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The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd38(ClO4)6} ( 1) and {Gd48Cl2(NO3)} ( 2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd38(ClO4)6}, encapsulating six ClO4− ions, features a cage core composed of twelve vertex-sharing {Gd4} tetrahedrons and one Gd⋅⋅⋅Gd pillar. When Cl− and NO3− were incorporated in the reaction instead of ClO4−, {Gd48Cl2(NO3)} is obtained with a barrel shape constituted by twelve vertex-sharing {Gd4} tetrahedrons and six {Gd5} pyramids. What is more, the cage-like {Gd38} can be dynamically converted into the barrel-shaped {Gd48} upon Cl− and NO3− stimulus. To our knowledge, it is the first time that the linear M-O-M′ fashion and the unique μ8-ClO4− mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg−1 K−1 and mJ cm−3 K−1 on account of the weak antiferromagnetic exchange, the high NGd/ MW ratio (magnetic density), and the relatively compact crystal lattice (mass density). [ABSTRACT FROM AUTHOR]

Two kinds of inorganic gadolinium(III)-hydroxy 'ladders', [2× n] and [3× n], were successfully trapped in succinate (suc) coordination polymers, [Gd2(OH)2(suc)2(H2O)] n ⋅ 2 n H2O ( 1) and [Gd6(OH)8(suc)5(H2O)2] n ⋅4 n H2O ( 2), respectively. Such coordination polymers could be regarded as alternating inorganic-organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (Δ H=70 kG) 42.8 J kg−1 K−1 for complex 1 and 48.0 J kg−1 K−1 for complex 2. The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm−3 K−1 for complexes 1 and 2, respectively. [ABSTRACT FROM AUTHOR]