离子对间电荷转移配合物：阴离子…π作用及近红外吸收(英文)

Observation of Anion…π Interaction and Near IR Absorption in an Ion-Pair Charge Transfer Complex

合成并表征了一种离子对配合物1,[Cl2Bz-1-Apy]2[Ni(mnt)2],其中,Cl2Bz-1-Apy为(E)-1-(3,4-二氯苯亚甲基氨基)吡啶一价阳离子,mnt是马来二睛基二硫烯二价阴离子。在配合物1的晶体中,阴离子和阳离子中吡啶环之间存在阴离子…π相互作用。DFT电荷密度分布分析表明,阴离子…π相互作用主要源自离子对间的Coulomb吸引力。在固体和乙腈溶液电子吸收光谱近红外区,配合物1都有一个宽的弱吸收带,该吸收带可归属为二价阴离子[Ni(mnt)2]2-内的d-d电子跃迁和阴阳离子对间的电荷转移跃迁。

An ion-pair complex, [Cl2Bz-1-Apy]2[Ni（mnt）2] （Cl2Bz-1-Apy^＋=（E）-1-（3,4-di-chlorobenzylideneamino） pyridinium and mnt^2-=maleonitriledithiolate）, was synthesized and characterized. The anion …π interaction is observed. Based on the DFT analysis, the intermolecular interaction can be attributed to Coulomb interaction. The UV-Vis-NIR spectra of the ion-pair complex in solid state and acetonitrile solution exhibit a weak absorption band in the near IR region, which might originate from the d-d transition in [Ni（mnt）2]^2- dianion or IPCT （ion-pair charge transfer） transition between the cation and anion.