Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion

doi:10.1016/j.cjche.2025.07.013

中国化学工程学报 ›› 2025, Vol. 88 ›› Issue (12): 142-151.DOI: 10.1016/j.cjche.2025.07.013

Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion

Yumei Shu^1,2, Jinxiu Hu¹, Lin Yang^1,2, Tehreem Yaqub^1,2, Minhua Ai^1,2, Yang Liu³, Dandan Shi⁴, Kang Xue^1,2, Chengxiang Shi^1,2, Xiangwen Zhang^1,2, Jijun Zou^1,2, Lun Pan^1,2

1. Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
2. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China;
3. Qinghai Yanhu Industry Co., LTD, Geermu 816000, China;
4. School of Ecology and Environmental Science, Qinghai Institute of Technology, Xining 810016, China

收稿日期:2025-03-26 修回日期:2025-07-02 接受日期:2025-07-02 出版日期:2026-02-09 发布日期:2025-08-16
通讯作者: Minhua Ai,E-mail:aiminhua@tju.edu.cn;Lun Pan,E-mail:panlun76@tju.edu.cn
基金资助:
The authors appreciate the support from the National Natural Science Foundation of China (22222808, 22408272, U24A20547), the China National Postdoctoral Program for Innovative Talents (BX20240251), the Natural Science Foundation of Tianjin (24JCQNJC01820), the China Postdoctoral Science Foundation (2023M742592), the Aeronautical Science Foundation of China (2023Z073048003) and the Haihe Laboratory of Sustainable Chemical Transformations.

Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion

Yumei Shu^1,2, Jinxiu Hu¹, Lin Yang^1,2, Tehreem Yaqub^1,2, Minhua Ai^1,2, Yang Liu³, Dandan Shi⁴, Kang Xue^1,2, Chengxiang Shi^1,2, Xiangwen Zhang^1,2, Jijun Zou^1,2, Lun Pan^1,2

1. Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
2. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China;
3. Qinghai Yanhu Industry Co., LTD, Geermu 816000, China;
4. School of Ecology and Environmental Science, Qinghai Institute of Technology, Xining 810016, China

Received:2025-03-26 Revised:2025-07-02 Accepted:2025-07-02 Online:2026-02-09 Published:2025-08-16
Contact: Minhua Ai,E-mail:aiminhua@tju.edu.cn;Lun Pan,E-mail:panlun76@tju.edu.cn
Supported by:
The authors appreciate the support from the National Natural Science Foundation of China (22222808, 22408272, U24A20547), the China National Postdoctoral Program for Innovative Talents (BX20240251), the Natural Science Foundation of Tianjin (24JCQNJC01820), the China Postdoctoral Science Foundation (2023M742592), the Aeronautical Science Foundation of China (2023Z073048003) and the Haihe Laboratory of Sustainable Chemical Transformations.

摘要/Abstract

摘要： Intramolecular [2 + 2] photocycloaddition is a reliable way to synthesize high-strained cyclobutyl-containing structures for high-value chemicals. Here we propose a photosensitized dimer of methyl cyclopentadiene (DMCPD) intramolecular [2 + 2] cycloaddition to synthesize an intriguing liquid caged fuel, namely 3,8-dimethylpentacyclic [5.3.0.0^2,5.0^3,9.0^4.8] decane (MPCD), with two four-membered rings, four five-membered rings and two methyl branched chains. The reaction conditions are optimized to obtain a high DMCPD conversion of 80.95% as well as a high MPCD selectivity of 74.19%. Based on the quenching experiment and low-temperature phosphorescence test, intramolecular [2 + 2] photocycloaddition complies with the Dexter triplet-energy-transfer mechanism, which is essentially double electron exchange between excited photosensitizer and DMCPD. Through kinetic studies, the reaction order (α = 1) and the reaction kinetic equation related to light intensity and DMCPD concentration are obtained. MPCD has excellent physicochemical properties, with a high density of 0.964 g·cm^-3, high net heat of combustion of 42.63 MJ·kg^-1, relatively low kinetic viscosity of 25.03 mm²·s^-1 at (20 ℃), and high specific impulse of 328.19 s.

关键词: Intramolecular photocycloaddition, Dexter triplet-energy-transfer, Kinetics, Highly-strained fuel, Caged structure

Abstract: Intramolecular [2 + 2] photocycloaddition is a reliable way to synthesize high-strained cyclobutyl-containing structures for high-value chemicals. Here we propose a photosensitized dimer of methyl cyclopentadiene (DMCPD) intramolecular [2 + 2] cycloaddition to synthesize an intriguing liquid caged fuel, namely 3,8-dimethylpentacyclic [5.3.0.0^2,5.0^3,9.0^4.8] decane (MPCD), with two four-membered rings, four five-membered rings and two methyl branched chains. The reaction conditions are optimized to obtain a high DMCPD conversion of 80.95% as well as a high MPCD selectivity of 74.19%. Based on the quenching experiment and low-temperature phosphorescence test, intramolecular [2 + 2] photocycloaddition complies with the Dexter triplet-energy-transfer mechanism, which is essentially double electron exchange between excited photosensitizer and DMCPD. Through kinetic studies, the reaction order (α = 1) and the reaction kinetic equation related to light intensity and DMCPD concentration are obtained. MPCD has excellent physicochemical properties, with a high density of 0.964 g·cm^-3, high net heat of combustion of 42.63 MJ·kg^-1, relatively low kinetic viscosity of 25.03 mm²·s^-1 at (20 ℃), and high specific impulse of 328.19 s.

Key words: Intramolecular photocycloaddition, Dexter triplet-energy-transfer, Kinetics, Highly-strained fuel, Caged structure

Yumei Shu, Jinxiu Hu, Lin Yang, Tehreem Yaqub, Minhua Ai, Yang Liu, Dandan Shi, Kang Xue, Chengxiang Shi, Xiangwen Zhang, Jijun Zou, Lun Pan. Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion[J]. 中国化学工程学报, 2025, 88(12): 142-151.

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Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion

Synthesis of liquid caged hydrocarbon fuel by intramolecular [2+2] photocycloaddition for advanced propulsion

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