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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. [ABSTRACT FROM AUTHOR]

The designed synthesis of chiral luminescent molecules with excellent circularly polarized luminescence (CPL) performance and high quantum yield (QY) levels has attracted great interest but remains very challenging. Herein, we report three pairs of chiral europium-titanium-oxo clusters featuring both modest CPL characteristics and high QY levels (up to 79%), which can be regulated by switching between different ligand substituents. [ABSTRACT FROM AUTHOR]

Charge transfer always occurs in molecular valence tautomers, leading to the redistribution of electron density and exhibiting electrical, optical, and magnetic properties, and can be further controlled by multiple external stimuli such as temperature, light and electric field. The design of molecule-based materials capable of charge transfer remains a challenge. Herein, a linear Cu3 compound [(CH3)3NCH2CH2Br]2[Cu3L4(H2O)2] (H2L = chloranilic acid) (1) with a multi-center donor–acceptor architecture was constructed using the redox-active chloranilic acid quinoid ligand. Temperature-dependent dielectric measurement was performed to capture the charge transfer valence tautomer transition because it is difficult to detect this transition by crystal structure and magnetism analysis. Temperature-dependent XPS and EPR further confirmed that the charge transfer valence tautomer transition is based on the CuII–L2− to CuI–L−˙ multi-center charge transfer. Thus, the present work builds a charge transfer compound with a multi-center donor–acceptor architecture and proves that dielectric measurement is a very effective means to detect charge transfer. [ABSTRACT FROM AUTHOR]

A double–heptagon–containing C70H6 (dihept-C70H6) was isolated and unambiguously characterized in the soot of low-pressure combustion, which shares the identical heptagonal cage as dihept-C70Cl6 previously identified in the products of carbon arc, and thus represents the first nonclassical fullerene isolable in both carbon arc and combustion. [ABSTRACT FROM AUTHOR]

Herein, a hetero(S,N)‐quintuple [9]helicene (SNQ9H) molecule with an azacorannulene core was synthesized, currently representing the highest hetero‐helicene reported in the field of multiple [n]helicenes. X‐ray crystallography indicated that SNQ9H includes not only a propeller‐shaped conformer SNQ9H‐1, but also an unforeseen quasi‐propeller‐shaped conformer SNQ9H‐2. Different conformers were observed for the first time in multiple [n≥9]helicenes, likely owing to the doping of heteroatomic sulfurs in the helical skeletons. Remarkably, the ratio of SNQ9H‐1 to SNQ9H‐2 can be regulated in situ by the reaction temperature. Experimental studies on the photophysical and redox properties of SNQ9H and theoretical calculations clearly demonstrated that the electronic structures of SNQ9H depend on their molecular conformations. The strategy of introducing heteroatomic sulfurs into the helical skeleton may be useful in constructing various conformers of higher multiple [n]helicenes in the future. [ABSTRACT FROM AUTHOR]

Herein, a hetero(S,N)‐quintuple [9]helicene (SNQ9H) molecule with an azacorannulene core was synthesized, currently representing the highest hetero‐helicene reported in the field of multiple [n]helicenes. X‐ray crystallography indicated that SNQ9H includes not only a propeller‐shaped conformer SNQ9H‐1, but also an unforeseen quasi‐propeller‐shaped conformer SNQ9H‐2. Different conformers were observed for the first time in multiple [n≥9]helicenes, likely owing to the doping of heteroatomic sulfurs in the helical skeletons. Remarkably, the ratio of SNQ9H‐1 to SNQ9H‐2 can be regulated in situ by the reaction temperature. Experimental studies on the photophysical and redox properties of SNQ9H and theoretical calculations clearly demonstrated that the electronic structures of SNQ9H depend on their molecular conformations. The strategy of introducing heteroatomic sulfurs into the helical skeleton may be useful in constructing various conformers of higher multiple [n]helicenes in the future. [ABSTRACT FROM AUTHOR]

Unlike traditional small molecule drugs, fullerene is an all-carbon nanomolecule with a spherical cage structure. Fullerene exhibits high levels of antiviral activity, inhibiting virus replication in vitro and in vivo. In this review, we systematically summarize the latest research regarding the different types of fullerenes investigated in antiviral studies. We discuss the unique structural advantage of fullerenes, present diverse modification strategies based on the addition of various functional groups, assess the effect of structural differences on antiviral activity, and describe the possible antiviral mechanism. Finally, we discuss the prospective development of fullerenes as antiviral drugs. [ABSTRACT FROM AUTHOR]

Magnetic refrigeration material is the key to adiabatic demagnetization refrigeration technology. In this work, two magnetic refrigerants, Gd5(C4O4)(HCOO)3(CO3)2(OH)6·2.5H2O (1) and Gd2(OH)4SO4 (2), were prepared through hydrothermal reaction. Magnetic study reveals that their magnetic entropy changes are 24.8 J kg−1 K−1 for 1 and 15.1 J kg−1 K−1 for 2 at 2 K and 2 T, respectively. The magnetic entropy changes of 1 and 2 at T = 2 K and ∆H = 2 T exceed most gadolinium hydroxyl compounds, indicating that magnetic refrigerants with large magnetic entropy changes at low magnetic fields can be obtained by introducing more weak magnetic exchange ligands to replace hydroxyl groups in gadolinium hydroxyl compounds. [ABSTRACT FROM AUTHOR]

