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首页> 外文期刊>RSC Advances >Structural and magnetic properties of heptacoordinated MnII complexes containing a 15-membered pyridine-based macrocycle and halido/pseudohalido axial coligands
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Structural and magnetic properties of heptacoordinated MnII complexes containing a 15-membered pyridine-based macrocycle and halido/pseudohalido axial coligands

机译：含有15-元吡啶基大环和哈利诺/伪己二核苷酸轴颈Coligands的略微庚络型MnII络合物的结构和磁性

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摘要

A series of heptacoordinated Mn ~(II) compounds with a pentadentate 15-membered pyridine-based macrocycle 15-pyN _(3) O _(2) (3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) and two axially coordinated halido/pseudohalido coligands (X), having a monomeric [Mn(15-pyN _(3) O _(2) )X _(2) ] (X = Br ~(?) ( 1 ), I ~(?) ( 2 ), N _(3) ~(?) ( 3 ), NCS ~(?) ( 4 )) or polymeric {[Mn(15-pyN _(3) O _(2) )X](ClO _(4) )} _( n ) (X = CN ~(?) ( 5 )) composition, was prepared and thoroughly characterized. Single crystal X-ray analysis of 2 , 3 and 4 determined the distorted pentagonal-bipyramidal geometry of the complexes. The analysis of the magnetic data of complexes 1–4 revealed non-zero values of the axial zero-field splitting parameter D (| D | < 0.7 cm ~(?1) ) and weak antiferromagnetic intermolecular interactions (molecular field correction parameter zj ≈ ?0.1 cm ~(?1) ). As for the 1D polymeric complex 5 , a small antiferromagnetic exchange coupling was found between Mn ~(II) centres, with J = ?1.72 cm ~(?1) . The experimentally obtained magnetic parameters ( J or zj ) were compared with those theoretically calculated at the DFT level in order to reveal the magnetic exchange pathways in 2–4 and to support the polymeric structure of 5 ( J ~(EXP) = ?2.79 cm ~(?1) vs. J ~(R) / J ~(Y) = ?2.54/?3.06 cm ~(?1) , when the dinuclear spin Hamiltonian was used). It has been also found that extensive systems of hydrogen bonds, non-covalent contacts and π–π stacking interactions present in the crystal structures of 2 , 3 and 4 have an impact on the formation of supramolecular 1D chains, and as a consequence of this on the magnetic properties of the complexes. Contrary to non-covalent contacts, the influence of the axial ligands on the magnetic nature of the complexes seems to be negligible.
机译：一系列庚烷等Mn〜（II）化合物，其具有戊向15-元吡啶基大环15-PYN _（3）O _（2）（3,12,18-Triaza-6,9-Dioxabicyclo [12.3.1] ] OctAdeca-1（18），14,16-三烯）和两个轴向协调的哈利诺/假卤酰基水菌（x），具有单体[Mn（15-pyn _（3）O _（2））x _（2） ]（x = Br〜（？）（1），I〜（？）（2），n _（3）〜（3），NCS〜（α）（4））或聚合物{[MN（ 15-pyn _（3）o _（2））x]（CLO _（4））} _（n）（x = CN〜（α）（5））组合物，制备并彻底表征。单晶X射线分析为2,3和4确定复合物的扭曲五角形 - 双吡酰胺几何形状。 ascy的磁性数据分析1-4透露了轴向零场分裂参数d（| <0.7cm〜（α1））的非零值（分子校正参数Zj≈）弱反铁磁分子间相互作用？0.1cm〜（？1））。对于1D聚合物复合物5，在Mn〜（II）中心之间发现小的反铁磁性交换偶联，J =Δ1.72cm〜（？1）。将实验获得的磁性参数（J或ZJ）与在DFT水平下理论上计算的磁性参数（J或ZJ）进行了比较，以便在2-4中露出磁交换途径并支持5（J〜（Exp）=Δ2.79cm的聚合物结构〜（？1）与j〜（r）/ j〜（y）=？2.54 /？3.06 cm〜（？1），当使用了Dialclec Spin Hamiltonian）。还发现，在2,3和4的晶体结构中存在的氢键，非共价触点和π-π堆叠相互作用的广泛系统对超分子1D链的形成产生影响，并且因此关于配合物的磁性。与非共价触点相反，轴向配体对复合物的磁性的影响似乎可以忽略不计。

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