In organic–inorganic hybrid materials' (HMs) synthesis, it is intrinsically challenging to, at the same time, achieve (i) the concomitant synthesis of the components, (ii) nanoscopic interpenetration of the components, and (iii) covalent linking of the components. We here report the one-pot hydrothermal synthesis (HTS) of inorganic–organic HMs consisting of perylene bisimide (PBI) dyes and silica, using nothing but water as the medium and directly from the corresponding bisanhydrides, n-alkyl amines, and alkoxysilane precursors. First, in the absence of a functionalized alkoxysilane for linking, a mixture of the products, PBI and SiO₂, is obtained. This evinces that the two products can be synthesized in parallel in the same vessel. Except for minor micromorphological changes, the concomitant synthesis does not affect each component's physicochemical properties. The PBI/SiO₂ mixtures do not show synergistic properties. Second, through adding the linker aminopropyltriethoxysilane (APTS), covalently-linked class II hybrids are obtained. These PBI@SiO₂ class II hybrids show synergistic materials properties: increased thermal stability is obtained in combination with nanoscopic homogeneity. The PBI moieties are dissolved in the solid SiO₂ matrix, while being covalently linked to the matrix. This leads to solution-like fluorescence with vibronic fine-structure of the dyes. Moreover, through tuning the SiO₂ amount, the band gaps of the class II hybrid materials can be systematically shifted. We exploit these optoelectronic properties by using the PBI@SiO₂ hybrids as heterogeneous and reusable photoredox catalysts for the reduction of aryl halides. Finally, we present a detailed small-angle X-ray scattering and powder X-ray diffraction study of PBI@SiO₂ synthesized at various reaction times, revealing the existence of an ordered PBI-oligomeric silesquioxane-type intermediate, which subsequently further condenses to the final nanoscopically homogeneous PBI@SiO₂ material. These ordered intermediates point at HTS′ propensity to favor crystallinity (to date known for organic and inorganic compounds, respectively) to also apply to hybrid structures, and shed additional light on the long-standing question of structure formation in the early stages of sol–gel processes: they corroborate Brown's hypothesis (1965) that trifunctional hydroxysilanes form surprisingly well controlled oligomers in the early stages of polycondensation.

中文翻译：

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绿色水热合成产生具有溶液状荧光和光氧化还原活性的苝双酰亚胺-SiO2杂化材料

在有机-无机杂化材料 (HMs) 合成中，同时实现 (i) 组分的伴随合成，(ii) 组分的纳米级互穿，以及 (iii)组件。我们在此报告了由苝双酰亚胺 (PBI) 染料和二氧化硅组成的无机-有机 HMs 的一锅水热合成 (HTS)，仅使用水作为介质，直接来自相应的双酐、正烷基胺和烷氧基硅烷前体. 首先，在没有用于连接的官能化烷氧基硅烷的情况下，产物 PBI 和 SiO _{2的混合物}, 得到。这表明两种产物可以在同一容器中平行合成。除了微小的微形态变化外，伴随合成不影响每个组分的物理化学性质。PBI/SiO ₂混合物不显示协同特性。其次，通过添加连接基氨基丙基三乙氧基硅烷（APTS），获得共价连接的II类杂化物。这些 PBI@SiO ₂ II 类杂化物显示出协同的材料特性：增加的热稳定性与纳米级均匀性相结合。PBI部分溶解在固体SiO _2中矩阵，同时与矩阵共价连接。这导致具有染料的振动精细结构的溶液状荧光。此外，通过调节SiO ₂的量，可以系统地改变II类杂化材料的带隙。_{我们通过使用 PBI@SiO 2}杂化物作为多相和可重复使用的光氧化还原催化剂来还原芳基卤化物，从而利用这些光电特性。_{最后，我们对在不同反应时间合成的 PBI@SiO 2}进行了详细的小角 X 射线散射和粉末 X 射线衍射研究，揭示了有序 PBI-低聚倍半硅氧烷型中间体的存在，该中间体随后进一步浓缩为最终的纳米级均匀 PBI@SiO ₂材料。这些有序中间体表明 HTS 倾向于有利于结晶度（迄今为止分别用于有机和无机化合物）也适用于杂化结构，并进一步阐明了溶胶早期阶段结构形成的长期问题。凝胶过程：它们证实了 Brown 的假设 (1965)，即三官能羟基硅烷在缩聚的早期阶段形成了令人惊讶的良好控制的低聚物。