2-茂铁基-4,5-二苯基咪唑离子液体的合成及对高氯酸铵热分解的催化作用

doi:10.7503/cjcu20170708

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 889.doi: 10.7503/cjcu20170708

2-茂铁基-4,5-二苯基咪唑离子液体的合成及对高氯酸铵热分解的催化作用

王吉成¹, 袁耀锋^1,², 卓继斌¹, 杨思涵¹, 林芬³

1. 福州大学化学学院, 福州 350116
2. 中国科学院福建物质结构研究所结构化学国家重点实验室, 福州 350002
3. 福州大学测试中心, 福州 350116

收稿日期:2017-11-06 出版日期:2018-04-21 发布日期:2018-04-21
作者简介:
联系人简介: 袁耀锋, 男, 博士, 教授, 博士生导师, 主要从事功能有机分子的设计合成与性能方面的研究. E-mail: yaofeng_yuan@fzu.edu.cn
基金资助:
国家自然科学基金(批准号: 21642009, 21772023)、福建省科技计划项目(批准号: 2015H6010)和中国科学院福建物质结构研究所结构化学国家重点实验室项目(批准号: 20180020)资助.

Synthesis of 2-Ferrocenyl-4,5-diphenylimidazolium Ionic Liquids and Their Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate^†

WANG Jicheng¹, YUAN Yaofeng^1,^2,^*, ZHUO Jibin¹, YANG Sihan¹, LIN Fen³

1. College of Chemistry, Fuzhou University, Fuzhou 350116, China
2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
3. Testing Center, Fuzhou University, Fuzhou 350116, China

Received:2017-11-06 Online:2018-04-21 Published:2018-04-21
Contact: YUAN Yaofeng
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21642009 and 21772023), the Project of Science and Technology of Fujian Province, China(No.2015H6010) and the Research Fund for the State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences(No.20180020).

摘要/Abstract

摘要：

以2-二茂铁基-4,5-二苯基-1-氢咪唑(1)为原料, 用较强碱NaH拔氢, 经不同卤代烃取代制得化合物2a~2f, 再与碘甲烷反应生成相应的咪唑离子碘盐(3a~3f), 最后与六氟磷酸铵进行离子交换得到咪唑的六氟磷酸盐(4a~4f). 通过红外光谱(IR)、核磁共振波谱(NMR)、质谱(MS)、高分辨质谱(HRMS)及X射线单晶衍射对目标化合物的结构进行了表征. 运用循环伏安法(CV)探讨了其氧化还原过程, 利用热重分析(TG)及差示扫描量热法(DSC)研究了化合物对高氯酸铵(AP)的燃速催化性能. 电化学测试结果表明, 化合物均仅有一组氧化还原峰, 归属于分子中茂环(Fc/Fc⁺)的氧化还原过程, 且电极反应动力学基本受扩散控制. 热分析结果表明, 目标化合物对AP均具有优良的燃速催化效果, 其中负离子为I^-的化合物的催化分解效果明显优于负离子为P $F 6 -$ 的化合物. 尤为突出的是化合物3b, 其第二分解峰几乎消失, 而第一分解峰则提前到270.5 ℃, 将AP分解温度提前了180 ℃.

关键词: 二茂铁衍生物, 咪唑, 离子液体, 高氯酸铵, 热分解

Abstract:

Compounds 2a—2f were synthesized by the substitution reaction of 2-ferrocenyl-4,5-diphenylimi-dazole(1) with different halohydrocarbons. Then compounds 2a—2f were reacted with iodomethane to get compounds 3a—3f. Finally, compounds 3a—3f were exchanged anion with ammonium hexafluorophosphate to get compounds 4a—4f. All these compounds were structurally characterized by means of infrared(IR), mass spectrometry(MS), nuclear magnetic resonance(NMR), high-resolution mass spectrometry(HRMS) and X-ray crystal diffraction. Electrochemical properties of these compounds were studied by cyclic voltammetry(CV). Thermal behavior and catalytic performance for thermal decomposition of ammonium perchlorate(AP) were studied by thermogravimetric(TG) and differential scanning calorimetry(DSC). The results indicate that all the synthetic products have efficient catalytic effect on the thermal decomposition of AP. The iodized salts(3a—3f) indicate better catalytic effect than the hexafluorophosphate(4a—4f). The most outstanding compound is 3b, which makes the second decomposition stage of AP disappear, and the first stage is advanced to 270.5 ℃. The novel dinuclear ferrocen-based imidazolium derivatives would have great value in preparing high-burning-rate catalyst for composite solid propellants.

