Effects of Counterions, Coordination Anions, and Coordination Solvent Molecules on Single-Molecule Magnetic Behaviors and Nonlinear Optical Properties of Chiral Zn 2 Dy Schiff Base Complexes
Effects of Counterions, Coordination Anions, and Coordination Solvent Molecules on Single-Molecule Magnetic Behaviors and Nonlinear Optical Properties of Chiral Zn 2 Dy Schiff Base Complexes
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抗衡离子、配位阴离子和配位溶剂分子对手性 Zn 2 Dy 希夫碱配合物单分子磁行为和非线性光学性质的影响
DOI：
10.1021/acs.inorgchem.2c02743
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发表时间：
2022
影响因子：
4.6
通讯作者：
Xi-Li Li
中科院分区：
文献类型：
--
作者：
Cai-Ming Liu;Rong Sun;Bing Wu Wang;Xiang Hao;Xi-Li Li
通过改变对离子（clo4 -和cf3so3 -）和。配位阴离子（Cl−和Br−），考察了它们的影响。一类zn2dy手性单分子的结构和性能。基于一对手性席夫碱R，R- h 2l席夫和S，S- h 2l席夫的磁体(SMMs) = 2-((E)-(（1R,2R)-2-（(E)-2-.羟基-3-甲氧基苄基氨基）环己基甲基）-6-甲基。希夫= 2-((E)-（（1S,2S)-2-(E)-2-羟基-3-.甲氧基苄基氨基）环己基甲基）-6-甲氧基苯酚}。通过反应得到了三对手性zn2 / Dy席夫碱配合物。[dyzn2 (R,R- l Schiff)Cl 2 (h2o)]（cl4）·0.0.5 meoh·0.25 h2o （R-1）和[dyzn2 (S,S- l Schiff)Cl 2 (h2o)][dyzn2 (S,S- l)]。L Schiff) cl2 (MeOH)](clo4) 2·MeOH·0.5 h2o (S-1), [dyzn2 (R,R-L Schiff)-]。Cl 2 (h2o)]（cf3so3）·0.5MeOH （R-2）和[dyzn2 (S,S- l Schiff)Cl 2 (h2o)]-。[dyzn2 (S,S- l Schiff)Cl 2 (MeOH)](cf3so3) 2·MeOH （S-2）和[dyzn2 (R,R- l Schiff)Br 2 (h2o)]（cf3so3）·0.25MeOH （R-3）和。[dyzn2 (S,S- l Schiff) br2 (h2o)][dyzn2 (S,S- l Schiff) br2 (MeOH)](cf3so3) 2 （S-3）。他们都表现出良好的SMM行为，他们的。磁弛豫不仅受反离子（clo4−和cf3so3−）的调控，还受配位阴离子（Cl−和Br−）的调控；这些阴离子对二次谐波产生（SHG）和三次谐波产生（THG）也有重要影响。非线性光学性质。有趣的是，在s构型配合物中，配位溶剂分子上的dy3 +离子。一半的分子是甲醇分子而不是水分子。配位溶剂分子的变化可以。也显著影响SMM行为和SHG和THG非线性光学性质。此外，从头计算。合理地解释了SMM的性质。
By changing the counterions (ClO 4 − and CF 3 SO 3 − ) and.the coordination anions (Cl − and Br − ), we investigated their influences on.the structures and performances of a class of Zn 2 Dy chiral single-molecule.magnets (SMMs), which are based on a pair of chiral Schiff bases R,R-.H 2 L Schiff and S,S-H 2 L Schiff {R,R-H 2 L Schiff = 2-((E)-((1R,2R)-2-((E)-2-.hydroxy-3-methoxybenzylideneamino)cyclohexylimino)methyl)-6-me-.thoxyphenol and S,S-H 2 L Schiff = 2-((E)-((1S,2S)-2-((E)-2-hydroxy-3-.methoxybenzylideneamino)cyclohexylimino)methyl)-6-methoxyphenol}..Three pairs of chiral Zn 2 Dy Schiff base complexes were obtained by.directed synthesis, which are [DyZn 2 (R,R-L Schiff )Cl 2 (H 2 O)](ClO 4 )·.0.5MeOH·0.25H 2 O (R-1) and [DyZn 2 (S,S-L Schiff )Cl 2 (H 2 O)][DyZn 2 (S,S-.L Schiff )Cl 2 (MeOH)](ClO 4 ) 2 ·MeOH·0.5H 2 O (S-1), [DyZn 2 (R,R-L Schiff )-.Cl 2 (H 2 O)](CF 3 SO 3 )·0.5MeOH (R-2) and [DyZn 2 (S,S-L Schiff )Cl 2 (H 2 O)]-.[DyZn 2 (S,S-L Schiff )Cl 2 (MeOH)](CF 3 SO 3 ) 2 ·MeOH (S-2), and [DyZn 2 (R,R-L Schiff )Br 2 (H 2 O)](CF 3 SO 3 )·0.25MeOH (R-3) and.[DyZn 2 (S,S-L Schiff )Br 2 (H 2 O)][DyZn 2 (S,S-L Schiff )Br 2 (MeOH)](CF 3 SO 3 ) 2 (S-3). They all exhibit good SMM behaviors, and their.magnet relaxation is regulated by not only the counterions (ClO 4 − and CF 3 SO 3 − ) but also the coordination anions (Cl − and Br − );.these anions also have important effects on the second-harmonic generation (SHG) and third harmonic generation (THG).nonlinear optical properties. Interestingly, in the S-configuration complexes, the coordination solvent molecule of the Dy 3+ ion on.half of the molecules is the methanol molecule instead of the water molecule. This change in the coordinating solvent molecule can.also significantly affect the SMM behaviors and the SHG and THG nonlinear optical properties. Moreover, ab initio calculations.were applied to rationally explain the SMM properties.