A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds

Fraser Hector W. L.; Smythe Lucy; Dey Sourav; Nichol Gary S.; Piligkos Stergios; Rajaraman Gopalan; Brechin Euan K.

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A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds

机译：构建铁磁性耦合Cr（III）化合物的简单方法

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A large family of chromium(iii) dimers has been synthesised and magneto-structurally characterised using a combination of carboxylate and diethanolamine type ligands. The compounds have the general formula [Cr-2(R-1-deaH)(2)(O2CR2)Cl-2]Cl where R-1 = Me and R-2 = H (1), Me (2), CMe3 (3), Ph (4), 3,5-(Cl)(2)Ph (5), (Me)(5)Ph (6), R-1 = Et and R-2 = H (7), Ph (8). The compound [Cr-2(Me-deaH)(2)Cl-4] (9) was synthesised in order to study the effect of removing/adding the carboxylate bridge on the observed magnetic behaviour. Direct current (DC) magnetic susceptibility measurements showed ferromagnetic (FM) exchange interactions between the Cr(iii) centres in the carboxylate bridged family with coupling constants in the range +0.37 J +8.02 cm(-1). Removal of the carboxylate to produce the dialkoxide-bridged compound 9 resulted in antiferromagnetic (AFM) exchange between the Cr(iii) ions. DFT calculations reveal the ferromagnetic exchange is the result of an orbital counter-complementarity effect occuring upon introduction of the bridging carboxylate.

机译：已经合成了大型铬（III）二聚体和磁性结构表征，使用羧酸盐和二乙醇胺类型配体的组合。该化合物具有通式[Cr-2（R-1-DEAH）（2）（2）（O2CR2）Cl-2] Cl，其中R-1 = Me和R-2 = H（1），Me（2），CME3 （3），pH（4），3,5-（CL）（2）pH（5），（ME）（5）pH（6），R-1 = ET和R-2 = H（7）， pH（8）。合成化合物[Cr-2（ME-DEAH）（2）CL-4]（9）以研究除去/加入羧酸桥对观察到的磁性行为的影响。直流（DC）磁性敏感性测量显示羧酸盐桥接家族中Cr（III）中心之间的铁磁性（FM）交换相互作用，其+ 0.37°且偶联常数在+ 0.37°且厚度范围内。 j＆ +8.02 cm（-1）。除去羧酸盐以产生二烷氧化物桥接化合物9，导致Cr（III）离子之间的反铁磁体（AFM）交换。 DFT计算揭示了铁磁交换是在引入桥接羧酸盐时行动的轨道反互补效果的结果。

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《Dalton transactions: An international journal of inorganic chemistry》 |2018年第24期|共10页
作者
Fraser Hector W. L.; Smythe Lucy; Dey Sourav; Nichol Gary S.; Piligkos Stergios; Rajaraman Gopalan; Brechin Euan K.;
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Univ Edinburgh EaStCHEM Sch Chem David Brewster Rd Edinburgh EH9 3FJ Midlothian Scotland;

Univ Edinburgh EaStCHEM Sch Chem David Brewster Rd Edinburgh EH9 3FJ Midlothian Scotland;

Indian Inst Technol Dept Chem Bombay 400076 Maharashtra India;

Univ Edinburgh EaStCHEM Sch Chem David Brewster Rd Edinburgh EH9 3FJ Midlothian Scotland;

Univ Copenhagen Dept Chem Univ Pk 5 DK-2100 Copenhagen Denmark;

Indian Inst Technol Dept Chem Bombay 400076 Maharashtra India;

Univ Edinburgh EaStCHEM Sch Chem David Brewster Rd Edinburgh EH9 3FJ Midlothian Scotland;

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中图分类化学;无机化学;
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A simple methodology for constructing ferromagnetically coupled Cr(iii) compounds

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