Key words: Ferrocenyl derivative, Imidazole, Ionic liquid, Ammonium perchlorate, Thermal decomposition

中图分类号:

O626.2

TrendMD:

王吉成, 袁耀锋, 卓继斌, 杨思涵, 林芬. 2-茂铁基-4,5-二苯基咪唑离子液体的合成及对高氯酸铵热分解的催化作用. 高等学校化学学报, 2018, 39(5): 889.

WANG Jicheng,YUAN Yaofeng,ZHUO Jibin,YANG Sihan,LIN Fen. Synthesis of 2-Ferrocenyl-4,5-diphenylimidazolium Ionic Liquids and Their Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate^†. Chem. J. Chinese Universities, 2018, 39(5): 889.

图/表 11

Table 1 Appearance, yields, melting points, MS and IR data for compounds 2a—2f and 3a—3f

Compd.	Appearance	Yield^a(%)	m. p./℃	MS, m/z[M+H]⁺	IR(KBr), $ν ˙$ /cm^-1
2a	Yellow solid	88	196—198	419.32	3062, 2922, 1596, 774, 697
2b	Yellow solid	92	165—166	433.32	3062, 2984, 1600, 1500, 702
2c	Yellow solid	94	161—162	447.39	3068, 2965, 1600, 1497, 702
2d	Yellow solid	82	133—134	517.44	3062, 2926, 1600, 1503, 695
2e	Yellow solid	86	143—144	445.29	3068, 2958, 1600, 1452, 695
2f	Yellow solid	85	122—123	495.31	3056, 3030, 1600, 1458, 702
3a	Orange solid	60	>236^b	433.31	3056, 2961, 1507, 767, 690
3b	Orange solid	58	>191^b	447.32	3056, 2926, 1600, 1503, 708
3c	Orange solid	61	95—96	461.37	3049, 2965, 1600, 1491, 702
3d	Orange solid	52	$c$	531.49	3056, 2920, 1594, 1497, 708
3e	Orange solid	48	> 178^b	459.27	3068, 3056, 3023, 1639, 702
3f	Orange solid	55	122—123	509.33	3049, 2913, 1503, 1445, 702

Table 1 Appearance, yields, melting points, MS and IR data for compounds 2a—2f and 3a—3f

Compd.	Appearance	Yield^a(%)	m. p./℃	MS, m/z[M+H]⁺	IR(KBr), $ν ˙$ /cm^-1
2a	Yellow solid	88	196—198	419.32	3062, 2922, 1596, 774, 697
2b	Yellow solid	92	165—166	433.32	3062, 2984, 1600, 1500, 702
2c	Yellow solid	94	161—162	447.39	3068, 2965, 1600, 1497, 702
2d	Yellow solid	82	133—134	517.44	3062, 2926, 1600, 1503, 695
2e	Yellow solid	86	143—144	445.29	3068, 2958, 1600, 1452, 695
2f	Yellow solid	85	122—123	495.31	3056, 3030, 1600, 1458, 702
3a	Orange solid	60	>236^b	433.31	3056, 2961, 1507, 767, 690
3b	Orange solid	58	>191^b	447.32	3056, 2926, 1600, 1503, 708
3c	Orange solid	61	95—96	461.37	3049, 2965, 1600, 1491, 702
3d	Orange solid	52	$c$	531.49	3056, 2920, 1594, 1497, 708
3e	Orange solid	48	> 178^b	459.27	3068, 3056, 3023, 1639, 702
3f	Orange solid	55	122—123	509.33	3049, 2913, 1503, 1445, 702