Stepwise assembly starting from a preassembled metalloligand is a promising approach to obtain otherwise unattainable silver nanoclusters, but hard to be intrinsically identified due to the lack of convincing evidence to justify such a process. Herein, hexagonal and rectangular Ag18 nanoclusters are constructed from the [Mo2O5(PTC4A)2]6− (H4PTC4A=p‐phenyl‐thiacalix[4]arene) metalloligand through stepwise assembly. The formation of the metalloligand is confirmed by electrospray ionization mass spectrometry, then assembled with silver ions to form two geometrically different Ag18 nanoclusters in different solvents. The cyclization from the metalloligand to [(Mo2O5PTC4A)6]12− can be realized without alcohols and otherwise blocked by them. The installation of this metalloligand not only provides comprehensive understanding of how the solvents regulate the silver nanocluster structures, but also brings new insights for the controllable ligand metallization and subsequent condensation. [ABSTRACT FROM AUTHOR]

Stepwise assembly starting from a preassembled metalloligand is a promising approach to obtain otherwise unattainable silver nanoclusters, but hard to be intrinsically identified due to the lack of convincing evidence to justify such a process. Herein, hexagonal and rectangular Ag18 nanoclusters are constructed from the [Mo2O5(PTC4A)2]6− (H4PTC4A=p‐phenyl‐thiacalix[4]arene) metalloligand through stepwise assembly. The formation of the metalloligand is confirmed by electrospray ionization mass spectrometry, then assembled with silver ions to form two geometrically different Ag18 nanoclusters in different solvents. The cyclization from the metalloligand to [(Mo2O5PTC4A)6]12− can be realized without alcohols and otherwise blocked by them. The installation of this metalloligand not only provides comprehensive understanding of how the solvents regulate the silver nanocluster structures, but also brings new insights for the controllable ligand metallization and subsequent condensation. [ABSTRACT FROM AUTHOR]

Due to the partially reduced π-conjugation of the fullerene cage, multi-functionalized fullerene derivatives exhibit remarkable fluorescent properties compared to pristine fullerenes, which have high potential for application in organic light-emitting diodes (OLEDs). In this study two multi-functionalized C70 derivatives, C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2, with excellent fluorescence properties, were designed and synthesized. Compared with C70(OCH3)10 containing a single kind of functional group, both the C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2 exhibited enhanced fluorescence properties with blue fluorescence emission. The fluorescence quantum yields of the C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2 were 1.94% and 2.30%, respectively, which were about ten times higher than that of C70(OCH3)10. The theoretical calculations revealed that the multi-functionalization of the C70 increased the S1–T1 energy gap, reducing the intersystem crossing efficiency, resulting in the higher fluorescence quantum yield of the C70 derivatives. The results indicate that multi-functionalization is a viable strategy to improve the fluorescence of fullerene derivatives. [ABSTRACT FROM AUTHOR]

Hybrid materials integrated with a variety of physical properties, such as spin crossover (SCO) and fluorescence, may show synergetic effects that find applications in many fields. Herein we demonstrate a promising post-synthetic approach to achieve such materials by grafting fluorophores (1-pyrenecarboxaldehyde and Rhodamine B) on one-dimensional SCO FeII structures. The resulting hybrid materials display expected one-step SCO behavior and fluorescent properties, in particular showing a coupling between the transition temperature of SCO and the temperature where the fluorescent intensity reverses. Consequently, synergetic effect between SCO and fluorescence is incorporated into materials despite different fluorophores. This study provides an effective strategy for the design and development of novel magnetic and optical materials. [ABSTRACT FROM AUTHOR]

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. [ABSTRACT FROM AUTHOR]

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report the Gd44Co28 crown and Gd95Co60 cage, formulated as [Gd44Co28(IDA)20 (OH)72(CO3)12(OAc)28(H2O)64]⋅(ClO4)24 and [Na4Gd95 Co60(IDA)40(OH)150(CO3)40(OAc)58(H2O)164] ⋅ (ClO4)41 (H2IDA=iminodiacetic acid), respectively, by providing a library containing multiple low‐nuclearity units. The heart‐like units and crown‐like tetramer found in both compounds indicate unprecedented assembly levels, leading to an atypical geometry characteristic compared to the giant clusters directly assembled by regular units. These two clusters not only significantly increase the size of Ln−Co clusters but also exhibit the enhanced magnetic entropy change at ultra‐low temperatures. This work provided an effective way to fabricate cluster compounds with giant size and geometry complexity simultaneously. [ABSTRACT FROM AUTHOR]

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi‐component building block [Ln3Ti(HSA)6(SA)4(H2O)]− ({Ln3Ti‐SA}, H2SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3Tix‐MSA} (H2MSA=5‐methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3]2− units. The obtained {Ln3Tix‐MSA} can further assemble into a chiral Ln22Ti14 ring with the formulae [Eu22Ti14(MSA)48(HMSA)22(CH3COO)4(H2O)10(iPrOH)] and [Gd22Ti14(MSA)46(HMSA)26(CH3COO)4(H2O)8]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4]4− unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3]2− further triggers interesting chiral‐sorting behavior. Finally, the electronic adsorption and magneto‐optic responses of these molecular rings are investigated. [ABSTRACT FROM AUTHOR]

