کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1334485 | 1500258 | 2014 | 8 صفحه PDF | دانلود رایگان |
The azophenine N,N′,N″,N‴-tetra-4-ethylphenyl-2,5-diamino-1,4-benzoquinonediimine (4-EtApH2), its diprotonated species [4-EtApH4](ClO4)2 (1) and complexes, the bis(boron difluoride) complex [(BF2)2(μ-4-EtAp)] (2), the mono- and dinuclear nickel(II) complexes [Ni(4-EtApH2)3](ClO4)2 (3) and [{Ni(acac)}2(μ-4-EtAp)] (4), respectively, and the dinuclear iridium(III) complex [{Ir(cp∗)Cl}2(μ-4-EtAp)] (5), have been prepared. The molecular structures of these compounds were determined by X-ray analysis. The coordination environments around the boron center of 2 and the Ni centers of 3 and 4 were tetrahedral, octahedral and square-planar, respectively. Furthermore, each Ir center of 5 was coordinated by two nitrogen atoms from 4-EtAp2−, Cl− and η5-cp∗. Coordination of the ligand to Ni to form 3 caused an isomerization from the para-benzoquinonediimine of 4-EtApH2 to the ortho form, with a bond alternation at each of the two N–C–C–C–N π-systems. Diprotonation and dinuclear complex formation to construct 1, 2, 4 and 5 led to a delocalization of six π-electrons over each of the two N–C–C–C–N moieties connected by single bonds. The π–π∗ transition absorption gradually shifted to longer wavelengths (4-EtApH2 ≈ 3→2→1→4 ≈ 5), suggesting an extension of the π-conjugation range. Cyclic voltammograms of 3 and 4 showed one and two redox potential(s), respectively.
Protonation and dinuclear complex formation with B(III), Ni(II), and Ir(III) centers provide a change in the bond alternating π-systems of an azophenine derivative to conjugated ones, resulting in π-electrons being delocalized between the metal centers.Figure optionsDownload as PowerPoint slide
Journal: Polyhedron - Volume 81, 15 October 2014, Pages 715–722