electrodeposited Polyoxometalate-Cu 2+1 O Hybrid on Copper Foam: Synergistic Electron Transfer for Efficient Nitrate Electroreduction to Ammonia 泡沫铜上电沉积多金属氧酸- cu 2+ O杂化物：协同电子转移对硝酸盐高效电还原制氨的影响

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03106k

Kaiqun Bai, Xinming Wang, Gang Li, Haijun Pang, Huiyuan Ma

Electrocatalytic nitrate reduction (NO3RR) is a sustainable strategy to address nitrate pollution and replace the energyintensive Haber-Bosch process for ammonia synthesis, but it is hindered by complex multi-electron transfer pathways and severe hydrogen evolution competition. Herein, a hybrid electrocatalyst (Mo7/Cu2+1O/Cu@CF) was successfully fabricated via electrodeposition, integrating [Mo7O24] 6-(noted as Mo7) with Cu2+1O on copper foam (CF). The optimized catalyst exhibits exceptional NO3RR performance in neutral media: at -0.7 V vs. reversible hydrogen electrode (RHE), it achieves a high ammonia yield rate of 7.16 mg h -1 cm -2 and a Faradaic efficiency (FE) of 95.7%, along with outstanding stability over 10 hours of continuous electrolysis. Structural characterizations (XRD, XPS, and TEM) confirm the formation of a hybrid structure with strong electronic coupling at the Mo7/Cu2+1O interface, facilitating efficient interfacial electron transfer. In situ Fouriertransform infrared (FTIR) spectroscopy reveals the reaction pathway as NO3 -→ *NO3 → *NO2 → *NO → *NH2OH → *NH3, while 15 N isotope-labeling experiments verify that NH3 originates exclusively from nitrate. The superior performance stems from the synergistic effect between Mo7 (electron reservoir) and Cu2+1O (active site matrix), which optimizes the electronic structure of active sites and suppresses the hydrogen evolution reaction. This work provides a promising catalyst for sustainable ammonia production and a general design principle for high-performance electrocatalysts via polyoxometalatemetal oxide hybridization.

电催化硝酸还原（NO3RR）是解决硝酸盐污染和取代高能耗的Haber-Bosch合成氨工艺的一种可持续策略，但它受到复杂的多电子转移途径和激烈的析氢竞争的阻碍。本文通过电沉积方法成功制备了一种杂化电催化剂（Mo7/Cu2+ 10o /Cu@CF），将[Mo7O24] 6-（记为Mo7）与Cu2+ 10o集成在泡沫铜（CF）上。优化后的催化剂在中性介质中表现出优异的NO3RR性能：在-0.7 V时，相对于可逆氢电极（RHE），它的氨产率高达7.16 mg h -1 cm -2，法拉第效率（FE）达到95.7%，并且在连续电解10小时内具有出色的稳定性。结构表征（XRD， XPS和TEM）证实了在Mo7/Cu2+ 10界面处形成了具有强电子耦合的杂化结构，促进了高效的界面电子转移。原位傅里叶变换红外（FTIR）光谱分析表明，反应途径为NO3 -→*NO3→*NO2→*NO→*NH2OH→*NH3，而15个N同位素标记实验证实NH3完全来源于硝酸盐。优异的性能源于Mo7（电子库）与Cu2+ 10o（活性位点基质）之间的协同作用，优化了活性位点的电子结构，抑制了析氢反应。这项工作为可持续氨生产提供了一种有前途的催化剂，并通过多金属氧和金属氧杂化提供了高性能电催化剂的一般设计原则。

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引用次数: 0

A multifunctional reconfigurable terahertz chiral metasurface based on VO₂ and graphene. 基于VO2和石墨烯的多功能可重构太赫兹手性超表面。