Table 2 1H NMR data for compounds 2a—2f and 3a—3f*

Compd.	¹H NMR(400 MHz, CDCl₃), δ
2a	7.55(d, J=7.6 Hz, 2H, PhH), 7.46—7.50(m, 3H, PhH), 7.41(dd, J=7.6, 1.6 Hz, 2H, PhH), 7.23(t, J=7.6 Hz, 2H, PhH), 7.15(t, J=7.6 Hz, 1H, PhH), 4.82(t, J=2.0 Hz, 2H, CpH), 4.41(t, J=2.0 Hz, 2H, CpH), 4.27(s, 5H, CpH), 3.68(s, 3H, CH₃)
2b	7.49—7.54(m, 5H, PhH), 7.43(dd, J=7.2, 2.0 Hz, 2H, PhH), 7.22(t, J=7.2 Hz, 2H, PhH), 7.14(t, J=7.2 Hz, 1H, PhH), 4.81(t, J=1.6 Hz, 2H, CpH), 4.40(t, J=1.6 Hz, 2H, CpH), 4.30(s, 5H, CpH), 4.12(q, J=7.2 Hz, 2H, CH₂), 1.20(t, J=7.2 Hz, 3H, CH₃)
2c	7.53—7.54(m, 1H, PhH), 7.51—7.52(m, 1H, PhH), 7.47—7.50(m, 3H, PhH), 7.40—7.42(m, 2H, PhH), 7.22(t, J=7.6 Hz, 2H, PhH), 7.12—7.16(m, 1H, PhH), 4.77(t, J=1.6 Hz, 2H, CpH), 4.39(t, J=1.6 Hz, 2H, CpH), 4.29(s, 5H, CpH), 3.96—4.00(m, 2H, CH₂), 1.54—1.61(m, 2H, CH₂), 0.81(t, J=7.6 Hz, 3H, CH₃)
2d	7.53—7.54(m, 1H, PhH), 7.50—7.52(m, 1H, PhH), 7.47—7.50(m, 3H, PhH), 7.40—7.42(m, 2H, PhH), 7.19—7.24(m, 2H, PhH), 7.12—7.16(m, 1H, PhH), 4.78(t, J=2.0 Hz, 2H, CpH), 4.39(t, J=2.0 Hz, 2H, CpH), 4.29(s, 5H, CpH), 3.99—4.03(m, 2H, CH₂), 1.51—1.58(m, 2H, CH₂), 1.25—1.30(m, 2H, CH₂), 1.16—1.21(m, 8H, CH₂), 0.89(t, J=7.2 Hz, 3H, CH₃)
2e	7.56(dd, J=8.8, 1.2 Hz, 2H, PhH), 7.46(t, J=3.2 Hz, 3H, PhH), 7.39—7.41(m, 2H, PhH), 7.23(t, J=7.2 Hz, 2H, PhH), 7.13—7.17(m, 1H, PhH), 5.86—5.95(m, 1H, —CH=C—), 5.25(dd, J=10.4, 0.8 Hz, 1H, CH), 4.94(dd, J=17.2, 0.8 Hz, 1H, CH), 4.85(t, J=2.0 Hz, 2H, CH₂), 4.70—4.72(m, 2H, CpH), 4.37(t, J=2.0 Hz, 2H, CpH), 4.26(s, 5H, CpH)
2f	7.60(s, 2H, PhH), 7.34(d, J=6.8 Hz, 4H, PhH), 7.30(d, J=2.0 Hz, 1H, PhH), 7.26(s, 1H, PhH), 7.21—7.24(m, 4H, PhH), 7.16—7.18(m, 1H, PhH), 7.00(d, J=7.2 Hz, 2H, PhH), 5.33(s, 2H, —CH₂Ph), 4.67(t, J=2.0 Hz, 2H, CpH), 4.29(t, J=2.0 Hz, 2H, CpH), 4.22(s, 5H, CpH)
3a	7.56(dd, J=7.2, 1.6 Hz, 4H, PhH), 7.39—7.42(m, 6H, PhH), 5.08(t, J=1.6 Hz, 2H, CpH), 4.73(t, J=1.6 Hz, 2H, CpH), 4.49(s, 5H, CpH), 3.97(s, 6H, CH₃)
3b	7.60(d, J=15.2 Hz, 4H, PhH), 7.41(d, J=8.0 Hz, 6H, PhH), 5.03(s, 2H, CpH), 4.74(s, 2H, CpH), 4.50(s, 7H, CpH, CH₂), 4.04(s, 3H, CH₃), 1.19(s, 3H, CH₃)
3c	7.56(d, J=19.2 Hz, 4H, PhH), 7.38(s, 6H, PhH), 5.01(s, 2H, CpH), 4.73(s, 2H, CpH), 4.49(s, 5H, CpH), 4.29(s, 2H, CH₂), 4.07(s, 3H, Im⁺CH₃), 1.72—1.77(m, 2H, CH₂), 1.51—1.62(m, 3H, CH₃)
3d	7.53—7.58(m, 4H, PhH), 7.39(d, J=8.4 Hz, 6H, PhH), 5.00(s, 2H, CpH), 4.73(s, 2H, CpH), 4.49(s, 5H, CpH), 4.32(t, J=7.2 Hz, 2H, CH₂), 4.06(s, 3H, CH₃), 1.43—1.47(m, 2H, CH₂), 1.19—1.22(m, 2H, CH₂), 1.05—1.07(m, 8H, CH₂), 0.84(t, J=7.2 Hz, 3H, CH₃)
3e	7.65(t, J=3.6 Hz, 2H, PhH), 7.53(d, J=7.2 Hz, 2H, PhH), 7.35—7.40(m, 6H, PhH), 5.91—6.00(m, 1H, CH), 5.34(d, J=14 Hz, 1H, CH), 5.03—5.09(m, 5H, CH, CH₂, 2CpH), 4.71(s, 2H, CpH), 4.49(s, 5H, CpH), 4.04(s, 3H, CH₃)
3f	7.67(d, J=3.6 Hz, 2H, PhH), 7.38—7.40(m, 5H, PhH), 7.36(s, 2H, PhH), 7.31(s, 1H, PhH), 7.27(s, 1H, PhH), 7.22(d, J=7.2 Hz, 2H, PhH), 6.98(d, J=7.2 Hz, 2H, PhH), 5.72(s, 2H, CH₂), 4.98(s, 2H, CpH), 4.65(s, 2H, CpH), 4.48(s, 5H, CpH), 4.10(s, 3H, CH₃)