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi‐component building block [Ln3Ti(HSA)6(SA)4(H2O)]− ({Ln3Ti‐SA}, H2SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3Tix‐MSA} (H2MSA=5‐methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3]2− units. The obtained {Ln3Tix‐MSA} can further assemble into a chiral Ln22Ti14 ring with the formulae [Eu22Ti14(MSA)48(HMSA)22(CH3COO)4(H2O)10(iPrOH)] and [Gd22Ti14(MSA)46(HMSA)26(CH3COO)4(H2O)8]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4]4− unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3]2− further triggers interesting chiral‐sorting behavior. Finally, the electronic adsorption and magneto‐optic responses of these molecular rings are investigated. [ABSTRACT FROM AUTHOR]

A 3D borate–carbonate framework, GdB(OH)4CO3 (1), was synthesized. Magnetic study reveals that its MCE is up to 33.5 J kg−1 K−1 at 2 K and 2 T, due to the introduction of a long magnetic exchange path of Gd–O–B–O–Gd leading to 1 exhibiting weak magnetic interaction. [ABSTRACT FROM AUTHOR]

Photosynthesis in nature uses the Mn4CaO5 cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo3 (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn4O5 cluster. Anchoring LnCo3 on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo3/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo3 for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting. [ABSTRACT FROM AUTHOR]

Polar organic–inorganic hybrid materials have been applied in ferroelectricity, as well as in devices based on nonlinear optical and piezoelectricity properties. Here, we used a rectangular pyramid structure of [VOCl4]2− to construct a polar compound (C5NH13Cl)2VOCl4 (1). Compound 1 crystallized in the monoclinic P21 space group. Coexistence of nonlinear optical switching behavior (space-group change from P21 to P21/n) and two-staged thermosensitive dielectric switching properties could be achieved under the stimulus of temperature. Our findings provide an effective approach for construction of polar materials. [ABSTRACT FROM AUTHOR]

Here we report for the first time soluble lanthanide-transition-metal clusters Ln36Co12 (Ln = Eu, Gd and Dy) as effective homogeneous water oxidation electrocatalysts. The stable 48-metal Ln36Co12 clusters show an effective water oxidation activity under acidic conditions because of the synergistic effect between lanthanide and transition metals in O-O bond formation. [ABSTRACT FROM AUTHOR]

Three series of copper hydride clusters [Cu8H6L6]2+ (1), [Cu4HX2L4]+ where X− = Cl− (2a), Br− (2b), I− (2c), N3− (2d) and SCN− (2e), and [Cu4HX3L3] where X− = Br− (3b) and I− (3c) (L = 2-(diphenylphosphino)pyridine, dppy) were synthesized and characterized by single-crystal X-Ray crystallography and standard spectroscopic techniques. The metal core of 1, Cu8, can be described as a bicapped octahedron, while those of 2 and 3 series adopt tetrahedral structures. The hydride positions were deduced from difference electron density maps and corroborated by NMR and DFT calculations. For 1, there are two μ4-H−, one each in the two tetrahedral cavities of the two capping atoms and four μ3-H− on the six triangular faces around the waist of the octahedron. For [Cu4HX2L4]+ and [Cu4HX3L3] series, the single μ4-H− resides in the center of the Cu4 tetrahedron. It was found that these three series of copper clusters are intimately connected and can convert from one to another under specific reaction conditions. Their transformation pathways were investigated in detail. Spontaneous resolution to form optically pure enantiomeric single crystals was observed for [Cu4H(SCN)2L4]+ (2e) and [Cu4HBr3L3] (3b). Photoluminescence was observed for [Cu4HX2L4]+, as well as [Cu4HX3L3] with strong emissions from green to yellow regions. [ABSTRACT FROM AUTHOR]

Conical carbon, specifically multi‐walled carbon nanocones (CNCs) and single‐walled carboncones, is a new class of sp2‐hybridized carbon allotrope, in addition to fullerene, carbon nanotubes (CNTs), and graphene. Characterized by a conical and delocalized aromatic configuration, the conical carbon structure is considered the intermediate structure between planar graphene and open‐cage fullerene. CNCs can be stiffer than CNTs and exhibit intriguing physical and chemical properties owing to their unique hollow conical structure, which make these materials promising for application as field emission sources and scanning probes. The research on conical carbon structures is in its nascent stage, mainly because of the limitations in the synthesis and purification of conical carbons. This review summarizes the significant progress in the synthesis of CNCs and carboncones. Particularly, the synthetic methods, which can be divided into traditional physical‐chemical synthesis methods for multi‐walled CNCs and emerging bottom‐up organic synthesis methods for single‐walled carboncones, are comprehensively discussed. In addition, the advantages and disadvantages of the various synthetic methods as well as the possible formation and growth mechanisms of CNCs and carboncones are discussed. Finally, some outlooks on the potential solutions to the synthesis of single‐walled carboncones with uniform apex angles are presented. [ABSTRACT FROM AUTHOR]