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d6dt00001k

Hongrun Xu, Zhen Cui

Despite advancements in high integration and miniaturization, terahertz (THz) devices still face challenges such as limited functionality, tunability, and narrow application ranges. To resolve the above concerns, we present a multifunctional reconfigurable THz chiral metasurface based on vanadium dioxide (VO₂) and graphene. This structure exploits VO₂'s phase transition and graphene's electrical tunability, enabling multifunctional responses. The metasurface exhibits a triple-band circular dichroism (CD) response within 1.0-3.5 THz, with peaks at 1.62 THz, 2.89 THz, and 3.19 THz, reaching values of 0.944, 0.83, and 0.88, respectively. Dynamic switching of CD peak numbers is achieved through the synergistic control of VO₂ and graphene. Under linearly polarized light incidence, the metasurface shows a single-band linear dichroism (LD) response in the 4.0-4.2 THz range, with a peak value of 0.9 at 4.093 THz. The intensity of the LD response can be reversibly tuned by adjusting the Fermi level of graphene and the incident polarization angle. Additionally, the metasurface efficiently converts polarization under both x-polarized and left-handed circularly polarized light. This multifunctional metasurface offers new opportunities for THz applications, such as CD supermirrors, intelligent switches, chiral photodetectors, and polarization digital imaging systems.

尽管在高集成度和小型化方面取得了进步，但太赫兹（THz）器件仍然面临着诸如有限的功能、可调性和狭窄的应用范围等挑战。为了解决上述问题，我们提出了一种基于二氧化钒（VO2）和石墨烯的多功能可重构太赫兹手性超表面。这种结构利用了VO2的相变和石墨烯的电可调性，实现了多功能响应。超表面在1.0 ~ 3.5 THz范围内呈现三波段圆二色性（CD）响应，峰值分别在1.62 THz、2.89 THz和3.19 THz处，分别达到0.944、0.83和0.88。通过VO2和石墨烯的协同控制，实现了CD峰数的动态切换。在线偏振光入射下，超表面在4.0 ~ 4.2 THz范围内呈现出单波段线性二色性（LD）响应，在4.093 THz处峰值为0.9。通过调节石墨烯的费米能级和入射偏振角，可以可逆地调节LD响应的强度。此外，超表面在x偏振光和左旋圆偏振光下都能有效地转换极化。这种多功能超表面为太赫兹应用提供了新的机会，如CD超镜、智能开关、手性光电探测器和偏振数字成像系统。

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引用次数: 0

Boronate esters for the binding and detection of low molecular weight volatile amines 硼酸酯用于结合和检测低分子量挥发性胺

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02760h

Xiaoning Li, James Boyt, Min Cai, Steven Sloope, Luke T. Lackovic, Mark D. Smith, John J. Lavigne

Conjugated thiophene-based diboronate esters, 1–4, were synthesized to investigate how substituents on catechol alter the Lewis acidity and accessibility to boron, and influence binding interactions with low molecular weight Lewis basic amines. Crystallographic analysis indicated that both boron centres bind analyte and that Lewis base coordination induces deplanarization of the conjugated system. Spectroscopic studies demonstrate that amine binding disrupts conjugation, producing distinct and reproducible optical responses that depend on analyte basicity and structure, with association constants in organic solvent ranging from 10³ to 10⁶ M⁻¹. Quantitative binding analyses indicate strong negative cooperativity between the two boron sites. These results establish design principles for cross-reactive optical sensor arrays capable of differentiating volatile amines relevant to environmental monitoring, food quality assessment, and biomedical diagnostics.

