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首页> 外文期刊>Chemistry: A European journal >Supramolecular Architecture and Magnetic Properties of Copper(II) and Nickel(II) Porphyrinogen-TCNQ Electron-Transfer Salts
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Supramolecular Architecture and Magnetic Properties of Copper(II) and Nickel(II) Porphyrinogen-TCNQ Electron-Transfer Salts

机译：铜（II）和镍（II）卟啉原-TCNQ电子转移盐的超分子结构和磁性

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The compounds [Cu(Tz)(MeOH)_2](TCNQ)_2 (1), [Ni(Tz)(MeOH)_2](TCNQ)_2 (1), [Cu(Tz)_2(TCNQ))7 (3) and [Ni(Tz)_2](TCNQ)_7 (4 (Tz = 2,7,12,17-tetramethyl-1,6,11,16-tetraazaporphyrinogen) were obtained by metathesis reaction of [M(Tz)](ClO_4)_2 with LiTCNQ and Et_3NH(TCNQ)_2, respectively. They were characterized by a combination of spectroscopic and physical methods. Compound 1 crystallizes in the monoclinic space group P2_1 with a = 8.310(1), b = 25.180(4), c = 20.727(4) A, #beta# = 93.58(2)°; Z = 4. Compound 3 crystallizes in the triclinic space group P1 with a = 11.244(1), b = 156.700(1), c = 17.321(1)A, #alpha# = 113.47(1), #beta# = 108.52(1), #gamma# = 96.12(1)°; Z = 2. The asymmetric unit of the compound 1 is formed by cationic [Cu(Tz)(MeOH)_2]~(2+) and by two crystallographiccally non equivalent TCNQ~(·-) anions; these anions from dimeric units by overlap of the #pi# clouds. The dimers form hyrogen bonds with the metallomacrocyclic cation through the methanol ligands. According to this structure the compound is paramgnetic and behaves as an insulator in the temperature range studied. The paramagnetism arises only from the metal-complex moieties. Compound 3 shows an unprecedented structure due to the steric reuirements of the macrocycle that favors the stacking of the TCNQ groups. The structure consists of infinite stacks of TCNQ units separated by the metal-macrocyclic units; there are seven TCNQ molecules per formula unit, one of which is formally mono-anionic, while the other six bear one half of an electron per molecule. The copper is six-coordinate in a very distorted octahedral environment. The Tz ligand is located in the equatorial plane and the aical nitrogens of the nitrile groups of two TCNQ moleculs complete the coordination around the copper. The compound is a semiconductor and its magnetic behavior can be exlained by the sum of the Curie contribution of the metal complex and the contribution arising from the magnetci-exchange interactions of the spins located on the TCNQ units. The latter is found to be typial of one-dimensional antiferromagnetic distorted chains of S = 1/2 spins and can be fitted according to a one-dimensional Heisenberg antiferromagnetic model.
机译：化合物[Cu（Tz）（MeOH）_2]（TCNQ）_2（1），[Ni（Tz）（MeOH）_2]（TCNQ）_2（1），[Cu（Tz）_2（TCNQ））7（ 3）和[Ni（Tz）_2]（TCNQ）_7（4（Tz = 2,7,12,17-四甲基-1,6,11,16-四氮杂卟啉原））通过[M（Tz） ]（ClO_4）_2分别用LiTCNQ和Et_3NH（TCNQ）_2表征，通过光谱和物理方法相结合进行表征，化合物1在单斜空间群P2_1 / n中结晶，a = 8.310（1），b = 25.180 （4），c = 20.727（4）A，＃beta＃= 93.58（2）°; Z =4。化合物3在三斜空间群P1中结晶，a = 11.244（1），b = 156.700（1）， c = 17.321（1）A，＃alpha＃= 113.47（1），＃beta＃= 108.52（1），＃gamma＃= 96.12（1）°; Z =2。化合物1的不对称单元由阳离子[Cu（Tz）（MeOH）_2]〜（2+）和两个晶体学上不等价的TCNQ〜（·-）阴离子;这些阴离子是由二聚体通过＃pi＃云的重叠而形成的。通过甲醇配体的金属大环阳离子。这种结构的化合物是准磁性的，在所研究的温度范围内具有绝缘性。顺磁性仅由金属络合物部分产生。由于有利于TCNQ基团堆叠的大环的空间取代，化合物3显示出前所未有的结构。该结构由被金属大环单元分隔的TCNQ单元的无限堆栈组成。每个分子式单元中有七个TCNQ分子，其中一个形式上是单阴离子，而另外六个分子中每个分子带有一半的电子。铜在非常扭曲的八面体环境中为六坐标。 Tz配体位于赤道平面，两个TCNQ分子的腈基的铝氮原子完成了铜周围的配位。该化合物是一种半导体，可以通过金属络合物的居里贡献和位于TCNQ单元上的自旋的磁交换相互作用产生的贡献来解释其磁行为。后者是S = 1/2自旋的一维反铁磁扭曲链的典型形式，可以根据一维Heisenberg反铁磁模型进行拟合。

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