The assembly of gigantic heterometallic metal clusters remains a great challenge for synthetic chemistry. Herein, based on the slow release strategy of lanthanide ions and in situ formation of lacunary polyoxometalates, two giant 3d‐4f polyoxometalate inorganic clusters [LaNi12W35Sb3P3O139(OH)6]23− (LaNi12) and [La10Ni48W140Sb16P12O568(OH)24(H2O)20]86− (La10Ni48) are obtained. The nanoscopic inorganic cluster La10Ni48 possesses a super tetrahedron structure, which can be viewed as assembly from four LaNi12 molecules encapsulating a central [La6(SbO3)4(H2O)20]6+ octahedron core. This giant aesthetic La10Ni48 tetrahedron containing 214 metal ions is the largest 3d‐4f cluster reported thus far in polyoxometalate system. More interestingly, the LaNi12 and La10Ni48 display high stability in solution and La10Ni48 displays excellent proton conductivity. [ABSTRACT FROM AUTHOR]

A decanuclear cerium-oxo cluster CeIII 4 CeIV 6 featuring mixed valence was prepared by only using the trivalent cerium salt. Single-crystal structure and the distribution of Ce ions in different valence states are determined. The oxidation process and influencing factors of CeIII to CeIV was revealed. Based on the unique structure with mixed valence, the CeIII 4 CeIV 6 cluster exhibits efficient photocurrent response with photocurrent density 0.98 μA cm−2 at 0.5 V. [Display omitted] • A mixed valence cerium-oxo cluster CeIII 4 CeIV 6 only using the trivalent cerium salt was prepared. • The oxidation process of CeIII to CeIV in the initial reaction was revealed. • The unique structure and composition lead to the effective photocurrent response. Cerium-oxo clusters with mixed valence exhibit distinctive redox properties due to cerium ions switch between +3/+4 valence states. However, the design and synthesis of these clusters present formidable challenges, resulting in limited availability of such species, often necessitating the use of both CeIII and CeIV reactants. Herein, we successfully obtained a mixed valence cerium-oxo cluster CeIII 4 CeIV 6 (µ 3 -O) 4 (µ 4 -O) 4 (acac) 14 (CH 3 O) 6 (CH 3 OH) 2 (CeIII 4 CeIV 6 , Hacac = acetylacetone) through low-temperature crystallization only using the trivalent cerium salt. The coexistence as well as the distribution of Ce ions in different valence states have been determined from a multifaceted analysis. In addition, the stability of the synthesized cluster was confirmed by the HRESI-MS study through redissolution of the single crystal sample in fresh methanol. Importantly, Importantly, this study reveals the mechanism for the generation of +4 valence state. Under alkaline conditions, the presence of trace oxygen and the involvement of acetylacetone ligand facilitated the partial oxidation of CeIII to CeIV. The cluster CeIII 4 CeIV 6 has strong ultraviolet absorption and long visible light absorption. As the electrode precursor, CeIII 4 CeIV 6 showed clear photocurrent response and high photocurrent intensity due to CeIII/CeIV redox reaction. [ABSTRACT FROM AUTHOR]

Incorporating metal clusters within the skeleton of the organic polymers through a click reaction cannot only effectively prepare cluster–polymer composites, but also effectively avoid the cluster aggregation. Herein, an azide‐containing lanthanide–titanium oxo cluster of Eu8Ti10‐N3 (Eu8Ti10‐N3=[Eu8Ti10(μ3‐O)14(H2O)4(OAc)2(tbba)30(paza)4(THF)2]⋅4 THF⋅8 H2O (1), Htbba=4‐tert‐butylbenzoic acid, Hpaza=4‐azidobenzoate, HOAc=acetic acid, THF=tetrahydrofuran) through an in situ solvothermal reaction of 4‐azidobenzoic acid and 4‐tert‐butylbenzoic acid. Reaction of 1 with PEG (PEG=methoxypoly(ethyleneglycol)alkyne, 2000 g mol−1) through CuI‐catalyzed click chemistry generates a lanthanide–polymer composite of Eu8Ti10‐N3@PEG (2). Investigation with IR, 1H NMR and ICP‐OES of 2 indicates that the structural integrity of 1 is maintained in 2. Study of the luminescent properties of 1 and 2 reveals that the quantum yield of 1 itself basically remains unchanged in 2. Significantly, the formation of 2 cannot only effectively prevent the cluster 1 from aggregation, but also greatly enhance its solubility and adhesion to the substrate. Owing to the solubility and adhesion of luminescent materials being the key to their practical application, present work is thus of great significance for the development of metal cluster–polymer composite luminescent materials. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: Because of its unsaturated bonds, C60 is susceptible to polymerize into dimers. The implications of nitrogen doping on the geometrical and electronic structure of C60 dimers have been ambiguous for years. A quarter‐century after the discovery of azafullerene dimer (C59N)2, we reported its single crystallographic structure in 2019. Herein, the unambiguous crystal structure information of (C59N)2 is elucidated specifically, revealing that the inter‐cage C—C single bond length of (C59N)2 is comparable with that of an ordinary C(sp3)‐C(sp3) single bond, and that the most stable conformer of (C59N)2 is gauche‐conformer with a dihedral angle of 66°. To amend the structural deviations, geometrical structure of (C59N)2 is optimized by a B3LYP‐D3BJ function, which is proved to be more consistent with its single crystal structure than those by the commonly used B3LYP function. Moreover, the calculation method is also suitable for other representative fullerene dimers, such as (C60)2 and its divalent anion. Additionally, the dissociation of (C59N)2 at 473 K under mass spectrometric conditions suggests the inter‐cage C—C bond is relatively weaker than an ordinary C—C single bond, which can be explained by the interaction energies of inter‐cages. [ABSTRACT FROM AUTHOR]