合成了噻吩基共轭二硼酸酯1-4，以研究邻苯二酚上的取代基如何改变刘易斯酸度和对硼的可及性，以及影响与低分子量刘易斯碱胺的结合相互作用。晶体学分析表明，两个硼中心结合分析物，路易斯碱配位引起共轭体系的去平面化。光谱研究表明，胺结合破坏偶联，产生不同的和可重复的光学反应，这取决于分析物的碱度和结构，在有机溶剂中的缔合常数范围为103至106 M−1。定量结合分析表明两个硼位点之间具有很强的负协同性。这些结果建立了能够区分与环境监测、食品质量评估和生物医学诊断相关的挥发性胺的交叉反应性光学传感器阵列的设计原则。

引用次数: 0

Rational design and applications of artificial metalloenzymes based on neuroglobin 基于神经球蛋白的人工金属酶的合理设计与应用

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d6dt00067c

Lijuan Sun, Ying-Wu Lin

The rational design of artificial metalloenzymes enables the expansion of the functionalities of natural metalloenzymes, which has become a research hotspot in biocatalysis. As a member of the globin family, neuroglobin (Ngb) has a stable structure and possesses a tunable intramolecular disulfide bond of Cys46-Cys55, making it an ideal protein scaffold for the rational design of artificial metalloenzymes. This article systematically reviews recent progress in the rational design and applications of artificial metalloenzymes based on Ngb. It highlights strategies such as optimizing the microenvironment in the heme center, substituting key amino acid residues, constructing additional intramolecular disulfide bond, and introducing metal cofactors such as Co-porphyrin, which have successfully endowed Ngb-based artificial metalloenzymes with functions including nitrite reductase, monooxygenase, peroxidase, carbene transferase, hydrogenase, and even carbon monoxide detoxification capabilities. These advances not only deepen the understanding of the structure-function relationships of heme enzymes but also provide new insights in the rational design of artificial metalloenzymes. Artificial metalloenzymes based on Ngb and other protein scaffolds are expected to play significant roles in areas such as green synthesis, biocatalysis, environmental remediation, and biomedicine, etc.

人工金属酶的合理设计使天然金属酶的功能得以拓展，已成为生物催化领域的研究热点。神经球蛋白（neuroglobin, Ngb）作为珠蛋白家族的一员，具有稳定的结构，具有可调节的Cys46-Cys55分子内二硫键，是合理设计人工金属酶的理想蛋白支架。本文系统地综述了近年来基于Ngb的人工金属酶的合理设计和应用研究进展。重点介绍了优化血红素中心微环境、替换关键氨基酸残基、构建分子内二硫键、引入co -卟啉等金属辅因子等策略，成功赋予了基于ngb的人工金属酶亚硝酸盐还原酶、单加氧酶、过氧化物酶、碳转移酶、氢化酶甚至一氧化碳解毒能力。这些进展不仅加深了对血红素酶结构-功能关系的认识，而且为人工金属酶的合理设计提供了新的见解。基于Ngb等蛋白质支架的人工金属酶有望在绿色合成、生物催化、环境修复、生物医学等领域发挥重要作用。

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引用次数: 0

Investigations of Co(II) to Co(III) oxidation mechanisms at Fe3-δO4 nanoparticle surface Fe3-δO4纳米颗粒表面Co（II）到Co（III）氧化机理的研究

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03034j

Laura Fablet, Mathieu Pédrot, Fadi Choueikani, Anthony Beauvois, Thomas Stephant, Valérie Briois, Rémi Marsac

Understanding and predicting the interaction mechanisms between Co and spinel iron oxides (Fe3-δO4; including magnetite, maghemite and their solid solutions) is of major interest in both the environmental and industrial contexts. While the surface complexation of Co2+, its polymerization and the surface precipitation of Fe3-δO4@CoO have been well been documented, the oxidation of Co2+ to Co3+ and interaction mechanisms between Co3+ and Fe3-δO4 nanoparticles in the presence of O2 have attracted less attention. In this study, experimental and modeling results, combined with XAS and XMCD analyses at the L2,3-edges, as well as TEM and XRD analysis, allowed the differentiation of several Co-species according to the Co concentration, at pH 8 under atmospheric O2. At the lowest Co concentrations investigated, Co2+ prevailed as surface complexes, incorporated into Fe3-δO4 nanoparticles, or as Co(OH)2-like surface precipitates. Increasing Co concentration lead to the formation of an additional Co3O4-like phase on the surface of Fe3-δO4 nanoparticles. Quick-XAS measurements at the Co K-edge allowed to follow the kinetics of Co sorption and oxidation on Fe3-δO4 nanoparticles, supporting the equilibrium observations. These results provide a more detailed understanding of Co sorption mechanisms onto Fe3-δO4 nanoparticles under oxic conditions, which offers an environmentally friendly route for the synthesis alternative of Co-doped Fe3-δO4 nanoparticles. In addition, this allows to understand the potential interaction between Co and Fe3-δO4 nanoparticles in environmental systems.

