An inverted triplesalen ligand by a convergent synthesis and its influence on trinuclear Fe_3~Ⅲ complexes  

作　　者：FELDSCHER Bastian KRICKEMEYER Erich MOSELAGE Marc THEIL Hubert HOEKE Veronika KAISER Yvonne STAMMLER Anja BGGE Hartmut GLASER Thorsten 

机构地区：[1]Lehrstuhl für Anorganische Chemie I, Fakultt für Chemie, Universitt Bielefeld, Universittsstr. 25, D-33615 Bielefeld, Germany

出　　处：《Science China Chemistry》2012年第6期951-966,共16页中国科学（化学英文版）

基　　金：supported by the Deutsche Forschungsgemeinschaft(FOR945 ‘Nanomagnets: from Synthesis via Interactions with Surfaces to Function’);the Fonds der Chemischen Industrie;Bielefeld University

摘　　要：The inverted triplesalen ligand H6feldMe has been synthesized from 2,4,6-triformyl-phloroglucinol and a ketimine salen half-unit in a convergent synthesis. NMR, IR, and UV-vis spectroscopy reveal that this ligand is not in the O-protonated tau- tomer but in the N-protonated tautomer with substantial heteroradialene contribution. This ligand and the conventional triple- salen ligand H6talent-au2 have been used to synthesize the trinuclear Fem complexes [（feldMe）（FeCl）3] and [（talent-Bu2）（FeC1）3], respectively. The molecular structures of these complexes were obtained by single-crystal X-ray diffraction. Two trinuclear Fem complexes of [（feldMe）（FeCl）3] dimerize via two Fe-phenolate bonds, whereas due to steric hindrance no dimerization is observed for [（talent-Bu2）（FeC1）3]. The structural data also reveal some heteroradialene contribution in the trinuclear complexes. Whereas UV-vis and MOlSbauer spectroscopy are not suitable to distinguish between the two complexes, FT-IR spectra show characteristic features due to the different substitution patterns of the conventional and the inverted triplesalen ligands. Another handle is provided by electrochemistry. Whereas both complexes exhibit an irreversible oxidation wave （0.94 V vs. Fc＋/Fc for [（feldMe）（FeC1）3] and 0.84 V vs. Fc~/Fc for [（talent-Bu2）（FeC1）3]）, which is assigned to the oxidation of the central backbone, higher potential oxidations are reversible for [（talent-Bu2）（FeC1）3]） but irreversible for [（feldMe）（FeC1）3]. This is attributed to the reversible oxidation of the terminal phenolates in the di-tert-butyl substituted [（talentBu2）（FeCl）3] in contrast to the mono-methyl-substituted phenolates in [（feld^ae）（FeC1）3]. The magnetic properties of [（talen^-Bu2）（FeC1）3] reveal a very small ferromagnetic coupling with significant zero-field splitting of the Feul S = 5/2 ions. In contrast, the dimerization of two trinu- clear complexes in [（feldMe）（FeCl）3] resultsThe inverted triplesalen ligand H 6 feld Me has been synthesized from 2,4,6-triformyl-phloroglucinol and a ketimine salen half-unit in a convergent synthesis. NMR, IR, and UV-vis spectroscopy reveal that this ligand is not in the O-protonated tautomer but in the N-protonated tautomer with substantial heteroradialene contribution. This ligand and the conventional triplesalen ligand H 6 talen t-Bu 2 have been used to synthesize the trinuclear Fe III complexes [(feld Me )(FeCl) 3 ] and [(talen t-Bu 2 )(FeCl) 3 ], respectively. The molecular structures of these complexes were obtained by single-crystal X-ray diffraction. Two trinuclear Fe III complexes of [(feld Me )(FeCl) 3 ] dimerize via two Fe-phenolate bonds, whereas due to steric hindrance no dimerization is observed for [(talen t-Bu 2 )(FeCl) 3 ]. The structural data also reveal some heteroradialene contribution in the trinuclear complexes. Whereas UV-vis and M bauer spectroscopy are not suitable to distinguish between the two complexes, FT-IR spectra show characteristic features due to the different substitution patterns of the conventional and the inverted triplesalen ligands. Another handle is provided by electrochemistry. Whereas both complexes exhibit an irreversible oxidation wave (0.94 V vs. Fc + /Fc for [(feld Me )(FeCl) 3 ] and 0.84 V vs. Fc + /Fc for [(talen t-Bu 2 )(FeCl) 3 ]), which is assigned to the oxidation of the central backbone, higher potential oxidations are reversible for [(talen t-Bu 2 )(FeCl) 3 ]) but irreversible for [(feld Me )(FeCl) 3 ]. This is attributed to the reversible oxidation of the terminal phenolates in the di-tert-butyl substituted [(talen t-Bu 2 )(FeCl) 3 ] in contrast to the mono-methyl-substituted phenolates in [(feld Me )(FeCl) 3 ]. The magnetic properties of [(talen t-Bu 2 )(FeCl) 3 ] reveal a very small ferromagnetic coupling with significant zero-field splitting of the FeⅢ S = 5/2 ions. In contrast, the dimerization of two trinuclear complexes in [(feld Me )(FeCl) 3 ] results in antiferromagnetic interactions betwe

关 键 词：magnetic properties iron complexes SPIN-POLARIZATION triplesalen 

分 类 号：O614.811[理学—无机化学]