Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław, Poland.
Molecules. 2022 Mar 11;27(6):1839. doi: 10.3390/molecules27061839.
A new antimony(III)-phthalocyanine complex with the formula of [(SbPc)(SbI)(SbBr)] has been obtained in the reaction of pure antimony powder with phthalonitrile under the oxidation conditions by iodine monobromide vapors. The complex crystallizes in the centrosymmetric space group of the triclinic system. Both independent (SbPc) units exhibit non-planar conformation, since the Sb(III) is larger than the equilibrium cavity size of the ring and cannot be accommodated without its expansion; thus, the metal protrudes out of the cavity, forming a saucer shape. The centrosymmetric anionic unit of the crystal consists of two (SbI) interacted anionic units forming (SbI) anionic complex that interacts with two SbBr molecules to form [SbIBr] anionic aggregate. Each [SbIBr] anionic aggregate is surrounded by four (SbPc) cations forming a supramolecular centrosymmetric (SbPc)[SbIBr] complex. Translationally related (SbPc)[SbIBr] molecules form a stacking structure along the [100] and [011] directions with N-N distances of 3.55 and 3.53 Å, respectively, between the back-to-back-oriented saucer-shaped (SbPc) units. The interaction between the building units of the crystal was analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. The UV-Vis absorption spectra of crystal were taken in CHCl and toluene solutions in the concentration range from 10 to 10 mol/L. No significant changes related to aggregation in solutions were observed. The Q-band in toluene solution is red shifted by ~15 nm in comparison to that in CHCl solution. Oxidation of (SbPc)[SbIBr] yields SbPc derivative. Both Sb and Sb phthalocyanine derivatives absorb near infrared light (600-900 nm), which should be intriguing from the point of view of potential use as photosensitizers for PDT and as an infrared cut filter for plasma display and silicon photodiodes.
一种新的锑(III)-酞菁配合物[(SbPc)(SbI)(SbBr)]已通过纯锑粉与邻苯二甲腈在碘单溴蒸气的氧化条件下反应得到。该配合物在中心对称的三斜晶系空间群中结晶。两个独立的(SbPc)单元呈现非平面构象,因为 Sb(III) 大于环的平衡腔尺寸,不能在不扩张的情况下容纳;因此,金属从腔中突出,形成碟形。晶体的中心对称阴离子单元由两个相互作用的(SbI)阴离子单元组成,形成(SbI)阴离子配合物,与两个 SbBr 分子相互作用形成[SbIBr]阴离子聚集体。每个[SbIBr]阴离子聚集体被四个(SbPc)阳离子包围,形成一个超分子中心对称的(SbPc)[SbIBr]配合物。翻译相关的(SbPc)[SbIBr]分子沿着[100]和[011]方向形成堆积结构,背对背取向的碟形(SbPc)单元之间的 N-N 距离分别为 3.55 和 3.53 Å。晶体的构建单元之间的相互作用使用 Hirshfeld 表面和二维指纹图的分析进行了分析。在 CHCl 和甲苯溶液中,从 10 到 10 mol/L 的浓度范围内,对晶体的紫外-可见吸收光谱进行了测量。在溶液中未观察到与聚集相关的显著变化。与在 CHCl 溶液相比,甲苯溶液中的 Q 带红移约 15nm。(SbPc)[SbIBr]的氧化产物为 SbPc 衍生物。Sb 和 Sb 酞菁衍生物都吸收近红外光(600-900nm),从潜在用作 PDT 的光敏剂和作为等离子体显示器和硅光电二极管的红外截止滤光片的角度来看,这应该是有趣的。
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