Table 2 1H NMR data for compounds 2a—2f and 3a—3f*

Compd.	¹H NMR(400 MHz, CDCl₃), δ
2a	7.55(d, J=7.6 Hz, 2H, PhH), 7.46—7.50(m, 3H, PhH), 7.41(dd, J=7.6, 1.6 Hz, 2H, PhH), 7.23(t, J=7.6 Hz, 2H, PhH), 7.15(t, J=7.6 Hz, 1H, PhH), 4.82(t, J=2.0 Hz, 2H, CpH), 4.41(t, J=2.0 Hz, 2H, CpH), 4.27(s, 5H, CpH), 3.68(s, 3H, CH₃)
2b	7.49—7.54(m, 5H, PhH), 7.43(dd, J=7.2, 2.0 Hz, 2H, PhH), 7.22(t, J=7.2 Hz, 2H, PhH), 7.14(t, J=7.2 Hz, 1H, PhH), 4.81(t, J=1.6 Hz, 2H, CpH), 4.40(t, J=1.6 Hz, 2H, CpH), 4.30(s, 5H, CpH), 4.12(q, J=7.2 Hz, 2H, CH₂), 1.20(t, J=7.2 Hz, 3H, CH₃)
2c	7.53—7.54(m, 1H, PhH), 7.51—7.52(m, 1H, PhH), 7.47—7.50(m, 3H, PhH), 7.40—7.42(m, 2H, PhH), 7.22(t, J=7.6 Hz, 2H, PhH), 7.12—7.16(m, 1H, PhH), 4.77(t, J=1.6 Hz, 2H, CpH), 4.39(t, J=1.6 Hz, 2H, CpH), 4.29(s, 5H, CpH), 3.96—4.00(m, 2H, CH₂), 1.54—1.61(m, 2H, CH₂), 0.81(t, J=7.6 Hz, 3H, CH₃)
2d	7.53—7.54(m, 1H, PhH), 7.50—7.52(m, 1H, PhH), 7.47—7.50(m, 3H, PhH), 7.40—7.42(m, 2H, PhH), 7.19—7.24(m, 2H, PhH), 7.12—7.16(m, 1H, PhH), 4.78(t, J=2.0 Hz, 2H, CpH), 4.39(t, J=2.0 Hz, 2H, CpH), 4.29(s, 5H, CpH), 3.99—4.03(m, 2H, CH₂), 1.51—1.58(m, 2H, CH₂), 1.25—1.30(m, 2H, CH₂), 1.16—1.21(m, 8H, CH₂), 0.89(t, J=7.2 Hz, 3H, CH₃)
2e	7.56(dd, J=8.8, 1.2 Hz, 2H, PhH), 7.46(t, J=3.2 Hz, 3H, PhH), 7.39—7.41(m, 2H, PhH), 7.23(t, J=7.2 Hz, 2H, PhH), 7.13—7.17(m, 1H, PhH), 5.86—5.95(m, 1H, —CH=C—), 5.25(dd, J=10.4, 0.8 Hz, 1H, CH), 4.94(dd, J=17.2, 0.8 Hz, 1H, CH), 4.85(t, J=2.0 Hz, 2H, CH₂), 4.70—4.72(m, 2H, CpH), 4.37(t, J=2.0 Hz, 2H, CpH), 4.26(s, 5H, CpH)