了解和预测Co与尖晶石氧化铁（Fe3-δO4，包括磁铁矿、磁铁矿及其固溶体）之间的相互作用机制在环境和工业背景下都具有重要意义。虽然Co2+的表面络合，其聚合和Fe3-δO4@CoO的表面沉淀已经得到了很好的记录，但在O2存在下Co2+氧化成Co3+以及Co3+与Fe3-δ o4纳米颗粒之间的相互作用机制却很少受到关注。在本研究中，结合实验和建模结果，结合L2、3边的XAS和XMCD分析，以及TEM和XRD分析，在大气O2下pH为8时，可以根据Co浓度区分几种Co-species。在最低Co浓度下，Co +以表面配合物的形式存在，结合到Fe3-δO4纳米颗粒中，或以Co(OH)2样表面沉淀的形式存在。Co浓度的增加导致Fe3-δO4纳米颗粒表面形成额外的co3o4样相。在Co - k边缘的快速xas测量允许跟踪Co在Fe3-δO4纳米颗粒上的吸附和氧化动力学，支持平衡观察。这些结果为在氧化条件下Co在Fe3-δO4纳米颗粒上的吸附机理提供了更详细的了解，为合成可替代的共掺杂Fe3-δO4纳米颗粒提供了一条环保途径。此外，这也有助于了解环境系统中Co和Fe3-δO4纳米颗粒之间的潜在相互作用。

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引用次数: 0

Post-synthetic citrate modification of Eu(III) doped hydroxyapatite nanoparticles for enhanced cellular uptake in bioimaging applications 合成后柠檬酸修饰Eu（III）掺杂羟基磷灰石纳米颗粒增强生物成像应用中的细胞摄取

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02785c

Thoudam Chanchan Devi, Pritam Das, Souma Ghosh, Rajkumar Banerjee, David Thiyam

Interest for the development of various innovative synthesis approaches for producing biomimetic nanoparticles (NPs) arises from their remarkable ability to achieve effective cellular uptake for various biomedical applications. In this study, citrate, one of the main organic constituent in natural bones, serves as an efficient post-synthesis surface modifier for Eu(III) doped hydroxyapatite nanoparticles (Eu:HAp NPs) enabling effective functionalization of the as-synthesized material. The as-prepared (both bared and citrate modified) Eu:HAp NPs are characterized by various analytical techniques like XRD, FTIR, FESEM, TEM, DLS, etc. Characterization studies indicated that this synthesis method alters only the surface characteristic properties, while the core structural properties of particles remains unaffected. FTIR and DLS-zeta potential studies reveal citrate modification occurs on the NPs surface via chemisorptions, inducing negatively charged carboxylate (COO-) sites and improving colloidal stability. Interestingly, citrate modification does not affect the photoluminescent emission characteristics of as-prepared NPs. Additionally, biocompatibility and cell imaging properties are analyzed to evaluate the effect of citrate modification of NPs on cellular uptake capacity. Both bared and citrate modified Eu:HAp NPs do not show any significant toxicity in HEK-293 and MDA-MB-231 cell lines. Also, cells treated with citrate modified Eu:HAp NPs exhibits more red-color luminescence in confocal images and enhanced cellular uptake in FACS analysis compared to bared Eu:HAp NPs treatment. Therefore, due to their excellent biocompatibility and cellular uptake, the synthesized NPs are best suited for bioimaging applications. Further, this approach can also be applied for surface modification with various targeting ligands for diverse use.

