Porous metal oxides nanomaterials with controlled morphology have received great attention because of their promising applications in catalysis, energy storage and conversion, gas sensing, etc. In this paper, porous Co3O4 concave nanocubes extremely high specific surface area (120.9 m(2)·g(-1)) were synthesized simply by calcining Co-based metal-organic framework (Co-MOF, ZIF-67) templates at the optimized temperature (300 °C), formation mechanism such highly structures as well influence...

Metal–organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well catalysis. In contrast, research concerning potential uses electronic devices (such sensors) is its infancy, which might be due to a great challenge the fabrication of MOFs semiconductor composites with well-designed structures. this paper, we proposed simple self-template strategy fabricate metal oxide semiconductor@MOF core–shell...

Four 52-metal-ion 3d-4f cluster complexes featuring a common core of Ln(42)M(10) (Ln = Gd(3+), Dy(3+); M Co(2+/3+), Ni(2+)) were obtained through self-assembly the metal ions templated by mixed anions (ClO(4)(-) and CO(3)(2-)). Magnetic studies revealed that Gd(42)Co(10) Gd(42)Ni(10) clusters exhibit largest magnetocaloric effect (MCE) among any known complexes. Replacement Gd(3+) with anisotropic Dy(3+) caused significant changes in magnetic behavior clusters; both Dy(42)Co(10) Dy(42)Ni(10)...

The hydrolysis of Ln(ClO4)3 in the presence acetate leads to assembly three largest known lanthanide-exclusive cluster complexes, [Nd104(ClO4)6(CH3COO)60(μ3-OH)168(μ4-O)30(H2O)112]·(ClO4)18·(CH3CH2OH)8·xH2O (1, x ≈ 158) and [Ln104(ClO4)6(CH3COO)56(μ3-OH)168(μ4-O)30(H2O)112]·(ClO4)22·(CH3CH2OH)2·xH2O (2, Ln = Nd; 3, Gd; 140). structure common 104-lanthanide core, abbreviated as Ln8@Ln48@Ln24@Ln24, features a four-shell arrangement metal atoms contained an innermost cube (a Platonic solid)...

A chiral, cagelike, high-nuclearity lanthanide hydroxide cluster containing 60 Er(III) ions is reported. The core possesses a fascinating sodalite-like structure with 24 vertex-sharing cubane-like [Er(4)(mu(3)-OH)(4)](8+) units. hexagonal face of the sodalite cage features templating mu(6)-CO(3)(2-) ion. Magnetic studies revealed weak antiferromagnetic interactions.

A tubelike metal cluster containing 36 Gd and 12 Ni atoms was obtained by anion-templated self-assembly of the ions (see picture for arrangement 48 in core). The huge cryogenic magnetocaloric effects exhibited this plot magnetic entropy change ΔSm) can be rationalized terms its large metal/ligand mass ratio. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted...

Nanoscale inorganic wheel-shaped structures are one of the most striking types molecular aggregations. Here, we report synthesis a gigantic lanthanide wheel cluster containing 140 Gd3+ atoms. As largest reported thus far, {Gd140} features an attractive wheel-like structure with 10-fold symmetry. The nanoscopic possesses diameter 6.0 nm and displays high stability in solution, which allows direct visualization by scanning transmission electron microscopy. newly discovered represents new member family.

ConspectusHigh-nuclearity cluster-type metal complexes are a unique class of compounds, many which have aesthetically pleasing molecular structures. Their interesting physical and chemical properties arise primarily from the electronic and/or magnetic interplay between component ions. Among extensive studies in past two decades, those on lanthanide-containing clusters, lanthanide-exclusive or heterometallic with transition elements, most notable. The research was driven by both synthetic...

Metal-organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of Ni-containing polyoxometalate (POM) [Ni4 (H2 O)2 (PW9 O34 )2 ](10-) (Ni4 P2 ) into two highly stable and porous phosphorescent MOFs. The proximity Ni4 photosensitizers @MOF allows facile multi-electron transfer enable efficient visible-light-driven hydrogen evolution reaction...

Photocatalytic reduction of CO2 is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that large porous stable metal-organic framework featuring dinuclear Eu(III)2 clusters as connecting nodes Ru(phen)3-derived ligands linkers constructed catalyze visible-light-driven reduction. Photo-excitation the metalloligands initiates electron injection into generate...

The intelligent responsive drug delivery system has great application potential in cancer precision therapy. Although many antitumor methods have been developed based on systems, most of them yet suffer from poor efficiency. In this project, a near-infrared and pH dual-response multimodal collaborative platform for diagnosis treatment (PCN-DOX@PDA) was constructed. We used PCN-600 as vehicle loaded with antineoplastic drugs polydopamine (PDA). Under 633 nm laser irradiation, the ligand...

The discovery of fullerenes in 1985 opened a new chapter the chemistry highly symmetric molecules. Fullerene-like metal clusters, characterized by (multi)shell-like structures, are one rapidly developing class molecules that share this shape. In addition to creating aesthetically pleasing molecular ordered arrangement atoms within such frameworks provides opportunity develop materials with properties not readily achieved corresponding mononuclear or lower-nuclearity complexes. Account, we...

