An Interpenetrated Three-dimensional Framework Sodium Lanthanide Carboxylate Based on[Ho_4(μ_3-OH)_4]^(8+) Cluster

A novel sodium holmium carboxylate compound,namely Na 4 Ho 4 （μ 3-OH） 4 （1,4BDC） 6 ·6.25H 2 O （1,1,4-BDC=1,4-benzenedicarboxylate）,has been solvothermally synthesized and structurally characterized.The structure features a two-fold interpenetrated three-dimensional open-framework constructed by the [Ho 4 （μ 3-OH） 4 ] 8＋ clusters bridged by 1,4-BDC ligands.The Na ＋ ions and lattice water molecules are located in the channels.The structure is further stabilized by hydrogen-bonding and π-π stacking interactions.The thermal stability of the compound has been investigated via thermogravimetric analysis.

Polyoxometalate-based high-nuclear cobalt-vanadium-oxo cluster as efficient catalyst for visible light-driven CO2 reduction

A high-nuclear Co-V-O cluster was firstly isolated by lacunary polyoxoanion, resulting in the high-nuclear mixed metal-oxo cluster-containing polyoxometalate (POM), K4Na28[{Co4(O-H)3(VO4)}4(SiW9O34)4]· 66H2O (1). In 1, the{Co4(O-H)3(VO4)}4{Co16-V4}core, composed of a{Co4O4}cubane, four{Co4(OH)3}qusi-cubanes and four VO4 units, was stabilized by four lacunary A-α-{SiW9O34} units. Photocatalytic study reveals that 1 exhibits excellent photocatalytic activity for CO2-to-CO conversion with high selectivity under visible light irradiation. The turnover number (TON) and turnover frequency (TOF) reaches as high as 10492 and 0.29 s^-1, respectively. Compound 1 represents the first high nuclear TM cluster-containing POM (TM=transition-metal) with efficient visible light catalytic activity for CO2 reduction, and its photocatalytic activity is much higher than those of most reported molecular catalysts. Photoluminescence spectroscopy study reveals that photoexcitation of Ru-photosensitizer is followed by an efficient electron transfer to POMs to reduce CO2.

Largest 3d-4f 196-nuclear Gd_(158)Co_(38)clusters with excellent magnetic cooling

It is a meaningful and challenging work for structural and synthetic chemists to isolate nano-sized high-nuclearity cluster-molecules.In this work,two largest hetero-metallic nano-clusters Gd_(158)Co_(38) were obtained via the“multi-anions-template”method.Different from the reported giant hollow-nano-clusters,the Ln_(158) core in Gd_(158)Co_(38)(the protein-sized nano-clusters,ca.4.3 nm×3.6 nm×3.5 nm)has the highest Ln nuclear number,which is integrated by twelve halide ions(with the form of icosahedron)as key templates,while Co ions(as 3d metals)are located in its periphery.This emergence indicates a novel structure form of non-open Ln-containing high-nuclearity clusters,and affords a consummate pattern to analyse and assemble the complex cluster-molecules.In addition,Gd_(158)Co_(38)@Cl_(12)breaks the record magnetic entropy change of 3d-4f clusters with−∆S_(m)^(max)=46.95 J kg^(−1)K^(−1)at 7.0 T,2.0 K.

In situ synthesized homochiral dysprosium-oxo clusters with threonine Schiff bases

Chiral high-nuclearity lanthanide(4f)clusters have shown fantastic properties in various fields.However,their synthesis is still of great challenge.Herein,we report two pairs of enantiomers of highnuclearity Dy-oxo clusters synthesized through in situ strategy.They are[Dy18(^(R/S)Hftp)4(^(R/S)H_(2)btp)4(μ2-OH)_(8)(μ3-OH)20(μ6-O)(NO_(3))_(4)(μ-H_(2)O)_(8)]·[solvents](1R and 1S)and[Dy9(^(R/S)Hftp)2(^(R/S)H_(2)btp)_(2)(OAc)_(6)(μ3-OH)_(10)(H_(2)O)_(6)](OAc)·[solvents](2R and 2S),where^(R/S)Hftp2−and^(R/S)H_(2)btp^(3−)represent in situ formed 2-formyl-6-[N-(threonine)iminomethyl]-4-methylphenol and 2,6-bis[N-(threonine)iminomethyl]-4-methylphenol anions,respectively.These in situ formed clusters were endowed with not only homochirality via introducing^(R/S)Hftp2−and^(R/S)H_(2)btp^(3−)ligands,but also rich oxo-bridges by controlling the hydrolysis of Dy^(III)ions.Different anions from DyIII salts further induced structural variation between two sets of clusters.1R and 1S feature an unprecedent four-blade propeller shaped{Dy18}core,whose centered octahedral{Dy6}unit are surrounded by four triangular{Dy3}units.Strikingly,they represent the second largest chiral 4f cluster species so far.2R and 2S display a sandglass-like{Dy9}skeleton that consist of two square pyramid{Dy5}units sharing a Dy^(III)vertex.Magnetic investigation revealed possible antiferromagnetic interactions between the Dy^(III)centers in these clusters.

The chain-shaped coordination polymers based on the bowl-like Ln_(18)_(Ni24(23.5))clusters exhibiting favorable low-field magnetocaloric effect

The design of assembling high-nuclearity transition-lanthanide(3d-4f) clusters along with excellent magnetocaloric effect(MCE) is one of the most prominent fields but is extremely challenging. Herein, two heterometallic metal coordination polymers are constructed via the “carbonatetemplate” method, formulated as {[Gd_(18)Ni_(24)(IDA)_(22)(CO_(3))_(7)(μ_(3)-OH)_(32)(μ_(2)-OH)_(3)(H_(2)O)_(5)Cl]·Cl_(8)·(H_(2)O)_(14)}nand{[Eu_(18)Ni_(23.5)(IDA)_(22)(CO_(3)_(7)(μ_(3)-OH)_(32)(H_(2)O)_(5)(IN)(CH_(3)COO)_(2)(NH_(2)CH_(2)COO)Cl]·C_(l6)·(H_(2)O)_(17)}n[abbreviated as 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))n respectively;H_(2)IDA = iminodiacetic acid;HIN = isonicotinic acid]. Concerning the structures, compounds 1-(Gd_(18)Ni_(24))nand 2-(Eu_(18)Ni_(23.5))nboth feature the one-dimensional(1D) chain-like structure which is rarely reported in high-nuclearity metal complexes. Meanwhile, the large presences of Gd3+ ions in compound 1-(Gd18Ni24)nare conducive to the fantastic MCE, and the value of-ΔS_(m)is 35.30 J kg^(-1)K^(-1) at 3.0 K and ΔH = 7.0 T. And more significantly, compound 1-Gd_(18)Ni_(24)n shows the large low-field magnetic entropy change(-ΔS_(m)= 20.95 J kg(-1) K(-1) at 2.0 K and ΔH = 2.0 T)among the published 3 d-4 f mixed metal clusters.