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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterization of homo- and heterovalent tetra- hexa- hepta- and decanuclear manganese clusters using pyridyl functionalized β-diketone, carboxylate and triethanolamine ligands
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Synthesis and characterization of homo- and heterovalent tetra- hexa- hepta- and decanuclear manganese clusters using pyridyl functionalized β-diketone, carboxylate and triethanolamine ligands

机译：吡啶基官能化的β-二酮，羧酸盐和三乙醇胺配体的合成和表征四价六方庚烷和十价六方锰簇

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摘要

The syntheses and characterizations are reported for six new homo- and heterovalent manganese clusters, utilizing pyridyl functionalized β-diketones ligands. The reaction of the trinuclear complex [Mn _3O(O_2CPh)_6(H_2O)(Py)_2] with 1,3-di(pyridine-2-yl)propane-1,3-dione (dppdH) in CH_2Cl _2 resulted in a mixed-valence Mn_3~(II)Mn _6~(III)Mn~(IV) decanuclear cluster of formula [Mn_(10)O_7(dppd)_3(O_2CPh) _(11)]·4CH_2Cl_2 (1). The structure of the core of 1 is based upon a centred tricapped trigonal prism. Reacting Mn(BF _4)_2·xH_2O with dppdH and triethylamine (NEt_3) in CH_2Cl_2-MeOH gave a rare, homoleptic hexanuclear cluster of formula [Mn~(II)_6(dppd) _8][BF_4]_4 (2) which has a triangular based core. Reaction of Mn(Y)_2·xH_2O, Y = NO_3~- or BF_4~-, with dppdH or 1-phenyl-3-(2-pyridyl) propane-1,3-dione (pppdH) in the presence of triethanolamine (teaH_3) and NEt_3 gave a heptanuclear 'disc' like manganese core of general formula [Mn~(II)_7(X)_6(tea)(OH)_3][Y] _2·solv (3) X = pppd~- or dppd~- and Y = NO_3~- or BF_4~-. The addition of N-(2-pyridinyl)acetoacetamide (paaH) to Mn(Y)_2·4H_2O Y = NO_3~- or ClO_4~- in MeOH gave a second divalent heptanuclear cluster with a 'disc'-like core of general formula [Mn_7(paa)_6(OMe)_6][X]_2·solv (4) (X = NO_3~- or ClO_4~-), whilst the addition of paaH to a mixture of Mn(NO_3)_2·4H _2O, teaH_3 and NEt_3 in CH_2Cl _2-MeOH resulted in the formation of a mixed-valence Mn _2~(II)Mn_2~(III) tetranuclear 'butterfly' complex of formula [Mn_4(paa)_4(teaH)_2][NO _3]_2·2MeOH·2CH_2Cl_2 (5). Compound 5 displays the rare Mn~(II/III) oxidation state distribution of the body positions being Mn~(II) while the wing tips are Mn ~(III). The in situ formation of the tetranuclear [Mn _4(teaH)_2(teaH_2)_2(O _2C(CH_3)_3)_2][O_2C(CH _3)_3]_2'butterfly' complex followed by the