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 heterometall...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.展开更多
基金supported by the Natural Science Foundation of China (No. 21571103)Jiangsu (No. BK20191359)the Project of Natural Science Foundation of the Higher Education Institutions of Anhui Province, China (No. KJ2019A0350)。
文摘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.
