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The magneto-optical response of chiral materials holds significant potential for applications in physics, chemistry, and biology. However, exploration of the near-infrared (NIR) magneto-optical response remains limited. Herein, we report the synthesis and strong NIR-II magneto-optical activity of three pairs of chiral 3d-4f clusters of R/S-Ln15Cu54 (Ln = Sm, Gd, and Dy). Structural analysis reveals that R/S-Ln15Cu54 features a triangular prism cage with C3 symmetry. Interestingly, magnetic circular dichroism (MCD) spectra exhibit remarkable magneto-optical response in the NIR-II region, driven by the f-f transition. The maximum g-factor of R/S-Sm15Cu54 reaches 5.5 × 10-3 T-1 around 1300-1450 nm, surpassing values associated with DyIII and CuII ions. This remarkable NIR-II magneto-optical activity may be attributed to strong magnetic-dipole-allowed f-f transitions and helix chirality of the structure. This work not only presents the largest Ln-Cu clusters to date but also demonstrate the key role of magnetic-dipole-allowed transitions on magneto-optical activity.
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The development of high-performance organic photovoltaic materials is of crucial importance for the commercialization of organic solar cells (OSCs). Herein, two structurally simple donor-π-conjugated linker-acceptor (D-π-A)-configured small-molecule donors with methyl-substituted triphenylamine as D unit, 1,1-dicyanomethylene-3-indanone as A unit, and thiophene or furan as π-conjugated linker, named DTICPT and DTICPF, are developed. DTICPT and DTICPF are facilely prepared via a two-step synthetic process with simple procedures. DTICPF with a furan π-conjugated linker exhibits stronger and broader optical absorption, deeper highest occupied molecular orbital (HOMO) energy levels, and better charge transport, compared to its thiophene analog DTICPT. As a result, vacuum-deposited OSCs based on DTICPF: C70 show an impressive power conversion efficiency (PCE) of 9.36% (certified 9.15%) with short-circuit current density (Jsc) up to 17.49 mA cm-2 (certified 17.56 mA cm-2), which is the highest Jsc reported so far for vacuum-deposited OSCs. Besides, devices based on DTICPT: C70 and DTICPF: C70 exhibit excellent long-term stability under different aging conditions. This work offers important insights into the rational design of D-π-A configured small-molecule donors for high efficient and stable vacuum-deposited OSCs.
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Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, [Ln210Al140(µ2-OH)210(µ3-OH)540(OAc)180(H2O)156](ClO4)120·(MeCN)x·(H2O)y, (Ln = Dy and x = 27, y = 300 for 1; Ln = Y and x = 28, y = 420 for 2). Remarkably, the 350 metal atoms in 1 and 2 display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron. The diameter of the cationic cluster in 1 is approximately 5.0 nm, with an inner cavity diameter of about 2.8 nm and a window diameter of roughly 0.66 nm. The cluster in 1 boasts an accessible inner void volume of up to 15,000 Å3. Notably, these cage clusters maintain stability in water, and the truncated icosidodecahedrons in 1 and 2 are the first of their kind synthesized to date. Given that the open hollow dodecahedral Ln-Al cage cluster has never been reported before, this work represents a member in the family of hollow open dodecahedral cages.
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Adiabatic demagnetization refrigeration (ADR) is a promising cooling technology with high efficiency and exceptional stability in achieving ultralow temperatures, playing an indispensable role at the forefront of fundamental and applied science. However, a significant challenge for ADR is that existing magnetic refrigerants struggle to concurrently achieve low magnetic ordering temperatures (T0) and substantial magnetic entropy changes (-ΔSm) at ultralow temperatures. In this work, we propose the combination of Gd3+ and Yb3+ to effectively regulate both -ΔSm and T0 in ultralow temperatures. Notably, the -ΔSm values for Gd0.1Yb0.9F3 (1) and Gd0.3Yb0.7F3 (2) in the 0.4-1.0 K range exceed those of all previously reported magnetic refrigerants within this temperature interval, positioning them as the most efficient magnetic refrigerants for the third stage to date. Although the -ΔSm values for Gd0.5Yb0.5F3 (3) in 1-4 K are less than those of the leading magnetic refrigerant Gd(OH)F2, the -ΔSm values for Gd0.7Yb0.3F3 (4) in 1-4 K at 2 T surpass those of all magnetic refrigerants previously documented within the same temperature range, making it the superior magnetic refrigerant for the fourth stage identified thus far.
