源自含叔丁基膦酸组装体系的一系列五核和四核锰（III）配合物的合成与表征

Synthesis and characterization of a family of penta- and tetra-manganese(III) complexes derived from an assembly system containing tert-butylphosphonic acid.

作者信息

Wang Mei, Ma Cheng-Bing, Yuan Da-Qiang, Wang Hui-Sheng, Chen Chang-Neng, Liu Qiu-Tian

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

出版信息

Inorg Chem. 2008 Jul 7;47(13):5580-90. doi: 10.1021/ic701343s. Epub 2008 Jun 10.

DOI:10.1021/ic701343s

PMID:18540593

Abstract

A family of manganese complexes, [Mn 5O 3( t-BuPO 3) 2(MeCOO) 5(H 2O)(phen) 2] ( 1), [Mn 5O 3( t-BuPO 3) 2(PhCOO) 5(phen) 2] ( 2), [Mn 4O 2( t-BuPO 3) 2(RCOO) 4(bpy) 2] (R = Me, ( 3); R = Ph, ( 4)), NBu (n) 4[Mn 4O 2(EtCOO) 3(MeCOO) 4(pic) 2] ( 5), NR' 4[Mn 4O 2( i-PrCOO) 7(pic) 2] (R' = Bu (n) , ( 6); R' = Et, ( 7)), were synthesized and characterized. The seven manganese clusters were all prepared from a reaction system containing tert-butylphosphonic acid, Mn(O 2CR) 2 (R = Me, Ph) and NR' 4MnO 4 (R' = Bu (n) , Et) with similar procedures except for using different N-containing ligands (1,10-phenanthroline (phen), 2,2'-bipyridine (bpy) and picolinic acid (picH)) as coligands. The structures of these complexes vary with the N-containing donors. Both the cores of complexes 1 and 2 feature three mu 3-O and two capping t-BuPO 3 (2-) groups bridging five Mn (III) atoms to form a basket-like cage structure. Complexes 3 and 4 both have one [Mn 4(mu 3-O) 2] (8+) core with four coplanar Mn (III) atoms disposed in an extended "butterfly-like" arrangement and two capping mu 3- t-BuPO 3 (2-) binding to three manganese centers above and below the Mn 4 plane. Complexes 5, 6, and 7 all possess one [Mn 4(mu 3-O) 2] (8+) core just as complexes 3 and 4, but they display a folded "butterfly-like" conformation with the four Mn (III) atoms nonplanar. Thus, the seven compounds are classified into three types, and three representative compounds 1.2H 2O.MeOH.MeCN , 3.6H 2O.2MeCOOH , and 5.0.5H 2O have been characterized by IR spectroscopy, ESI-MS spectroscopy, magnetic measurements and in situ UV-vis-NIR spectroelectrochemical analysis. Magnetic susceptibility measurements reveal the existence of both ferromagnetic and antiferromagnetic interactions between the adjacent Mn (III) ions in compound 1.2H 2O.MeOH.MeCN , and antiferromagnetic interactions in 3.6H 2O.2MeCOOH and 5.0.5H 2O. Fitting the experimental data led to the following parameters: J 1 = -2.18 cm (-1), J 2 = 6.93 cm (-1), J 3 = -13.94 cm (-1), J 4 = -9.62 cm (-1), J 5 = -11.17 cm (-1), g = 2.00 ( 1.2H 2O.MeOH.MeCN ), J 1 = -5.41 cm (-1), J 2 = -35.44 cm (-1), g = 2.13, zJ' = -1.55 cm (-1) ( 3.6H 2O.2MeCOOH ) and J 1 = -2.29 cm (-1), J 2 = -35.21 cm (-1), g = 2.02, zJ' = -0.86 cm (-1) ( 5.0.5H 2O ).

摘要

合成并表征了一系列锰配合物，[Mn₅O₃(t-BuPO₃)₂(MeCOO)₅(H₂O)(phen)₂] (1)、[Mn₅O₃(t-BuPO₃)₂(PhCOO)₅(phen)₂] (2)、[Mn₄O₂(t-BuPO₃)₂(RCOO)₄(bpy)₂] (R = Me, (3); R = Ph, (4))、NBu₄[Mn₄O₂(EtCOO)₃(MeCOO)₄(pic)₂] (5)、NR₄[Mn₄O₂(i-PrCOO)₇(pic)₂] (R = Bu₄, (6); R = Et, (7))。这七个锰簇合物均由包含叔丁基膦酸、Mn(O₂CR)₂ (R = Me, Ph) 和NR₄MnO₄ (R = Bu₄, Et) 的反应体系通过相似的步骤制备，只是使用了不同的含氮配体（1,10-菲咯啉 (phen)、2,2'-联吡啶 (bpy) 和吡啶甲酸 (picH)）作为共配体。这些配合物的结构随含氮供体的不同而变化。配合物1和2的核心均具有三个μ₃-O和两个盖帽的t-BuPO₃²⁻基团，它们桥连五个Mn(III)原子形成篮状笼状结构。配合物3和4均具有一个[Mn₄(μ₃-O)₂]⁸⁺核心，四个共面的Mn(III)原子呈伸展的“蝴蝶状”排列，两个盖帽的μ₃-t-BuPO₃²⁻与Mn₄平面上方和下方的三个锰中心结合。配合物5、6和7与配合物3和4一样，均具有一个[Mn₄(μ₃-O)₂]⁸⁺核心，但它们呈现出折叠的“蝴蝶状”构象，四个Mn(III)原子不共面。因此，这七个化合物分为三种类型，并且通过红外光谱、电喷雾电离质谱、磁性测量和原位紫外-可见-近红外光谱电化学分析对三种代表性化合物1·2H₂O·MeOH·MeCN、3·6H₂O·2MeCOOH和5·0·5H₂O进行了表征。磁化率测量表明，化合物1·2H₂O·MeOH·MeCN中相邻的Mn(III)离子之间同时存在铁磁和反铁磁相互作用，而在3·6H₂O·2MeCOOH和5·0·5H₂O中存在反铁磁相互作用。对实验数据进行拟合得到以下参数：J₁ = -2.18 cm⁻¹，J₂ = 6.93 cm⁻¹，J₃ = -13.94 cm⁻¹，J₄ = -9.62 cm⁻¹，J₅ = -11.17 cm⁻¹，g = 2.00 (1·2H₂O·MeOH·MeCN)，J₁ = -5.41 cm⁻¹，J₂ = -35.44 cm⁻¹，g = 2.13，zJ' = -1.55 cm⁻¹ (3·6H₂O·2MeCOOH) 以及J₁ = -2.29 cm⁻¹，J₂ = -35.21 cm⁻¹，g = 2.02，zJ' = -0.86 cm⁻¹ (5·0·5H₂O)。