Synthesis and magnetic properties of an annulated dinuclear copper(II) phthalocyanine peripherally having 2,6-dimethylphenoxy substituents
Synthesis and magnetic properties of an annulated dinuclear copper(II) phthalocyanine peripherally having 2,6-dimethylphenoxy substituents
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DOI：
10.1142/s1088424614500485
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发表时间：
2014-10
影响因子：
1.5
通讯作者：
T. Ikeue;N. Sawada;Naomi Matsumoto;A. Miyazaki;T. Sugimori;Masayuki Koikawa;I. Hiromitsu;K. Yoshino;M. Mikuriya;Y. Kataoka;M. Handa
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文献类型：
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作者：
T. Ikeue;N. Sawada;Naomi Matsumoto;A. Miyazaki;T. Sugimori;Masayuki Koikawa;I. Hiromitsu;K. Yoshino;M. Mikuriya;Y. Kataoka;M. Handa
合成并表征了一种在[CuPc]2骨架周围含有12个2，6-二甲基苯氧基的双核铜(II)酞菁配合物，其中[CuPc]单元通过一个普通的环状苯环相连，形成平面双核结构。引入的大体积2，6-二甲基苯氧基能有效地抑制双核配合物在甲苯溶液中的聚集，在838 nm处有一个明显红移的Q带。15K下冰冻甲苯溶液中的EPR谱和随温度变化的磁矩表明，铜(II)离子之间存在反铁磁相互作用。用Bleaney Bowers方程估算了S_1=S_2=1/2体系的交换积分J=-1.8 cm~(-1)。密度泛函理论计算结果证实了两个[CuPc]单元之间通过公共环状苯环的长程相互作用(铜-铜距离=10.7A)。
A dinuclear copper(II) phthalocyanine complex with 12 2,6-dimethylphenoxyl groups at the peripheral positions of the [CuPc]2 framework, where [CuPc] units are linked by a common annulated benzene ring to give the planar dinuclear structure, was prepared and characterized. The introduced bulky 2,6-dimethylphenoxyl groups were revealed to effectively suppress the aggregation of the dinuclear complex in the toluene solution, showing a considerably red-shifted Q-band at 838 nm. The EPR spectrum (measured in the frozen toluene solution at 15 K) and temperature-dependent magnetic moment indicated the existence of antiferromagnetic interaction between the copper(II) ions. The exchange integral J was estimated to be -1.8 cm-1 using Bleaney Bowers equation for the S1 = S2 = 1/2 system. The long-range interaction (Cu–Cu distance = 10.7 A) through the common annulated benzene ring between two [CuPc] units was confirmed by the DFT calculation result.