Domański Mateusz, Mazej Zoran, Grochala Wojciech
Center of New Technologies, University of Warsaw, Zwirki i Wigury 93, 02-089, Warsaw, Poland.
Department of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova cesta 39, 1000, Ljubljana, Slovenia.
Chemistry. 2023 Nov 8;29(62):e202302042. doi: 10.1002/chem.202302042. Epub 2023 Oct 5.
Copper(II) silver(II) sulfate crystallizes in a monoclinic CuSO -related structure with P2 /n symmetry. This quasi-ternary compound features Ag(SO ) layers, while the remaining cationic sites may be occupied either completely or partially by Cu cations, corresponding to the formula of (Cu Ag )[Ag(SO ) ], x=0.6-1.0. CuAg(SO ) is antiferromagnetic with large negative Curie-Weiss temperature of -140 K and shows characteristic ordering phenomenon at 40.4 K. Density functional theory calculations reveal that the strongest superexchange interaction is a two-dimensional antiferromagnetic coupling within Ag(SO ) layers, with the superexchange constant J of -11.1 meV. This renders CuAg(SO ) the rare representative of layered Ag -based antiferromagnets. Magnetic coupling is facilitated by the strong mixing of Ag d(x -y ) and O 2p states. Calculations show that M sites in MAg(SO ) can be occupied with other similar cations such as Zn , Cd , Ni , Co , and Mg .
硫酸铜（II）银（II）以单斜晶系与硫酸铜相关的结构结晶，具有P2 /n对称性。这种准三元化合物具有Ag(SO ) 层，而其余阳离子位点可能被铜阳离子完全或部分占据，对应于化学式(Cu Ag )[Ag(SO ) ]，x = 0.6 - 1.0。CuAg(SO )是反铁磁性的，居里 - 外斯温度为-140 K，在40.4 K时表现出特征性的有序现象。密度泛函理论计算表明，最强的超交换相互作用是Ag(SO ) 层内的二维反铁磁耦合，超交换常数J为-11.1 meV。这使CuAg(SO )成为层状银基反铁磁体的罕见代表。Ag d(x -y )和O 2p态的强混合促进了磁耦合。计算表明，MAg(SO )中的M位点可以被其他类似阳离子如Zn 、Cd 、Ni 、Co 和Mg 占据。