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Adiabatic demagnetization refrigeration is known to be the only cryogenic refrigeration technology that can achieve ultralow temperatures (âª1 K) at gravity-free conditions. The key indexes to evaluate the performance of magnetic refrigerants are their magnetic entropy changes (-ΔSm) and magnetic ordering temperature (T0). Although, based on the factors affecting the -ΔSm of magnetic refrigerants, one has been able to judge if a magnetic refrigerant has a large -ΔSm, how to accurately predict their T0 remains a huge challenge due to the fact that the T0 of magnetic refrigerants is related to not only magnetic exchange but also single-ion anisotropy and magnetic dipole interaction. Here, we, taking GdCO3F (1), Gd(HCOO)F2, Gd2(SO4)3·8H2O, GdF3, Gd(HCOO)3 and Gd(OH)3 as examples, demonstrate that the T0 of magnetic refrigerants with very weak magnetic interactions and small anisotropy can be accurately predicted by integrating mean-field approximation with quantum Monte Carlo simulations, providing an effective method for predicting the T0 of ultralow-temperature magnetic refrigerants. Thus, the present work lays a solid foundation for the rational design and preparation of ultralow-temperature magnetic refrigerants in the future.
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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 ß-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 ß-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.
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Here we report on the strong magneto-chiral dichroism (MChD) detected through visible and near-infrared light absorption up to 5.0 T on {Er5Ni6} metal clusters obtained by reaction of enantiopure chiral ligands and NiII and ErIII precursors. Single-crystal diffraction analysis reveals that these compounds are 3d-4f heterometallic clusters, showing helical chirality. MChD spectroscopy reveals a high gMChD dissymmetry factor of ca. 0.24 T-1 (T = 4.0 K, B = 1.0 T) for the 4I13/2 â 4I15/2 magnetic-dipole allowed electronic transition of the ErIII centers. This record value is 1 or 2 orders of magnitude higher than that of the d-d electronic transitions of the NiII ions and the others f-f electric-dipole induced transitions of the ErIII centers. These findings clearly show the key role that magnetic-dipole allowed transitions have in the rational design of chiral lanthanide systems showing strong MChD.
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A series of chiral heterometallic Ln-Co clusters, denoted as Co2Ln and Co3Ln2 (Ln = Dy and Er), were synthesized by reacting the chiral chelating ligand (R/S)-2-(1-hydroxyethyl)pyridine (Hmpm), CoAc2·4H2O, and Ln(NO3)3·6H2O. Co2Ln and Co3Ln2 exhibit perfect mirror images in circular dichroism within the 320-700 nm range. Notably, the Co2Er and Co3Er2 clusters display pronounced magnetic circular dichroism (MCD) responses of the hypersensitive f-f transitions 4I15/2-4G11/2 at 375 nm and 4I15/2-2H11/2 at 520 nm of ErIII ions. This study highlights the strong magneto-optical activity associated with hypersensitive f-f transitions in chiral 3d-4f magnetic clusters.
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Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu6, abbreviated as LnCu6-AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu6-IM (Ln = La and Nd; IM = Imidazole), and LnCu6-IDA (Ln = Nd; H2IDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu2+ ions around one Ln3+ ion in LnCu6, with variations in Cu···Cu distances attributed to different ligands. Electrocatalytic oxygen evolution reaction (OER) shows that these different LnCu6 clusters exhibit different OER activities with remarkable turnover frequency of 135 s-1 for NdCu6-AC, 79 s-1 for NdCu6-IM and 32 s-1 for NdCu6-IDA. Structural analysis and Density Functional Theory (DFT) calculations underscore the correlation between shorter Cu···Cu distances and improves OER catalytic activity, emphasizing the pivotal role of active-site distance in regulating electrocatalytic OER activities. These results provide valuable insights into the OER mechanism and contribute to the design of efficient homogeneous OER electrocatalysts.
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Five decanuclear lanthanide-iron clusters, formulated as [Ln2Fe8(hmp)10(µ2-OH)4(µ3-OH)2(µ4-O)4(H2O)6]·6ClO4·xH2O (x ≈ 8, Ln = Y for 1; x ≈ 6, Ln = Dy for 2; x ≈ 6, Ln = Ho for 3; x ≈ 7, Ln = Tb for 4; x ≈ 7, Ln = Gd for 5, Hhmp = 2-(hydroxymethyl)pyridine), have been synthesized and structurally characterized. Single-crystal structural analysis reveals that the cluster consists of six face-sharing defective cubane units. Dynamic magnetic investigations indicated that cluster 2 exhibits single-molecule magnet behavior under a zero dc field eliciting an effective energy barrier of Ueff = 17.76 K and a pre-exponential factor of τ0 = 7.93 × 10-8 s. Investigation of the performance of a series of FeIII-DyIII SMMs indicates that the relatively low energy barrier in 2 is associated with the weak ferromagnetic coupling between FeIII and DyIII ions, while the strength of ferromagnetic interaction in these clusters is mainly related to the bond distances between DyIII and O atoms coordinated to FeIII ions. Clusters 3 and 4 exhibit similar dual relaxation pathways under their respective optimal external applied dc field, where the direct relaxation process occurs in the low-frequency area, which impedes the extraction of the Ueff, while the secondary relaxation process appears at a higher frequency, which is probably a connection with intermolecularly driven relaxation. Our findings offer a magneto-structural correlation model for further investigating the single-molecule magnet behavior in lanthanide-iron systems.