2f	7.60(s, 2H, PhH), 7.34(d, J=6.8 Hz, 4H, PhH), 7.30(d, J=2.0 Hz, 1H, PhH), 7.26(s, 1H, PhH), 7.21—7.24(m, 4H, PhH), 7.16—7.18(m, 1H, PhH), 7.00(d, J=7.2 Hz, 2H, PhH), 5.33(s, 2H, —CH₂Ph), 4.67(t, J=2.0 Hz, 2H, CpH), 4.29(t, J=2.0 Hz, 2H, CpH), 4.22(s, 5H, CpH)
3a	7.56(dd, J=7.2, 1.6 Hz, 4H, PhH), 7.39—7.42(m, 6H, PhH), 5.08(t, J=1.6 Hz, 2H, CpH), 4.73(t, J=1.6 Hz, 2H, CpH), 4.49(s, 5H, CpH), 3.97(s, 6H, CH₃)
3b	7.60(d, J=15.2 Hz, 4H, PhH), 7.41(d, J=8.0 Hz, 6H, PhH), 5.03(s, 2H, CpH), 4.74(s, 2H, CpH), 4.50(s, 7H, CpH, CH₂), 4.04(s, 3H, CH₃), 1.19(s, 3H, CH₃)
3c	7.56(d, J=19.2 Hz, 4H, PhH), 7.38(s, 6H, PhH), 5.01(s, 2H, CpH), 4.73(s, 2H, CpH), 4.49(s, 5H, CpH), 4.29(s, 2H, CH₂), 4.07(s, 3H, Im⁺CH₃), 1.72—1.77(m, 2H, CH₂), 1.51—1.62(m, 3H, CH₃)
3d	7.53—7.58(m, 4H, PhH), 7.39(d, J=8.4 Hz, 6H, PhH), 5.00(s, 2H, CpH), 4.73(s, 2H, CpH), 4.49(s, 5H, CpH), 4.32(t, J=7.2 Hz, 2H, CH₂), 4.06(s, 3H, CH₃), 1.43—1.47(m, 2H, CH₂), 1.19—1.22(m, 2H, CH₂), 1.05—1.07(m, 8H, CH₂), 0.84(t, J=7.2 Hz, 3H, CH₃)
3e	7.65(t, J=3.6 Hz, 2H, PhH), 7.53(d, J=7.2 Hz, 2H, PhH), 7.35—7.40(m, 6H, PhH), 5.91—6.00(m, 1H, CH), 5.34(d, J=14 Hz, 1H, CH), 5.03—5.09(m, 5H, CH, CH₂, 2CpH), 4.71(s, 2H, CpH), 4.49(s, 5H, CpH), 4.04(s, 3H, CH₃)
3f	7.67(d, J=3.6 Hz, 2H, PhH), 7.38—7.40(m, 5H, PhH), 7.36(s, 2H, PhH), 7.31(s, 1H, PhH), 7.27(s, 1H, PhH), 7.22(d, J=7.2 Hz, 2H, PhH), 6.98(d, J=7.2 Hz, 2H, PhH), 5.72(s, 2H, CH₂), 4.98(s, 2H, CpH), 4.65(s, 2H, CpH), 4.48(s, 5H, CpH), 4.10(s, 3H, CH₃)