The formation mechanism of ferrihydrite is the key to understand its treatment of pollutants in waste water and purification of surface water and groundwater. Although emerging evidence suggests that formation of the ferrihydrite occurs through the aggregation of prenucleation clusters, rather than classical atom‐by‐atom growth, its formation mechanism remains unclear. Herein, an iron–oxo anionic cluster of [Fe22(μ4‐O)8(μ3‐OH)20(μ2‐OH)18(CH3COO)16(H2O)2]4− viewed as a dimer of bivacant β‐Keggin‐Fe13 clusters was for the first time obtained by using lanthanide ions as stabilizers. Upon dissolution in a mixed solution of isopropanol and water, the lacunary β‐Keggin‐Fe13 cluster can transform into an α‐Keggin‐Fe13 cluster, distinctly demonstrating that the Keggin‐Fe13 cluster rotational isomerization can be realized through the vacant Keggin‐Fe13 cluster. [ABSTRACT FROM AUTHOR]

Magnetodielectric response mechanisms are critical for the rational design and synthesis of molecule‐based magnetodielectric materials. Herein, the magnetodielectric response was investigated in the molecule‐based material [Fe3O(CH3COO)6(py)3](py) (1). Its magnetodielectric coefficient (MD) is −2.8 % for phase transition III and −4.1 % for phase transition I. Study of the mechanism of the magnetodielectric response in 1 reveals that its magnetodielectric response at phase transition I is induced by the charge‐frustration of the trinuclear iron cluster, while that at phase transition III is attributed to the spin‐frustration of the trinuclear iron cluster, providing a new route for the design of magnetodielectric materials. [ABSTRACT FROM AUTHOR]

Magnetodielectric response mechanisms are critical for the rational design and synthesis of molecule‐based magnetodielectric materials. Herein, the magnetodielectric response was investigated in the molecule‐based material [Fe3O(CH3COO)6(py)3](py) (1). Its magnetodielectric coefficient (MD) is −2.8 % for phase transition III and −4.1 % for phase transition I. Study of the mechanism of the magnetodielectric response in 1 reveals that its magnetodielectric response at phase transition I is induced by the charge‐frustration of the trinuclear iron cluster, while that at phase transition III is attributed to the spin‐frustration of the trinuclear iron cluster, providing a new route for the design of magnetodielectric materials. [ABSTRACT FROM AUTHOR]

A large room‐temperature magnetoelectric response is crucial for the practical application of magnetoelectric materials. However, such a response has never been achieved in molecular–ionic ferroelectric‐based laminated magnetoelectric composites. Herein, the laminated magnetoelectric composite of Metglas/1 (1 = [N(CH3)4][GaBrCl3] and Metglas = an amorphous FeBSi alloy) is prepared by combining the molecular–ionic ferroelectric 1 with Metglas in the longitudinally magnetized and transversely poled (L–T) mode. The room‐temperature magnetoelectric response of the composite is up to 8.74 V Oe−1 cm−1 at the resonance frequency (≈45 kHz), representing the largest room‐temperature magnetoelectric response reported for the molecular–ionic ferroelectric‐based laminated magnetoelectric composites to date. [ABSTRACT FROM AUTHOR]

A heterometallic 3d–4f compound formulated as {[Co III2 Dy3Na(CH3CH2COO)6(OH)6(NO3)4(H2O)2]·H2O}n (1) has been synthesized and structurally characterized. The Co2Dy3 metal core adopts trigonal bipyramidal (TBP) geometry. Compound 1 displays single-molecule magnet behavior with an energy barrier of 60.3 K under a zero dc field. [ABSTRACT FROM AUTHOR]

Atomically precise molecular metal‐oxo clusters provide ideal models to understand metal oxide surfaces, self‐assembly, and form‐function relationships. Devising strategies for synthesis and isolation of these molecular forms remains a challenge. Here, the synthesis of four Ln‐Fe oxo clusters that feature the ϵ‐{Fe13} Keggin cluster in their core is reported. The {Fe13} metal‐oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology, ferrihydrite (as the δ‐isomer) and magnetite (the ϵ‐isomer). The reported ϵ‐{Fe13} Keggin isomer as an isolated molecule provides the opportunity to study the formation of ferrihydrite and magnetite from this building unit. The four currently reported isostructural lanthanide‐iron‐oxo clusters are fully formulated [Y12Fe33(TEOA)12(Hyp)6(μ3‐OH)20(μ4‐O)28(H2O)12](ClO4)23⋅50 H2O (1, Y12Fe33), [Gd12Fe33(TEOA)12(Hyp)6(μ3‐OH)20(μ4‐O)32(H2O)12](ClO4)15⋅50 H2O (2, Gd12Fe33) and [Ln16Fe29(TEOA)12(Hyp)6(μ3‐OH)24(μ4‐O)28(H2O)16](ClO4)16(NO3)3⋅n H2O (Ln=Y for 3, Y16Fe29, n=37 and Ln=Gd for 4, Gd16Fe29n=25; Hyp=trans‐4‐Hydroxyl‐l‐proline and TEOA=triethanolamine). The next metal layer surrounding the ϵ‐{Fe13} core within these clusters exhibits a similar arrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides the opportunity to construct a family of compounds and optimize magnetic exchange in these molecules through composition tuning. Small‐angle X‐ray scattering (SAXS) and high‐resolution electrospray ionization mass spectrometry (HRESI‐MS) show that these clusters are stable upon dissolution in both water and organic solvents, as a first step to performing further chemistry towards building magnetic arrays or investigating ferrihydrite and magnetite assembly from pre‐nucleation clusters. [ABSTRACT FROM AUTHOR]

