机械化学向有机"盐"通过整数电荷转移共晶战略快速,高效,可扩展的近红外光热转换
Shun-Li Chen1, Meng-Meng Zhang1, Jiecheng Chen1
1College of Chemistry and Chemical Engineering, and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, 515063, P. R. China.
ChemSusChem
|June 6, 2023
概括
新的整数电荷转移 (integer-CT) 联合晶体有效地将近红外光转化为热. 通过机械化学合成的这些材料显示出可扩展的太阳能采集应用的前景.
科学领域:
- 材料科学 材料科学 材料科学
- 摄影化学的使用.
- 超分子化学 超分子化学
背景情况:
- 莫特绝缘器使用离子电荷转移复合体.
- 近红外 (NIR) 光热转换 (PTC) 对能源应用至关重要.
- 开发高效和稳定的PTC材料是一个持续的挑战.
研究的目的:
- 为高效的NIR光热转换 (PTC) 设计和合成新的整数电荷转移 (integer-CT) 共晶体.
- 研究这些共晶体的自我组装机制和结构-属性关系.
- 评估合成材料的PTC性能和稳定性.
主要方法:
- 通过机械化学和溶液方法,使用捐赠/接受单位 (氨基 styryl-pyridinium染料和F4TCNQ) 合成整数CT共晶.
- 共同晶体结构的表征,包括无形的"盐"和分离堆叠的"离子晶体"形式.
- 在808nm激光照明下测量光热转换效率.
主要成果:
- 整数CT共晶体通过D-A键 (C-H⋅⋅⋅X) 自组装.
- 强烈的电荷转移相互作用导致了从200-1500纳米范围广泛的光收获.
- "盐"和"离子晶体"形式都表现出出色的PTC效率,这是由于超快的非辐射衰变 (∼2 psi).
- 无形"盐"表现出良好的光/热稳定性.
结论:
- 整数CT共晶体是快速,高效和可扩展的PTC的有效平台.
- 机械化学提供了一步的方法来合成无形PTC材料.
- 无形整数-CT共晶体对于水性环境中的大规模太阳能采集应用特别有前途.
相关概念视频
01:26Photochemical Electrocyclic Reactions: Stereochemistry
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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
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01:17Thermal Electrocyclic Reactions: Stereochemistry
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The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
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Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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