开发各种创新合成方法来生产仿生纳米颗粒（NPs）的兴趣源于它们在各种生物医学应用中实现有效细胞摄取的卓越能力。在本研究中，天然骨骼中的主要有机成分之一柠檬酸盐作为Eu（III）掺杂羟基磷灰石纳米颗粒（Eu:HAp NPs）的有效合成后表面改性剂，使合成材料有效功能化。用XRD、FTIR、FESEM、TEM、DLS等分析技术对制备的（裸态和柠檬酸盐修饰的）Eu:HAp NPs进行了表征。表征研究表明，该合成方法仅改变了颗粒的表面特征性质，而不影响颗粒的核心结构性质。FTIR和DLS-zeta电位研究表明，柠檬酸盐通过化学吸附在NPs表面发生修饰，诱导带负电荷的羧酸盐（COO-）位点，提高胶体稳定性。有趣的是，柠檬酸盐改性并不影响制备的NPs的光致发光特性。此外，还分析了生物相容性和细胞成像特性，以评估柠檬酸修饰NPs对细胞摄取能力的影响。裸Eu:HAp NPs和柠檬酸修饰Eu:HAp NPs对HEK-293和MDA-MB-231细胞系均无明显毒性。此外，与裸Eu:HAp NPs处理相比，柠檬酸修饰的Eu:HAp NPs处理的细胞在共聚焦图像中显示出更多的红色发光，并且在FACS分析中增强了细胞摄取。因此，由于其优异的生物相容性和细胞摄取性，合成的NPs最适合生物成像应用。此外，该方法还可以应用于各种靶向配体的表面修饰，以实现不同的用途。

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引用次数: 0

Bicarbonate anion coordination assisted CO2 capture by using urea-morpholine hybrid receptors in water 碳酸氢盐阴离子配位通过在水中使用尿素-啉杂化受体辅助CO2捕获

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt03056k

Zhiwen Sun, Ji Wang, Qingling Nie, Na Li, Zhihua Liu, Xiao-Juan Yang, Wei Zhao, Biao Wu

The development of energy-efficient sorbents for aqueous CO₂ capture remains a significant challenge. This work presents a new design strategy by integrating a tertiary amine (morpholine) with urea motif into a single molecular receptor. This structure enables autonomous, base-free CO₂ capture in water, where the urea groups provide complementary hydrogen bonding sites for (bi)carbonate anions, while the morpholine moiety acts as an internal proton acceptor. The resulting receptors demonstrate a rapid uptake of CO₂ from a simulated flue gas (10% CO₂/N₂), achieving a capacity of up to 1.22 mmol/g. Spectroscopic studies (NMR, MS) and structural analysis of a model complex confirm that capture proceeds via hydrogen-bond-stabilized bicarbonate formation. Crucially, the captured CO₂ can be completely released under remarkably mild conditions, either by heating ca. 40 °C or by simple N₂ purging at ambient temperature. The receptors exhibit excellent recyclability over multiple capture-release cycles without capacity loss. This study highlights the potential of fine-tuning supramolecular interactions-particularly hydrogen bonding combined with a built-in base-to create low-energy, water compatible CO₂ capture systems.

开发用于水相CO2捕获的节能吸附剂仍然是一个重大挑战。这项工作提出了一种新的设计策略，将叔胺（morpholine）与尿素基序整合到一个单分子受体中。这种结构能够在水中自动捕获无碱的二氧化碳，其中尿素基团为（双）碳酸盐阴离子提供互补的氢键位点，而morpholine部分则充当内部质子受体。所得到的受体显示出从模拟烟气（10% CO2/N2）中快速吸收CO2的能力，达到1.22 mmol/g。光谱研究（核磁共振、质谱）和模型复合物的结构分析证实，捕获过程是通过氢键稳定的碳酸氢盐形成的。关键是，捕获的二氧化碳可以在非常温和的条件下完全释放，要么加热约40°C，要么在环境温度下进行简单的N2净化。该受体在多个捕获-释放循环中表现出优异的可回收性，而不会造成容量损失。这项研究强调了微调超分子相互作用的潜力——特别是氢键与内置碱基的结合——以创造低能耗、水兼容的二氧化碳捕获系统。