All previously reported C70 isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C70 species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept‐C70, grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C66 species undergoes successive C2 insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X‐ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π‐orbital axis vector in the fused pentagons to stabilize dihept‐C70. Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO–LUMO gap, which makes dihept‐C70Cl6 isolable by chromatography. The synthesis of dihept‐C70Cl6 offers precious clues with respect to the fullerene formation mechanism in the carbon‐clustering process. [ABSTRACT FROM AUTHOR]

All previously reported C70 isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C70 species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept‐C70, grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C66 species undergoes successive C2 insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X‐ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π‐orbital axis vector in the fused pentagons to stabilize dihept‐C70. Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO–LUMO gap, which makes dihept‐C70Cl6 isolable by chromatography. The synthesis of dihept‐C70Cl6 offers precious clues with respect to the fullerene formation mechanism in the carbon‐clustering process. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

cluster anions composed of carbon and sulfur atoms have been produced from laser vaporization of a sample mixed with sulfur and carbon powders in a 20:1 ratio. They were mass-selected and their molecular formula was determined by collision-induced dissociation. The clusters consist of even carbon atoms only and their number of clustering sulfur atoms equals or exceeds that of carbon atoms. Ab initio calculations at the ROHF/6-31G[sup *] level have been performed for the cluster anions containing two carbon atoms, C[sub 2]S[sub m][sup -] (1≼m≼10). Geometries of various isomeric structures of the clusters were optimized and their energies were compared to find the most stable isomers. For the singly charged anions, attachment of an additional electron leads to break their sulfur rings, and the isomers with two dangling sulfur atoms and a closed ring have the lowest energy. According to the experimental and theoretical investigations, the two carbon atoms form the bone of the clusters, and ejection of two sulfur atoms is the most competitive dissociation pathway of the cluster anions. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A photoactive MOF-based composite with simultaneously incorporated Ru-photosensitizer and Ni(II) molecular catalyst via a "ship-in-a-bottle" synthetic strategy, exhibits highly active, selective and robust, for photocatalytic CO 2 to CO conversion under visible-light illumination. Photocatalytic reduction of CO 2 to CO is a promising strategy for reducing atmospheric CO 2 levels and storing solar radiation as chemical energy. Here, we demonstrate that a molecular catalyst [NiII(bpet)(H 2 O) 2 ] successfully encapsulated into a highly robust and visible-light responsive metal–organic framework (Ru-UiO-67) to fabricate composite catalysts for photocatalytic CO 2 reduction. The composite Ni@Ru-UiO-67 photocatalysts show efficient visible-light-driven CO 2 reduction to CO with a TON of 581 and a selectivity of 99% after 20-h illumination, because of the facile electron transfer from Ru-photosensitizer to Ni(II) active sites in Ni@Ru-UiO-67 system. The mechanistic insights into photoreduction of CO 2 have been studied based on thermodynamical, electrochemical, and spectroscopic investigation, together with density functional theory (DFT) calculations. This work shows that encapsulating molecular catalyst into photoactive MOF highlights opportunities for designing efficient, stable and recyclable photocatalysts. [ABSTRACT FROM AUTHOR]

A diphosphine-protected 18-gold-atom nanocluster was isolated via a facile reduction of an AuI precursor by NaBH4. Its composition was identified as {[Au18(dppm)6Cl4]·C6H6·3Cl·PF6} (SD/Au18, SD = SunDi; dppm = bis-(diphenylphosphino)methane) by X-ray single crystal structural analysis. This nanocluster possesses a prolate shape and is built from an Au10 kernel (bi-octahedral Au6 units sharing one edge) fused with two Au7 caps via sharing six gold atoms. The identity of the Au18 cluster is further demonstrated by ESI-MS. The number of valence electrons of [Au18(dppm)6Cl4]4+ is 10 (n* = 18–4–4), which does not match with the known magic numbers according to the spherical jellium model, and elongated models must be considered. The special stability of the Au18 cluster likely arises from geometrical factors in the metallic core. Two charge states are reported for this system. This work not only presents the structure elucidation of a diphosphine-protected Au18 nanocluster, but also provides an important insight into the growth pattern of gold nanoclusters and the charge states they can achieve. [ABSTRACT FROM AUTHOR]

