Zhang Li-Chuan, Zhang Lizhi, Qin Guangzhao, Zheng Qing-Rong, Hu Ming, Yan Qing-Bo, Su Gang
Center of Materials Science and Optoelectronics Engineering , College of Materials Science and Opto-Electronic Technology , University of Chinese Academy of Sciences , Beijing 100049 , China . Email:
Peter Grünberg Institut and Institute for Advanced Simulation , Forschungszentrum Jülich , JARA , 52425 Jülich , Germany.
Chem Sci. 2019 Sep 25;10(44):10381-10387. doi: 10.1039/c9sc03816g. eCollection 2019 Nov 28.
Inspired by the successful synthesis of Fe/Cu-5,5'-bis(4-pyridyl)(2,2'-bipirimidine) (PBP), a family of two-dimensional (2D) metal-organic frameworks (MOFs) with the Shastry-Sutherland lattice, , transition metal (TM)-PBP (TM = Cr, Mn, Fe, Co, Ni, Cu, Zn) has been systematically investigated by means of first-principles density functional theory calculations and Monte Carlo simulations. Mn-PBP is discovered to be the first ferromagnetic 2D MOF with the Shastry-Sutherland lattice and the Curie temperature is predicted to be about 105 K, while Fe-PBP, TM-PBP (TM = Cr, Co, Ni) and TM-PBP (TM = Cu, Zn) are found to be stripe-order antiferromagnetic, magnetic-dimerized and nonmagnetic, respectively. The electronic structure calculations reveal that TM-PBP MOFs are semiconductors with band gaps ranging from 0.12 eV to 0.85 eV, which could be easily modulated by various methods. Particularly, Mn-PBP would exhibit half-metallic behavior under compressive strain or appropriate electron/hole doping and a Mn-PBP based spintronic device has been proposed. This study not only improves the understanding of the geometric, electronic and magnetic properties of the 2D TM-PBP MOF family, but also provides a novel spin lattice playground for the research of 2D magnetic systems, which has diverse modulating possibilities and rich potential applications.
受成功合成Fe/Cu - 5,5'-双(4 - 吡啶基)(2,2'-联嘧啶)(PBP)的启发，一系列具有沙斯特里 - 萨瑟兰晶格的二维(2D)金属有机框架(MOF)，即过渡金属(TM) - PBP(TM = Cr、Mn、Fe、Co、Ni、Cu、Zn)，已通过第一性原理密度泛函理论计算和蒙特卡罗模拟进行了系统研究。发现Mn - PBP是首个具有沙斯特里 - 萨瑟兰晶格的铁磁二维MOF，其居里温度预计约为105 K，而Fe - PBP、TM - PBP(TM = Cr、Co、Ni)和TM - PBP(TM = Cu、Zn)分别被发现为条纹有序反铁磁、磁二聚化和非磁性的。电子结构计算表明，TM - PBP MOF是带隙范围从0.12 eV到0.85 eV的半导体，可通过各种方法轻松调制。特别地，Mn - PBP在压缩应变或适当的电子/空穴掺杂下将表现出半金属行为，并已提出基于Mn - PBP的自旋电子器件。这项研究不仅增进了对二维TM - PBP MOF家族的几何、电子和磁性性质的理解，还为二维磁系统的研究提供了一个新颖的自旋晶格平台，具有多样的调制可能性和丰富的潜在应用。