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The water oxidation half reaction in water splitting for hydrogen production is extremely rate-limiting. This study reports the synthesis of two heterometallic clusters (Gd6Cu24-IM and Gd6Cu24-AC) for application as efficient water oxidation catalysts. Interestingly, the maximum turnover frequency of Gd6Cu24-IM in an NaAc solution of a weak acid (pH 6) was 319 s-1. The trimetallic catalytic site, H2O-GdIIICuII2-H2O, underwent two consecutive two-electron two-proton coupled transfer processes to form high-valent GdIII-O-O-CuIII2 intermediates. Furthermore, the O-O bond was formed via intramolecular interactions between the CuIII and GdIII centers. The results of this study revealed that synergistic catalytic water oxidation between polymetallic sites can be an effective strategy for regulating O-O bond formation.
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Single crystals with chiral shapes aroused the interest of chemists due to their fascinating polarization rotation properties. Although the formation of large-scale spiral structures is considered to be a potential factor in chiral crystals, the precise mechanism behind their formation remains elusive. Herein, we present a rare phenomenon involving the multitransfer and expression of chirality at micro-, meso-, and macroscopic levels, starting from chiral carbon atoms and extending to the double-helical secondary structure, ultimately resulting in the chiral geometry of crystals. The assembly of the chiral double helices is facilitated by the dual characteristics of amide groups derived from amino acids, which serve as both hydrogen bond donors and receptors, similar to the assembly pattern observed in DNA. Crystal face analysis and theoretical morphology reveal two critical factors for the mechanism of the chiral crystal: inherent intrinsically symmetrical distribution of crystal faces and their acquired growth. Importantly, the magnetic circular dichroism (MCD) study reveals the strong magneto-optical response of the hypersensitive f-f transition in the UV-vis-NIR region, which is much stronger than previously observed signals. Remarkably, an external magnetic field can reverse the CD signal. This research highlights the potential of lanthanide-based chiral helical structures as promising magneto-optical materials.
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Ratiometric luminescent thermometers with excellent performance often require the luminescent materials to possess high thermal stability and relative sensitivity (Sr). However, such luminescent materials are very rare, especially in physiological (298-323 K) and high-temperature (>373 K) regions. Here we report the synthesis and luminescent property of [Tb0.995Eu0.005(pfbz)2(phen)Cl] (3), which not only exhibits high Sr in physiological temperature but also has a Sr up to 7.47% K-1 at 440 K, the largest Sr at 440 K in known lanthanide-based coordination compound luminescent materials.
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The selective fluorination of C-H bonds at room temperature using heterogeneous visible-light catalysts is both interesting and challenging. Herein, we present the heterogeneous sandwich-type structure uranyl-polyoxotungstate cluster Na17{Na@[(SbW9O33)2(UO2)6(PO3OH)6]}·46H2O (denoted as U6P6) to regulate the selective fluorination of the C-H bond under visible light and room temperature. This is the first report in which uranyl participates in the fluorination reaction in the form of an insoluble substance. U6P6 is capable of the effective selective fluorination of cycloalkanes and the recyclability of the photocatalyst due to the synergistic effect of multiple uranyl (UO2)2+ and the insolubility of organic reagents of polyoxotungstate. In situ electron paramagnetic resonance spectroscopy captured the generation of cycloalkane radicals during the photoreaction, confirming the mechanism of direct hydrogen atom transfer.
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Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, the sensitive coordination bonds and vast synthetic space have limited their systematic exploration. Herein, two giant cage-like clusters featuring the organic ligand-directed inorganic skeletons of Ni4[La74Ni104(IDA)96(OH)184(C2O4)12(H2O)76]·(NO3)38·(H2O)120 (La74Ni104, 5 × 5 × 3 - C2O4) and [La84Ni132(IDA)108(OH)168(C2O4)24(NO3)12(H2O)116]·(NO3)72·(H2O)296 (La84Ni132, 5 × 5 × 5 - C2O4) were discovered by a high-throughput synthetic search. With the assistance of machine learning analysis of the experimental data, phase diagrams of the two clusters in a four-parameter synthetic space were depicted. The effect of alkali, oxalate, and other parameters on the formation of clusters and the mechanism regulating the size of two n × m × l clusters were elucidated. This work uses high-throughput synthesis and machine learning methods to improve the efficiency of 3d-4f cluster discovery and finds the highest-nuclearity 3d-4f cluster to date by regulating the size of the n × m × l inorganic cages through oxalate ions, which pushes the synthetic methodology study on elusive inorganic giant cages in a significantly systematic way.