An effective strategy is developed to synthesize high‐nuclearity Cu clusters, [Cu53(RCOO)10(C≡CtBu)20Cl2H18]+ (Cu53), which is the largest CuI/Cu0 cluster reported to date. Cu powder and Ph2SiH2 are employed as the reducing agents in the synthesis. As revealed by single‐crystal diffraction, Cu53 is arranged as a four‐concentric‐shell Cu3@Cu10Cl2@Cu20@Cu20 structure, possessing an atomic arrangement of concentric M12 icosahedral and M20 dodecahedral shells which popularly occurs in Au/Ag nanoclusters. Surprisingly, Cu53 can be dissolved in diethyl ether and spin coated to form uniform nanoclusters film on organolead halide perovskite. The cluster film can subsequently be converted into high‐quality CuI film via in situ iodination at room temperature. The as‐fabricated CuI film is an excellent hole‐transport layer for fabricating highly stable CuI‐based perovskite solar cells (PSCs) with 14.3 % of efficiency. An effective strategy is developed to synthesize high‐nuclearity Cu53 clusters that are surface‐capped by alkynyl and acetate ligands. These nanoclusters are unexpectedly soluble in ether, enabling the easy formation of high‐quality films. The cluster films are readily converted into high‐quality CuI thin films for applications as a hole transport layer in perovskite solar cells. [ABSTRACT FROM AUTHOR]

An effective strategy is developed to synthesize high‐nuclearity Cu clusters, [Cu53(RCOO)10(C≡CtBu)20Cl2H18]+ (Cu53), which is the largest CuI/Cu0 cluster reported to date. Cu powder and Ph2SiH2 are employed as the reducing agents in the synthesis. As revealed by single‐crystal diffraction, Cu53 is arranged as a four‐concentric‐shell Cu3@Cu10Cl2@Cu20@Cu20 structure, possessing an atomic arrangement of concentric M12 icosahedral and M20 dodecahedral shells which popularly occurs in Au/Ag nanoclusters. Surprisingly, Cu53 can be dissolved in diethyl ether and spin coated to form uniform nanoclusters film on organolead halide perovskite. The cluster film can subsequently be converted into high‐quality CuI film via in situ iodination at room temperature. The as‐fabricated CuI film is an excellent hole‐transport layer for fabricating highly stable CuI‐based perovskite solar cells (PSCs) with 14.3 % of efficiency. [ABSTRACT FROM AUTHOR]

Graphical abstract The synthetic strategy and building block about high-nuclearity lanthanide clusters are summarized, demonstrating the role of template anion in their assembly. Highlights • High-nuclearity lanthanide clusters, because of their unique physical and chemical properties and their potential application, have attracted great much attention in different fields. Owing to the final structures of the lanthanide clusters not only sensitive to starting materials used in the synthesis, but also to reaction conditions including metal ions/ligands ratio, pH, solvents, temperature, duration, rational design and synthesis of lanthanide clusters remains a great challenge. Thus, it is necessary to review the recent advance in the assembly of high-nuclearity lanthanide clusters. • In this review, the synthesis of high-nuclearity lanthanide clusters using the anion template strategy was outlined based on recently reported results. The presence of small anionic species appears to be essential as a template for modular build-up of higher-nuclearity cluster complexes. Compared with a single-anion template, the slow release of anions, multiple anions or mixed anions as templates is more conducive to the assembly of high-nuclearity lanthanide clusters because of their dispersive effect on the positive charges of the clusters. • Based on the structures of the lanthanide clusters recently achieved, the building blocks in the lanthanide clusters were analysed. Some of the high-nuclearity lanthanide clusters with sophisticated structures are assembled from two or more types of structural motifs. Using this building block strategy, abundant clusters featuring multiple combinations of these basic motifs have appeared at a fast rate. • Perspective in future study on the high-nuclearity clusters is discussed. For the rational design and synthesis of lanthanide clusters, future investigations should focus on the assembly mechanism of the lanthanide clusters, which not only being helpful to the rational design and construction of the high-nuclearity lanthanide clusters, but also to the properties study on the high-nuclearity lanthanide clusters. Abstract High-nuclearity lanthanide clusters have attracted much attention in different fields because of their unique physical and chemical properties and their potential applications. In this review, the synthetic strategy and building blocks for the assembly of high-nuclearity lanthanide clusters are outlined based on recently reported high-nuclearity lanthanide clusters. Perspectives for future studies on high-nuclearity lanthanide clusters are also discussed. We hope this review will provide insight into future research on high-nuclearity lanthanide clusters. [ABSTRACT FROM AUTHOR]

Six analogous dumbbell-shaped 3d–4f complexes MII5LnIII4 were obtained by the reaction of Ln(NO3)3 (Ln = Eu, Gd, Dy) and M(OAc)2 (M = Co, Ni) without any other organic ligands, and M5Gd4 exhibited a large magnetocaloric effect (−ΔSm = 31.0, 37.3 J kg−1 K−1 for Co5Gd4 and Ni5Gd4 respectively), while M5Dy4 and Co5Eu4 showed single molecule magnet behaviour. To the best of our knowledge, Co5Eu4 is the first Eu-based cluster to display single molecule magnet behaviour (Ueff = 16.4 K). [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. Assembling lanthanide–transition‐metal (4f–3d) clusters Ln52Ni56 (Ln=Eu, Pr, Nd and Gd) onto CdS composites achieved enhanced photocatalytic H2 production. Some Ni2+ ions in the clusters were exchanged by Cd2+ to form Ln52Ni56−xCdx/CdS composites. An Eu52Ni56−xCdx/CdS species shows the highest activity of 25 353 μmol h−1 g−1 and an apparent quantum efficiency of 42.4 %. [ABSTRACT FROM AUTHOR]

Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Gaseous compounds are usually on-line detectable on sensors. The limitations of conventional sensors are suffering from incapability for exactly identifying multiple components as well as incompatibility to possible toxicants in every odor sample. Herein, we discuss an inlet modification to the laboratory standard mass spectrometer, inspired by the sensitive olfactory systems of animals, for direct sniffing, established by connecting a mini pump to the nebulizer gas tubing. The modified mass spectrometry method—sniffing-mass spectrometry (sniffing-MS)—can acquire detailed fingerprint spectra of mixed odors and shows high tolerance to toxicants. Furthermore, the method has a low limit of detection in the order of parts per trillion and is a 'sampling-free' technique for analyzing various gaseous compounds simultaneously, thus offering versatility for smelling daily commodities, tracking diffusion, and locating position of odors. Sniffing-MS can mimic or even surpass the olfaction of animals and is applicable for analyzing gaseous/volatile compounds, especially those polar compounds, in a simple manner depending on the intrinsic molecular mass-to-charge ratio. [ABSTRACT FROM AUTHOR]

Compared to emissive silver-thiolate clusters, their alkynyl cousins are, however, usually luminescence silent. Herein we report a novel silver-alkynyl cluster based NbO-type framework (SD/Ag18) showing unprecedented triple emission spanning from the visible to near-infrared (NIR) region. It is a 3D framework constructed from a [Cl@Ag16] cluster based unit, which is further quadruply bridged by the surrounding four Ag atoms through Ag…Ag interactions, giving a 4-connected NbO topology. Although SD/Ag18 exhibits weak orange-red emission at room temperature, its emission becomes strong upon cooling, with three emission maxima at 524, 647 and 1036 nm, respectively, covering both the visible and NIR regions. The visible emissions involve triplet alkynyl-to-metal charge transfer mixed with a cluster-centered state, whereas the participation of cPrC≡C− in the frontier orbitals of the cluster may be responsible for the NIR emission. The unusual emissions, especially in the NIR-II region, are observed, for the first time, in silver complexes. [ABSTRACT FROM AUTHOR]

Introducing phenylphosphonic acid (H2PPA) into the Ag/tBuSH assembly system has produced a family of nanoscale‐sized, high‐atom number, silver thiolate/PPA nests (SD/Ag45 a, SD/Ag66 a, and SD/Ag73 a) with impressive core–shell features. SD/Ag45 a is a 45‐atom ellipsoid comprised of an Ag36 shell trapping an Ag9S2 three‐bladed rotor inside. SD/Ag66 a comprises an inner rod‐like Ag20 core and an outer Ag44 shell, giving a 64‐atom nest. These Ag64 nests are further extended by Ag(CN)2 linkers to form a one‐dimensional chain structure. SD/Ag73 a is a three‐shell 73‐nucleus silver nest with a central silver atom enclosed in a rhombicuboctahedron of 24 silver atoms, which is itself enclosed in the outermost shell of a rectified version of a 48‐Ag octahedral Goldberg 2,0 cage. The solution behaviors and optical absorption properties of the three nests are described in detail. Of note, SD/Ag45 a and SD/Ag73 a emit in the near‐infrared region and show different luminescent thermochromic behavior. This work demonstrates that the participation of H2PPA strongly influences the structures of silver thiolate nests, thus providing a new route to fabricate and modify them in a more rational way. A place to call home: Introducing phenylphosphonic acid into the Ag/tBuSH assembly system has led to a family of nanoscale‐sized high‐nuclearity silver thiolate/PPA nests (see figure) with impressive core–shell features, the core and shell structures consisting of Ag9S2@Ag36, Ag20@Ag44, and Ag@Ag24@Ag48 clusters. Two of the nests luminesce in the NIR region and show different luminescent thermochromic behavior. [ABSTRACT FROM AUTHOR]

Abstract: A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OiPr)4, Eu(acac)3, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu3Ti building block can be formed, but that it can further assemble into a Eu24Ti8 compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24Ti8 structure. Single‐crystal structural analysis demonstrates that the Eu24Ti8 has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date. [ABSTRACT FROM AUTHOR]

Abstract: A building blocks strategy is an effective approach for constructing the large molecular systems. Herein, we demonstrate that high‐resolution electro‐spray ionization mass spectrometry (HRESI‐MS) provides an effective chance to insight the assemble process of the building blocks and guides the construction of high‐nuclearity metal clusters on the basis of the reaction of Ti(OiPr)4, Eu(acac)3, and salicylic acid. The time‐dependent HRESI‐MS indicates that not only a Eu3Ti building block can be formed, but that it can further assemble into a Eu24Ti8 compound. Temperature‐dependent HRESI‐MS reveals that increase of the reaction temperature favors the formation and crystallization of the stable Eu24Ti8 structure. Single‐crystal structural analysis demonstrates that the Eu24Ti8 has a wheel‐like structure with diameter of ca. 4.1 nm and is the highest nuclearity lanthanide‐titanium oxo cluster reported to date. [ABSTRACT FROM AUTHOR]