Wang Qin, Wang Ji-Lei, Yu Ya-Ting, Xu Hu, Bai Xu, Zeng Ying-Ying, Kan Zhi-Yuan, Xu Yan
College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China.
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China.
Inorg Chem. 2024 Jan 8;63(1):613-620. doi: 10.1021/acs.inorgchem.3c03504. Epub 2023 Dec 15.
The self-assembly of the lanthanide metal-organic frameworks presents a formidable challenge but profound significance. Compared with the metal-organic frameworks based on 4f-3d ions, the chemistry of 4f-3p metal-organic frameworks has not been fully explored so far. In this study, two lanthanide-aluminum-based clusters [LnAl(IN)(μ-OH)(μ-O)(HO)]·HO ( = 2, Ln = Gd, abbreviated as ; = 2.5, Ln = Eu, abbreviated as ; HIN = isonicotinic acid) have been meticulously designed and obtained by hydrothermal reaction at low pH. The crystallographic study revealed that both and clusters exhibit an unprecedented sandwiched metal-organic framework holding a highly ordered honeycomb network. To our knowledge, it is the first case of Ln-Al-based cluster-organic frameworks. Furthermore, magnetic investigation of manifests a decent magnetic entropy change of -Δ = 28.8 J kg K at 2 K for Δ = 7.0 T. Significantly, the introduction of Al ions into the lanthanide metal-organic frameworks displays excellent solid-state luminescent capability with a lifetime of 371.6 μs and quantum yield of 6.64%. The construction and investigation of these two Ln-Al clusters represent great progress in the 4f-3p metal-organic framework.
