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Lanthanoid pyridyl-β-diketonate ‘triangles’. New examples of single molecule toroics
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-10-20 , DOI: 10.1039/d0dt02855j
Chiara Caporale 1, 2, 3, 4 , Alexandre N. Sobolev 4, 5, 6, 7, 8 , Wasinee Phonsri 4, 9, 10, 11 , Keith S. Murray 4, 9, 10, 11 , Abinash Swain 12, 13, 14, 15 , Gopalan Rajaraman 12, 13, 14, 15 , Mark I. Ogden 1, 2, 3, 4 , Massimiliano Massi 1, 2, 3, 4 , Rebecca O. Fuller 1, 2, 3, 4, 16
Affiliation  

Trinuclear lanthanoid clusters have been synthesised and investigated as toroidal spin systems. A pyridyl functionalised β-diketonate, 1,3-bis(pyridin-2-yl)propane-1,3-dione (o-dppdH) has been used to synthesise a family of clusters of the form [Dy3(OH)2(o-dppd)3Cl2(H2O)4]Cl2·7H2O (1), [Tb3(o-dppd)33-OH)2(CH3CH2OH)3Cl3][Tb3(o-dppd)33-OH)2(H2O)(CH3CH2OH)2Cl3]Cl2·H2O (2), [Ho3(OH)2(o-dppd)3Cl(H2O)5]Cl3·3H2O (3) and [Er3(OH)2(o-dppd)3Cl2(H2O)3(CH3OH)]Cl2·3H2O·CH3OH (4). Despite the previous occurrence of this structural motif in the literature, these systems have not been widely investigated in terms of torodic behaviour. Magnetic studies were used to further characterise the complexes. DC susceptibility studies support weak antiferromagnetic exchange in the complexes. Slow magnetic relaxation behaviour is observed in the dynamic AC magnetic studies for complex 1. Theoretical studies predict that complex 1 and 3 have a non-magnetic ground state based on a toroidal arrangement of spins. Changes to the coordination environment in 2 do not support a toroic spin state. The prolate nature of the ErIII centres in complex 4 and large transverse anisotropy do not support the toroidal arrangement of lanthanoid spins in the complex.

中文翻译:

镧系吡啶基-β-二酮酸酯的“三角形”。单分子环网的新例子

三核镧系簇已经合成并研究为环向自旋系统。吡啶基官能化的β-二酮酸酯1,3,3-双(吡啶-2-基)丙烷-1,3-二酮(o -dppdH)已用于合成[Dy 3(OH)2ø -dppd32(H 2 O)4 ]氯2 ·7H 2 O(1),[TB 3ø -dppd3(μ 3 -OH)2(CH 3 CH 2 OH)3CL 3 ] [TB 3ø -dppd3(μ 3 -OH)2(H 2 O)(CH 3 CH 2 OH)2 CL 3 ] CL 2 ·H 2 O(2),[HO 3(OH )2o -dppd3 Cl(H 2 O)5 ] Cl 3 ·3H 2 O(3)和[Er 3(OH)2o -dppd3 Cl 2(H 2 O) 3(CH 3 OH)] Cl 2 ·3H 2 O·CH 3 OH( 4)。尽管先前在文献中出现了这种结构基序,但尚未就环行行为研究这些系统。磁性研究用于进一步表征复合物。DC磁化率研究支持复合物中弱的反铁磁交换。在复合物1的动态AC磁研究中观察到慢的磁弛豫行为。理论研究预测复合物13具有基于自旋的环形排列的非磁性基态。2中对协调环境的更改不支持强力旋转状态。Er III中心在复合物4中的长圆形性质和较大的横向各向异性不支持镧系元素自旋在复合物中的环形排列。
更新日期:2020-11-22
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