Five Keggin-based 3D coordination polymers, namely, [Cu3(pz)3(PW12O40)] (pz = pyrazine) (1), [Cu3(2,3-Me2pz)3(PW12O40)] (2,3-Me2pz 2,3-dimethylpyrazine) (2), [Cu2(2,5-Me2pz)1.5(2,5-HMe2pz)(PW12O40)] (2,5-Me2pz 2,5-dimethylpyrazine) (3), [Cu3(2,3-Me2pz)3(PMo12O40)] (4), and [Ag3(pz)3(PW12O40)]·0.5H2O (5), were synthesized structurally characterized. Crystal data are as follows: trigonal, space group R3̄c, a 18.4070(14) Å, c 22.544(3) γ 120°, Z 6 for 1; orthorhombic, Pccn, 16.599(2) b...

A Russian doll: heterometallic 108-metal cluster featuring an unprecedented four-shell, nesting doll-like structure (see picture) and overall antiferromagnetic coupling is reported. Supporting information for this article available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z705731_s.pdf or from author. Please note: The publisher not responsible content functionality of any supporting supplied by authors. Any queries (other than missing content) should be directed to...

A structurally fascinating Keplerate magnetic cluster featuring an icosidodecahedron of Ni(II) ions encapsulating a dodecahedron La(III) was assembled under hydrothermal conditions starting with La(NO3)3, Ni(NO3)2, and iminodiacetic acid. The cage-like arrangement the two distinct sets metal manifests beauty symmetry as both ideally possess icosahedral (Ih) symmetry, highest possible for molecules. constitutes framework centers unusual spin topology. Interesting ferromagnetic interactions...

A series of polyoxometalates (POMs)-based coordination polymers, namely, {[Cu(2,3-Me2pz)(2,5-Me2pz)0.5]4(SiW12O40)(2,5-Me2pz)}n (2,3-Me2pz = 2,3-dimethylpyrazine; 2,5-Me2pz 2,5-dimethylpyrazine; 1), {[Cu2(4,4'-bipy)4(H2O)4](SiW12O40)(H2O)18}n (4,4'-bipy 4,4'-bipyridine; 2), {[Cu(2-Mepz)1.5]3(PMo12O40)(H2O)3.5}n (2-Mepz 2-methylpyrazine; 3), {[Ag(2,3-Me2pz)1.5]4(SiW12O40)}n (4), {[Cu(pz)1.5]4(SiW12O40)(H2O)3}n (pz pyrazine; 5), {[Cu(2,3-Me2pz)1.5]4(SiW12O40)}n (6),...

Two rarely seen 2D coordination polymers based on huge 36-metal pure lanthanide clusters, {[Gd36(NA)36(OH)49(O)6(NO3)6(N3)3(H2O)20]Cl2·28H2O}n (1) and {[Dy36(NA)36(OH)49(O)6(NO3)6(N3)3(H2O)20]Cl2·28H2O}n (2) (HNA = nicotinic acid), were synthesized structurally characterized. The spherical Ln36 skeleton can be viewed as the aggregation of one cyclohexane chair-like Ln24 wheel two identical tripod-like Ln6 units. carboxylic groups NA ligands with Ln(III) cations results in a square layer....

We report the rational design of coordination-driven self-assembly metal-organic nanostructures for multifunctional nanotheranostics. Zinc(II) coordination-based nano-formulations capable loading indocyanine green (ICG) and therapeutic genes were prepared to achieve a fluorescence/photoacoustic imaging-guided combination photo/gene therapy strategy. showed enhanced theranostic capability zinc(II)-dipicolylamine-assisted assembly ICG, as well simultaneous targeted gene delivery in an...

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 strategy enhanced hydrogen evolution by loading atomically precise 4f-3d Ln52 Ni56 on CdS photoabsorber surface. Interestingly, some Ni2+ ions in the were exchanged Cd2+ to form Ni56-x Cdx /CdS composites. Photocatalytic studies show that efficient multipath charge separation...

Two record-large odd-numbered Ln₂₇ lanthanide clusters, each one featuring CO₃²⁻ and eight ClO₄⁻ groups as mixed anion templates, were obtained by controlling the hydrolysis of Ln³⁺ ions in presence simple propionate ligands.

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 chance to insight assemble process of and guides construction high-nuclearity metal clusters on basis reaction Ti(Oi Pr)4 , Eu(acac)3 salicylic acid. The time-dependent HRESI-MS indicates not only a Eu3 Ti block can be formed, but it further into Eu24 Ti8 compound. Temperature-dependent...

The assembly of gigantic heterometallic metal clusters remains a great challenge for synthetic chemistry. Herein, based on the slow release strategy lanthanide ions and in situ formation lacunary polyoxometalates, two giant 3d-4f polyoxometalate inorganic [LaNi12 W35 Sb3 P3 O139 (OH)6 ]23- (LaNi12 ) [La10 Ni48 W140 Sb16 P12 O568 (OH)24 (H2 O)20 ]86- (La10 are obtained. nanoscopic cluster La10 possesses super tetrahedron structure, which can be viewed as from four LaNi12 molecules...