Comprehensive Summary Herein, we describe the synthesis of a carborane-supported octanuclear palladacycle complex, Pd 8 ( o -C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (CH 3 CN) 4 (complex 1 ), with B(3)–H activations on o -carborane ligand. The substitution reaction of 1 has been explored, and three of its substituted complexes Pd 8 ( o -C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (L) 4 (L = t BuNC, 2 ; L = C 5 H 5 N, 3 ; L = C 4 H 8 S, 4 ) have been synthesized. The m - and p -carborane disubstituted ligands m - and p -C 2 B 10 H 10 (CS 2 CH 3 ) 2 (ligands 5 and 6 ) as well as their B—H activated carborane complexes [ m -C 2 B 10 H 9 (CS 2 CH 3 ) 2 PdCl] ( 7 ) and [ p -C 2 B 10 H 8 (CS 2 CH 3 ) 2 ][PdCl( t BuNC)] 2 ( 8 ) have also been synthesized by the similar method. All of these complexes have been characterized, including X-ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.
A series of tetranuclear lanthanide-based clusters [Ln4(dbm)6(L)2(CH3OH)4]·2CH3OH (Ln(III) = Gd (1), Dy (2), and Ho (3); H3L = 2-[(2-(hydroxyimino)propanehydrazide)methyl]-2,3-dihydroxybenzaldehyde, Hdbm = dibenzoylmethane) and octanuclear lanthanide-based clusters [Ln8(HL)10(CH3O)4(CH3OH)2]·6CH3OH (Ln(III) = Gd (4), Dy (5)) were assembled using a polydentate Schiff-base ligand H3L and two different β-diketone salts via a solvothermal method, and their structures and magnetic properties have been characterized. Interestingly, β-diketones play an important role in assembling and affecting the structures of Ln4 to Ln8 clusters. This is the first use of β-diketone to affect the structures of polynuclear Ln(III)-based clusters from linear-shaped Ln4 clusters to Ln8 clusters. Magnetic studies revealed that antiferromagnetic interactions exist in clusters 1-Gd4 and 4-Gd8. More importantly, clusters 1-Gd4 and 4-Gd8 display significant cryogenic magnetic refrigeration properties (−ΔSm = 24.88 J kg−1 K−1 for 1-Gd4 and −ΔSm = 32.52 J kg−1 K−1 for 4-Gd8); the results show that cluster 4-Gd8 exhibits a larger magnetocaloric effect than 1-Gd4. Cluster 2-Dy4 shows remarkable single-molecule magnet (SMM) behavior (ΔE/kB = 67.5 K and τ0 = 3.06 × 10−7 s) under a zero dc field, and 5-Dy8 exhibits a field-induced SMM-like behavior (ΔE/kB = 39.83 K and τ0 = 2.12 × 10−7 s) under a 5000 Oe dc field.
Crown-ether-like octanuclear polyoxymolybdenum(V) cluster (NH4)4[Mo8O8(μ2-OH)4(μ2-O)8(dmtrz)8]·62.5H2O (dmtrz = 3,5-dimethyltriazole, 1) was successfully synthesized by a hydrothermal method. Its lithium additives Li4[Mo8O8(μ2-OH)4(μ2-O)8(dmtrz)8]·2(Hdmtrz)·27H2O (2), Li4[Mo8O8(μ2-OH)4(μ2-O)8(dmtrz)8]·20.5H2O (3) and Li4[Mo8O8(μ2-OH)4(μ2-O)8(dmtrz)8]·25H2O (4) have also been obtained and fully characterized respectively. The lithium cations are in the forms of mononuclear, dinuclear and tetranuclear units. X-ray structural analyses show that polyoxometalate-based materials 1–4 constitute round pores formed by eight molybdenum-oxygen groups connected sequentially with sizes of 4.6 Å. With 1 as the basic framework, 2–4 combine lithium cations in the forms of different hydrates, respectively. In addition, 1 stacked up intermolecularly with pores of sizes 10.0 × 18.0 Å2, while 4 stacked up inter-molecularly with 6.0 × 4.0 Å2 in the a axis and 8.0 × 5.8 Å2 in the c axis, respectively. The results show that 1 can selectively adsorb CO2 and O2, respectively.
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