Yang Meng, Xie Jing, Sun Zan, Li Licun, Sutter Jean-Pascal
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry and Tianjin Key Laboratory of Metal and Molecule-based Material Chemistry, College of Chemistry, Nankai University , Tianjin 300071, China.
Laboratoire de Chimie de Coordination (LCC), CNRS , 205 Route de Narbonne, F-31077 Toulouse, France.
Inorg Chem. 2017 Nov 6;56(21):13482-13490. doi: 10.1021/acs.inorgchem.7b02204. Epub 2017 Oct 9.
Ladder-type and chain 2p-3d-4f complexes based on a bridging nitronyl nitroxide radical, namely, [LnCu(hfac)(NIT-Ph-p-OCHtrz)]·0.5CH [Ln = Y (1a), Dy (1b)] and [LnCu(hfac)(NIT-Ph-p-OCHtrz)] [Ln = Y (2a), Dy (2b); NIT-Ph-p-OCHtrz = 2-[4-[(1H-1,2,4-triazol-1-yl)methoxy]phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; hfac = hexafluoroacetylacetonate) have been successfully achieved through a one-pot reaction of the NIT-Ph-p-OCHtrz radical with Cu(hfac) and Ln(hfac)·2HO. Complexes 1a and 1b feature a ladder-like structure, where the rails are made of Ln(III) and Cu(II) ions alternatively bridged by nitronyl nitroxide and the triazole units while the NIT-Ph-p-OCHtrz moieties act as the rungs of the ladder. Complexes 2a and 2b consist of one-dimensional nitronyl nitroxide bridged Ln coordination polymers with dangly Cu(II) units connected to the triazole moieties. All of compounds exhibit ferromagnetic NIT-Dy and/or NIT-Cu interactions. Both Dy derivatives (1b and 2b) show frequency-dependent out-of-phase magnetic susceptibility signals in a zero field indicating slow magnetic relaxation behavior.
基于桥连硝酰氮氧自由基的梯型和链状2p - 3d - 4f配合物，即[LnCu(hfac)(NIT - Ph - p - OCHtrz)]·0.5CH [Ln = Y (1a)，Dy (1b)]和[LnCu(hfac)(NIT - Ph - p - OCHtrz)] [Ln = Y (2a)，Dy (2b)；NIT - Ph - p - OCHtrz = 2 - [4 - [(1H - 1,2,4 - 三唑 - 1 - 基)甲氧基]苯基]-4,4,5,5 - 四甲基咪唑啉 - 1 - 氧基 - 3 - 氧化物；hfac = 六氟乙酰丙酮)已通过NIT - Ph - p - OCHtrz自由基与Cu(hfac)和Ln(hfac)·2HO的一锅法反应成功合成。配合物1a和1b具有梯状结构，其中“轨道”由Ln(III)和Cu(II)离子交替通过硝酰氮氧和三唑单元桥连而成，而NIT - Ph - p - OCHtrz部分充当梯子的“横档”。配合物2a和2b由一维硝酰氮氧桥连的Ln配位聚合物组成，带有连接到三唑部分的悬垂Cu(II)单元。所有化合物均表现出铁磁性的NIT - Dy和/或NIT - Cu相互作用。两种Dy衍生物(1b和2b)在零场中均显示出频率依赖性的异相磁化率信号，表明存在慢磁弛豫行为。