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引用次数: 0

Luminescent N-heterocyclic carbene Cu(I) complexes with N^O chelating ligands exhibit microsecond lifetimes and photocatalytic activity 具有N^O螯合配体的发光N-杂环碳烯Cu(I)配合物具有微秒寿命和光催化活性

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-02-02 DOI: 10.1039/d5dt02991k

Soumi Chakraborty, Erqian Mao, Thomas G. Gray, Thomas S. Teets

To replace precious noble metal-based photosensitizers in applications involving photoinduced charge separation, energy transfer, or photocatalysis, Cu(I) complexes are considered to be cost-effective, earth-abundant, and sustainable alternatives. An emerging and effective design principle in Cu(I) photosensitizers involves heteroleptic structures where the HOMO and LUMO are spatially separated over two different ligands. In the present work, we introduce a complementary class of heteroleptic, three-coordinate copper photosensitizers that pairs variable N^O chelating ligands (8-hydroxyquinoline and 10-hydroxybenzo[h]quinoline) with a bulky 2,6-diisopropylphenyl-substituted N-heterocyclic carbene (NHC). In this design, both frontier orbitals are localized on the same ligand, the N^O chelate, such that structural modulation of the electron-rich N^O-chelates can substantially tune the energy levels of the HOMO and LUMO, thereby controlling the photoluminescence properties. Detailed photophysical and electrochemical experiments as well as DFT calculations suggest charge-transfer transitions with intra-ligand charge transfer (ILCT) character, involving the N^O ligands. This strategy successfully produced long triplet excited-state lifetimes (up to 44 µs) in compounds that are strong photoreductants (E([Cu]⁺/*[Cu] as negative as −2.0 V vs. the ferrocenium/ferrocene couple). These properties allow these photosensitizers to be used as photocatalysts in various transformations of organic compounds, such as hydrogenation of substituted benzophenones, hydrodehalogenation of aryl/alkyl halides (including challenging C–Cl bond activation) and E/Z isomerization of (E)-stilbene (an example of triplet–triplet energy transfer).

在涉及光诱导电荷分离、能量转移或光催化的应用中，铜(I)配合物被认为是具有成本效益、地球资源丰富且可持续的替代品。在Cu(I)光敏剂中，一种新兴且有效的设计原理涉及到异交结构，其中HOMO和LUMO在两个不同的配体上空间分离。在目前的工作中，我们介绍了一类互补的杂电性三坐标铜光敏剂，它将可变N^O螯合配体（8-羟基喹啉和10-羟基苯喹啉）与一个庞大的2,6-二异丙基苯基取代的N-杂环卡宾（NHC）配对。在这个设计中，两个前沿轨道都定位在同一个配体上，即N^O螯合物，这样，富电子N^O螯合物的结构调制可以大大调节HOMO和LUMO的能级，从而控制光致发光性质。详细的光物理和电化学实验以及DFT计算表明，涉及N^O配体的电荷转移转变具有配体内电荷转移（ILCT）特征。该策略成功地在强光还原剂(E（[Cu]+/*[Cu]与二茂铁/二茂铁偶对相比负- 2.0 V）的化合物中产生了长三重态激发态寿命（高达44µs）。这些性质使得这些光敏剂可以用作各种有机化合物转化的光催化剂，例如取代二苯酮的氢化，芳基/烷基卤化物的氢卤化（包括挑战C-Cl键激活）和(E)-二苯乙烯的E/Z异构化（三重态-三重态能量转移的一个例子）。

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引用次数: 0