Table 3 Appearance, yields, melting points, HRMS and IR data for compounds 4a—4f

Compd.	Appearance	Yield^a(%)	m. p. /℃	HRMS(ESI), m/z[M-P $F 6 -$ ]⁺	IR(KBr), $ν ˙$ /cm^-1
4a	Orange solid	76	> 250^b	433.1342	3056, 2961, 1514, 1437, 704
4b	Orange solid	70	> 250^b	447.1504	3056, 2958, 1594, 1497, 702
4c	Orange solid	67	> 250^b	461.1659	3049, 2958, 1600, 1491, 702
4d	Orange solid	62	> 250^b	531.2444	3059, 2926, 1594, 1497, 702
4e	Orange solid	68	197—198	459.1505	3088, 3062, 2926, 1639, 1491, 1086
4f	Orange solid	75	99—101	509.1662	3013, 2966, 1594, 1503, 1051, 695

Table 3 Appearance, yields, melting points, HRMS and IR data for compounds 4a—4f

Compd.	Appearance	Yield^a(%)	m. p. /℃	HRMS(ESI), m/z[M-P $F 6 -$ ]⁺	IR(KBr), $ν ˙$ /cm^-1
4a	Orange solid	76	> 250^b	433.1342	3056, 2961, 1514, 1437, 704
4b	Orange solid	70	> 250^b	447.1504	3056, 2958, 1594, 1497, 702
4c	Orange solid	67	> 250^b	461.1659	3049, 2958, 1600, 1491, 702
4d	Orange solid	62	> 250^b	531.2444	3059, 2926, 1594, 1497, 702
4e	Orange solid	68	197—198	459.1505	3088, 3062, 2926, 1639, 1491, 1086
4f	Orange solid	75	99—101	509.1662	3013, 2966, 1594, 1503, 1051, 695