addition of Mn(O_2CMe)_2·4H_2O resulted in a mixed-valence Mn_4~(II)Mn~(III)Mn~(IV) hexanuclear species of formula [Mn_6O_2(teaH _2)_4(O_2CMe)_4][NO_3] _2[O_2CMe]·CH_2Cl _2·MeOH·2H_2O (6). The core of 6 displays a face sharing dicubane topology. Compounds 1 and 6 both display novel trapped-valence metal cores containing three different oxidation states on the manganese ion. Compounds 1, 2 and 3 are the first manganese based dppd clusters, while 4 and 5 are the first with the pyridylamino-substituted β-diketone ligand (paaH). The magnetic data for 1, 2, 3, 4, and 6 are dominated by antiferromagnetic interactions within the clusters, leading to small ground spin values of S = 1 for 1, S = 3 for 2, S = ~5/_2 for 3, S = ~5/_2 for 4 and S = ~1/_2 for 6. Compound 5, however, displays overall ferromagnetic interactions with the data indicating an S = 6 ground state. 5 also exhibits probable single molecule magnet behaviour as indicated by frequency dependent out-of-phase χ_M′′ peaks in the AC susceptibility measurements.
机译：报道了利用吡啶基官能化的β-二酮配体对六个新的同价和异价锰簇的合成和表征。三核络合物[Mn _3O（O_2CPh）_6（H_2O）（Py）_2]与1,3-二吡啶-2-基丙烷-1,3-二酮（dppdH）在CH_2Cl _2中的反应式[Mn_（10）O_7（dppd）_3（O_2CPh）_（11）]·4CH_2Cl_2（1）的混合价Mn_3〜（II）Mn_6〜（III）Mn〜（IV）十核簇。 1的核的结构基于居中的三棱柱三角棱镜。将Mn（BF _4）_2·xH_2O与dppdH和三乙胺（NEt_3）在CH_2Cl_2-MeOH中反应，得到一种稀有的均相六核簇，式[Mn〜（II）_6（dppd）_8] [BF_4] _4（2）基于三角形的核心。 Mn（Y）_2·xH_2O，Y = NO_3〜-或BF_4〜-在三乙醇胺存在下与dppdH或1-苯基-3-（2-吡啶基）丙烷-1,3-二酮（pppdH）的反应（ teaH_3）和NEt_3给出了类似通式[Mn〜（II）_7（X）_6（tea）（OH）_3] [Y] _2·solv（3）的锰核的七核“盘”，X = pppd〜-或dppd〜-和Y = NO_3〜-或BF_4〜-。将N-（2-吡啶基）乙酰乙酰胺（paaH）添加到MeOH中的Mn（Y）_2·4H_2O Y = NO_3〜-或ClO_4〜-中，得到第二个二价七核簇，其通式为“盘”状核心[Mn_7（paa）_6（OMe）_6] [X] _2·solv（4）（X = NO_3〜-或ClO_4〜-），同时在Mn（NO_3）_2·4H _2O的混合物中添加paaH， CH_2Cl _2-MeOH中的teaH_3和NEt_3导致形成式[Mn_4（paa）_4（teaH）_2] [NO _3]的混合价Mn _2〜（II）Mn_2〜（III）四核“蝴蝶”配合物_2·2MeOH·2CH_2Cl_2（5）。化合物5显示出罕见的Mn〜（II / III）氧化态分布，其身体位置为Mn〜（II），而翼尖为Mn〜（III）。四核[Mn _4（teaH）_2（teaH_2）_2（O _2C（CH_3）_3）_2] [O_2C（CH _3）_3] _2'蝴蝶'络合物的原位形成，然后添加Mn（O_2CMe） _2·4H_2O生成式[Mn_6O_2（teaH _2）_4（O_2CMe）_4] [NO_3] _2 [O_2CMe]·CH_2Cl _2的混合价态Mn_4〜（II）Mn〜（III）Mn〜（IV）六核物种·MeOH·2H_2O（6）。 6的核心显示一个共享面部的Dicubane拓扑。化合物1和6均显示出新颖的陷阱价金属核，在锰离子上含有三种不同的氧化态。化合物1、2和3是第一个基于锰的dppd簇，而化合物4和5是第一个具有吡啶基氨基取代的β-二酮配体（paaH）的簇。 1、2、3、4和6的磁数据受团簇内反铁磁相互作用的支配，从而导致较小的地面自旋值为S = 1等于1，S = 3等于2，S =〜5 / _2等于3 ，对于4，S =〜5 / _2，对于6，S =〜1 / _2，但是化合物5显示了总体铁磁相互作用，并且数据表明S = 6基态。图5还显示了可能的单分子磁体行为，如在交流磁化率测量中由频率相关的异相χ_M''峰所示。

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