College of Chemistry and Chemical Engineering & Henan Province Key laboratory of Utilization of Non-metallic Mineral in the South of Henan, Institute for Conservation and Utilization of Agro-bioresources in Dabie Mountains, Xinyang Normal University, Xinyang 464000, China.
Soft Matter. 2017 May 24;13(20):3802-3811. doi: 10.1039/c7sm00714k.
A thiophene-based hybrid organogel system consisting of complex iridium (Ir) and EuCl·6HO was designed and synthesized to realize dual responses to volatile acids and organic amine vapors. The photophysical properties and self-assembly of compound 1 and the hybrid organogel were also studied. Compound 1 could gelate some organic solvents and self-assemble into 3D nanofibers in the gels. The stable hybrid organogel 1-Ir-Eu could be obtained after addition of complex Ir and EuCl·6HO. FTIR spectral results showed that the hydrogen bond still remained even upon addition of complex Ir, EuCl·6HO, NaOH and CFCOOH to organogel 1. Interestingly, the emission properties of the hybrid organogel 1-Ir-Eu could undergo interconversion between cyan light and red light via addition of NaOH and CFCOOH. The emission properties of xerogel film 1-Ir-Eu obtained in the presence of NaOH could also undergo fast and reversible transition in response to volatile acids such as CFCOOH, formic acid, acetic acid, propionic acid and organic amine vapors such as ammonium hydroxide, EtN, tripropylamine, and ethylenediamine. The emission spectral change of Ir-Eu in the organogel or xerogel in the presence of base and acid demonstrated the formation of a new complex between complex Ir and EuCl·6HO. This dual-response process could be repeated many times. Contact angle experiment results further showed the morphology and internal components of the xerogel film surface in the process of response to gaseous CFCOOH and EtN. This work provides a method for producing multifunctional supramolecular materials for sensing volatile acids and organic amine vapors.
设计并合成了一种基于噻吩的杂化有机凝胶体系，由复杂的铱（Ir）和 EuCl·6HO 组成，以实现对挥发性酸和有机胺蒸气的双重响应。还研究了化合物 1 和杂化有机凝胶的光物理性质和自组装。化合物 1 可以凝胶化一些有机溶剂，并在凝胶中自组装成 3D 纳米纤维。加入复杂的 Ir 和 EuCl·6HO 后，可得到稳定的杂化有机凝胶 1-Ir-Eu。FTIR 光谱结果表明，即使加入复杂的 Ir、EuCl·6HO、NaOH 和 CFCOOH 后，氢键仍然存在于有机凝胶 1 中。有趣的是，通过加入 NaOH 和 CFCOOH，杂化有机凝胶 1-Ir-Eu 的发射性质可以在蓝绿光和红光之间进行相互转换。在存在 NaOH 的情况下，获得的 xerogel 薄膜 1-Ir-Eu 的发射性质也可以对挥发性酸（如 CFCOOH、甲酸、乙酸、丙酸）和有机胺蒸气（如氨、EtN、三丙胺、乙二胺）快速和可逆地响应。在存在碱和酸的情况下，Ir-Eu 在有机凝胶或 xerogel 中的发射光谱变化表明，在复杂的 Ir 和 EuCl·6HO 之间形成了一种新的配合物。这个双重响应过程可以重复多次。接触角实验结果进一步显示了在响应气态 CFCOOH 和 EtN 过程中 xerogel 薄膜表面的形貌和内部成分的变化。这项工作为生产用于感测挥发性酸和有机胺蒸气的多功能超分子材料提供了一种方法。
