Successive oxidation of bis[pyridine-phthalocyaninato(2-)iridium(II)] with iodine first yields mixed-valent bis[pyridine-phthalocyaninato(1,5-)iridium(II)] iodide ([(Ir(py)pc1.5-}2]I) and then pyridine-iodo-phthalocyaninato(2-)iridium(III)-pyridine ([Ir(py)(I)pc2-]·py). The latter crystallizes monoclinically with the following cell parameters: a = 10.258(1) Å, b = 17.589(3) Å, c = 19.723(2) Å, β = 92.95(1)°, space group P21/n, Z = 4. IrIII is in the centre of a slightly distorted pc2- ligand and coordinates pyridine and iodide in a trans-arrangement. The average Ir-Niso distance is 1.995(5) Å (Niso: isoindole N atom), the Ir-Npy and Ir-I distances are 2.102(5) and 2.657(1)Å, respectively. By a similar oxidation of [Rh(py)pc2- }2] only [Rh(py)(I)pc2- ]·py is obtained. Solid state spectral properties with diagnostic absorption bands at 1360. 1456, 5620 and 19800 cm-1 confirm the mixed-valent diphthalocyaninate(1.5-).
用碘连续氧化双[吡啶-酞菁(2-)铱(II)]首先产生混合价双[吡啶-酞菁(1,5-)铱(II)]碘化物([ (Ir(py)pc1.5-)}2]I),然后是吡啶-碘-酞菁(2-)铱(III)-吡啶([Ir(py)(I)pc2-]·py)。后者以单斜晶体结晶,具有以下晶胞参数:a = 10.258(1) Å,b = 17.589(3) Å,c = 19.723(2) Å,β = 92.95(1)°,空间群P21/n,Z = 4。IrIII位于稍微扭曲的pc2-配体中心,并以反式排列配位吡啶和碘。平均Ir-Niso距离为1.995(5) Å(Niso:异吲哚N原子),Ir-Npy和Ir-I距离分别为2.102(5) Å和2.657(1) Å。通过类似的氧化反应,只得到[ Rh(py)pc2- }2]的[ Rh(py)(I)pc2- ]·py。具有诊断性吸收带在1360、1456、5620和19800 cm-1处的固态光谱性质证实了混合价的二酞菁配位体(1.5-)。