Table 4 1H NMR, 13C NMR and 19F NMR data for compounds 4a—4f

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ	¹⁹F NMR(376 MHz, CDCl₃), δ
4a	7.45(d, J=2.0 Hz, 1H, PhH), 7.43(t, J=2.0 Hz, 3H, PhH), 7.42(s, 1H, PhH), 7.41(s, 4H, PhH), 7.39(s, 1H, PhH), 4.95(t, J=2.0 Hz, 2H, CpH), 4.72(t, J=2.0 Hz, 2H, CpH), 4.44(s, 5H, CpH), 3.89(s, 6H, CH₃)	149.7, 136.9, 136.0, 135.2, 134.2, 131.0, 76.5, 75.8, 75.6, 71.5, 60.1, 40.4	-153.70, -153.75
4b	7.59(dd, J=13.6, 6.4 Hz, 4H, PhH), 7.41(d, J=9.6 Hz, 6H, PhH), 5.01(s, 2H, CpH), 4.74(s, 2H, CpH), 4.50(s, 5H, CpH), 4.46(t, J=7.2 Hz, 2H, CH₂), 4.03(s, 3H, CH₃), 1.47(t, J=7.2 Hz, 3H, CH₃)	144.2, 133.1, 131.7, 131.2, 131.1, 130.1, 130.0, 129.0, 128.9, 125.9, 125.5, 71.4, 70.8, 70.8, 67.0, 42.3, 35.4, 15.5	-153.36, -153.41
4c	7.43—7.47(m, 4H, PhH), 7.35—7.38(m, 6H, PhH), 4.90(t, J=1.6 Hz, 2H, CpH), 4.72(t, J=1.6 Hz, 2H, CpH), 4.45(s, 5H, CpH), 4.26(t, J=8.0 Hz, 2H, CH₂), 4.00(s, 3H, CH₃), 1.41—1.47(m, 2H, CH₂), 0.68(t, J=7.2 Hz, 3H, CH₃)	144.4, 132.9, 132.0, 131.1, 131.0, 130.0, 129.9, 129.0, 128.9, 126.0, 125.7, 71.4, 70.8, 70.5, 67.3, 48.3, 34.9, 23.1, 10.8	-153.40, -153.53
4c	7.43—7.47(m, 4H, PhH), 7.35—7.38(m, 6H, PhH), 4.90(t, J=1.6 Hz, 2H, CpH), 4.72(t, J=1.6 Hz, 2H, CpH), 4.45(s, 5H, CpH), 4.26(t, J=8.0 Hz, 2H, CH₂), 4.00(s, 3H, CH₃), 1.41—1.47(m, 2H, CH₂), 0.68(t, J=7.2 Hz, 3H, CH₃)	145.2, 133.4, 132.1, 132.0, 131.3, 131.0, 130.1, 130.0, 129.0, 128.8, 125.7, 125.6, 118.6, 71.5, 70.7, 70.7, 66.6, 49.1, 35.3	-153.56, -153.61
4d	7.50(d, J=7.6 Hz, 4H, PhH), 7.39(d, J=7.6 Hz, 6H, PhH), 4.95(s, 2H, CpH ), 4.72(s, 2H, CpH), 4.47(s, 5H, CpH), 4.31(t, J=7.6 Hz, 2H, CH₂), 4.03(s, 3H, CH₃), 1.27(s, 1H, CH₂), 1.21(t, J=7.2 Hz, 2H, CH₂), 1.04(s, 9H, CH₂), 0.84(t, J=7.2 Hz, 3H, CH₃)	144.2, 132.9, 132.0, 131.2, 131.1, 130.1, 130.0, 129.0, 67.3, 46.9, 35.3, 31.6, 29.6, 28.7, 28.4, 26.2, 22.5, 14.1	-153.63, -153.68
4e	7.50(dd, J=6.8, 2.0 Hz, 2H, PhH), 7.42(s, 1H, PhH), 7.41(d, J=2.0 Hz, 1H, PhH), 7.37—7.39(m, 4H, PhH), 7.35(d, J=7.6 Hz, 2H, PhH), 5.84—5.93(m, 1H, CH), 5.30(d, J=10.4 Hz, 1H, CH), 4.97—5.04(m, 5H, CH, CH₂, 2CpH), 4.69(t, J=1.6 Hz, 2H, CpH), 4.44(s, 5H, CpH), 3.95(s, 3H, CH₃)	145.2, 133.4, 132.1, 132.0, 131.3, 131.0, 130.1, 130.0, 129.0, 128.8, 125.7, 125.6, 118.6, 71.5, 70.7, 70.7, 66.6, 49.1, 35.3	-153.56, -153.61
4f	7.65(s, 2H, PhH), 7.36—7.40(m, 5H, PhH), 7.36(s, 2H, PhH), 7.31(s, 1H, PhH), 7.26(s, 1H, PhH), 7.22(d, J=7.2 Hz, 2H, PhH), 6.98(d, J=6.4 Hz, 2H, PhH), 5.72(s, 2H, CH₂), 4.96(s, 2H, CpH), 4.65(s, 2H, CpH), 4.48(s, 5H, CpH), 4.09(s, 3H, CH₃)	145.7, 135.0, 133.6, 132.3, 131.1, 131.0, 130.0, 129.9, 129.2, 129.0, 128.7, 128.2, 125.9, 125.6, 125.5, 71.6, 70.8, 70.7, 66.6, 50.4, 35.6	-153.56, -153.61