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Correction for 'Multiple correlations between spin crossover and fluorescence in a dinuclear compound' by Chun-Feng Wang et al., Chem. Commun., 2016, 52, 14322-14325, https://doi.org/10.1039/C6CC07810A.
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Electrically conductive metal-organic frameworks (MOFs) have been extensively studied for their potential uses in energy-related technologies and sensors. However, achieving that goal requires MOFs to be highly stable and maintain their conductivity under practical operating conditions with varying solution environments and temperatures. Herein, we have designed and synthesized a new series of {[Ln4(µ4-O)(µ3-OH)3(INA)3(GA)3](CF3SO3)(H2O)6}n (denoted as Ln4-MOFs, Ln = Gd, Tm, and Lu, INA = isonicotinic acid, GA = glycolic acid) single crystals, where electrons are found to transport along the π-π stacked aromatic carbon rings in the crystals. The Ln4-MOFs show remarkable stability, with minimal changes in conductivity under varying solution pH (1-12), temperature (373 K), and electric field as high as 800â¯000 V/m. This stability is achieved through the formation of strong coordination bonds between high-valent Ln(III) ions and rigid carboxylic linkers as well as hydrogen bonds that enhance the robustness of the electron transport path. The demonstrated lanthanide MOFs pave the way for the design of stable and conductive MOFs.
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Endohedral metallofullerenes (EMFs) are sub-nano carbon materials with diverse applications, yet their formation mechanism, particularly for metastable isomers, remains ambiguous. The current theoretical methods focus mainly on the most stable isomers, leading to limited predictability of metastable ones due to their low stabilities and yields. Herein, we report the successful isolation and characterization of two metastable EMFs, Sc2C2@C1(39656)-C82 and Sc2C2@C1(51383)-C84, which violate the isolated pentagon rule (IPR). These two non-IPR EMFs exhibit a rare case of planar and pennant-like Sc2C2 clusters, which can be considered hybrids of the common butterfly-shaped and linear configurations. More importantly, the theoretical results reveal that despite being metastable, these two non-IPR EMFs survived as the products from their most stable precursors, Sc2C2@C2v(5)-C80 and Sc2C2@Cs(6)-C82, via a C2 insertion during the post-formation annealing stages. We propose a systematic theoretical method for predicting metastable EMFs during the post-formation stages. The unambiguous molecular-level structural evidence, combined with the theoretical calculation results, provides valuable insights into the formation mechanisms of EMFs, shedding light on the potential of post-formation mechanisms as a promising approach for EMF synthesis.
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Although cyclopentanone (CPO) is a promising bio-derived fuel, thermodynamic data of its low-temperature oxidation under high-pressure conditions are lacking. In this work, the low-temperature oxidation mechanism of CPO is investigated in a flow reactor in the temperature range of 500-800 K and at a total pressure of 3 atm by a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer. The electronic structure and pressure-dependent kinetic calculations are carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+G(d,p) level to explore the combustion mechanism of CPO. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPO radicals with O2 is HO2 elimination, yielding 2-cyclopentenone. The hydroperoxyalkyl radical (â¢QOOH) generated by 1,5-H-shifting is easily reacted with second O2 and forms ketohydroperoxide (KHP) intermediates. Unfortunately, the third O2 addition products are not detected. In addition, the decomposition pathways of KHP during the low-temperature oxidation of CPO are further assessed, and the unimolecular dissociation pathways of CPO radicals are confirmed. The results of this study can be used for future research on the kinetic combustion mechanisms of CPO under high pressure.
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Magnetoelectric (ME) materials induced by electron transfer are extremely rare. Electron transfer in these materials invariably occurs between the metal ions. In contrast, ME properties induced by electron transfer from an organic radical to a metal ion have never been observed. Here, we report the ME coupling effect in a mononuclear molecule-based compound [(CH3)3NCH2CH2Br][Fe(Cl2An)2(H2O)2] (1) [Cl2An = chloranilate, (CH3)3NCH2CH2Br+ = (2-bromoethyl)trimethylammonium]. Investigation of the mechanism revealed that the ME coupling effect is realized through electron transfer from the Cl2An to the Fe ion. Measurement of the magnetodielectric (MD) coefficient of 1 indicated a positive MD of up to â¼12% at 103.0 Hz and 370 K, which is very different from that of ME materials with conventional electron transfer for which the MD is generally negative. Thus, the current work not only presents a novel ME coupling mechanism, but also opens a new route to the synthesis of ME coupling materials.