Synthesis, Structure, and Magnetic Properties of Linear Trinuclear CuII and NiII Complexes of Porphyrin Analogues Embedded with Binaphthol Units
Synthesis, Structure, and Magnetic Properties of Linear Trinuclear CuII and NiII Complexes of Porphyrin Analogues Embedded with Binaphthol Units
复制标题
DOI：
10.3390/sym12101610
复制
发表时间：
2020-09
期刊：
影响因子：
--
通讯作者：
J. Setsune;Shintaro Omae;Yuki Tsujimura;T. Mochida;T. Sakurai;H. Ohta
中科院分区：
文献类型：
--
作者：
J. Setsune;Shintaro Omae;Yuki Tsujimura;T. Mochida;T. Sakurai;H. Ohta
在不降低原联萘酚单元光学纯度的前提下，合成了一种嵌有（S）-1，1 ′-联-2-萘酚单元的卟啉类似物。这种新的大环配体提供了六阴离子N4 O 4配位环境，使三个金属离子的线性阵列。也就是说，它为中心金属位点提供正方形平面O 4供体组，为末端金属位点提供扭曲的正方形平面N2 O2供体组。实际上，获得了Cu（1）-Cu（2）距离为2.910 μ m，Cu（1）-Cu（2）-Cu（1′）角为174.7°，并且具有非常平坦的Cu 2 O2金刚石芯的CuII 3配合物。可变温度的1H-NMR研究的CuII 3复合物表明随着温度的升高，萘基质子的顺磁位移增加，这表明强反铁磁耦合的CuII离子。磁化率的温度依赖性表明CuII 3络合物（J = −434 cm−1）和NiII 3络合物（J = −49 cm−1）都存在反铁磁耦合。由芳香族组分制成的刚性大环空腔中的线性（L）M（μ-OR）2 M（μ-OR）2 M（L）核心提供了在中心金属的顶端位点进行可逆连接的稳健金属络合物。
A porphyrin analogue embedded with (S)-1,1′-bi-2-naphthol units was synthesized without reducing optical purity of the original binaphthol unit. This new macrocyclic ligand provides the hexaanionic N4O4 coordination environment that enables a linear array of three metal ions. That is, it provides the square planar O4 donor set for the central metal site and the distorted square planar N2O2 donor set for the terminal metal sites. In fact, a CuII3 complex with a Cu(1)–Cu(2) distance of 2.910 Å, a Cu(1)–Cu(2)–Cu(1′) angle of 174.7°, and a very planar Cu2O2 diamond core was obtained. The variable-temperature 1H-NMR study of the CuII3 complex showed increasing paramagnetic shifts for the naphthyl protons as temperature increased, which suggests strong antiferromagnetic coupling of CuII ions. The temperature dependence of the magnetic susceptibility indicated antiferromagnetic coupling both for the CuII3 complex (J = −434 cm−1) and for the NiII3 complex (J = −49 cm−1). The linear (L)M(µ-OR)2M(µ-OR)2M(L) core in a rigid macrocycle cavity made of aromatic components provides robust metal complexes that undergo reversible ligation at the apical sites of the central metal.