Table 4 1H NMR, 13C NMR and 19F NMR data for compounds 4a—4f

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ	¹⁹F NMR(376 MHz, CDCl₃), δ
4a	7.45(d, J=2.0 Hz, 1H, PhH), 7.43(t, J=2.0 Hz, 3H, PhH), 7.42(s, 1H, PhH), 7.41(s, 4H, PhH), 7.39(s, 1H, PhH), 4.95(t, J=2.0 Hz, 2H, CpH), 4.72(t, J=2.0 Hz, 2H, CpH), 4.44(s, 5H, CpH), 3.89(s, 6H, CH₃)	149.7, 136.9, 136.0, 135.2, 134.2, 131.0, 76.5, 75.8, 75.6, 71.5, 60.1, 40.4	-153.70, -153.75
4b	7.59(dd, J=13.6, 6.4 Hz, 4H, PhH), 7.41(d, J=9.6 Hz, 6H, PhH), 5.01(s, 2H, CpH), 4.74(s, 2H, CpH), 4.50(s, 5H, CpH), 4.46(t, J=7.2 Hz, 2H, CH₂), 4.03(s, 3H, CH₃), 1.47(t, J=7.2 Hz, 3H, CH₃)	144.2, 133.1, 131.7, 131.2, 131.1, 130.1, 130.0, 129.0, 128.9, 125.9, 125.5, 71.4, 70.8, 70.8, 67.0, 42.3, 35.4, 15.5	-153.36, -153.41
4c	7.43—7.47(m, 4H, PhH), 7.35—7.38(m, 6H, PhH), 4.90(t, J=1.6 Hz, 2H, CpH), 4.72(t, J=1.6 Hz, 2H, CpH), 4.45(s, 5H, CpH), 4.26(t, J=8.0 Hz, 2H, CH₂), 4.00(s, 3H, CH₃), 1.41—1.47(m, 2H, CH₂), 0.68(t, J=7.2 Hz, 3H, CH₃)	144.4, 132.9, 132.0, 131.1, 131.0, 130.0, 129.9, 129.0, 128.9, 126.0, 125.7, 71.4, 70.8, 70.5, 67.3, 48.3, 34.9, 23.1, 10.8	-153.40, -153.53
4c	7.43—7.47(m, 4H, PhH), 7.35—7.38(m, 6H, PhH), 4.90(t, J=1.6 Hz, 2H, CpH), 4.72(t, J=1.6 Hz, 2H, CpH), 4.45(s, 5H, CpH), 4.26(t, J=8.0 Hz, 2H, CH₂), 4.00(s, 3H, CH₃), 1.41—1.47(m, 2H, CH₂), 0.68(t, J=7.2 Hz, 3H, CH₃)	145.2, 133.4, 132.1, 132.0, 131.3, 131.0, 130.1, 130.0, 129.0, 128.8, 125.7, 125.6, 118.6, 71.5, 70.7, 70.7, 66.6, 49.1, 35.3	-153.56, -153.61
4d	7.50(d, J=7.6 Hz, 4H, PhH), 7.39(d, J=7.6 Hz, 6H, PhH), 4.95(s, 2H, CpH ), 4.72(s, 2H, CpH), 4.47(s, 5H, CpH), 4.31(t, J=7.6 Hz, 2H, CH₂), 4.03(s, 3H, CH₃), 1.27(s, 1H, CH₂), 1.21(t, J=7.2 Hz, 2H, CH₂), 1.04(s, 9H, CH₂), 0.84(t, J=7.2 Hz, 3H, CH₃)	144.2, 132.9, 132.0, 131.2, 131.1, 130.1, 130.0, 129.0, 67.3, 46.9, 35.3, 31.6, 29.6, 28.7, 28.4, 26.2, 22.5, 14.1	-153.63, -153.68
4e	7.50(dd, J=6.8, 2.0 Hz, 2H, PhH), 7.42(s, 1H, PhH), 7.41(d, J=2.0 Hz, 1H, PhH), 7.37—7.39(m, 4H, PhH), 7.35(d, J=7.6 Hz, 2H, PhH), 5.84—5.93(m, 1H, CH), 5.30(d, J=10.4 Hz, 1H, CH), 4.97—5.04(m, 5H, CH, CH₂, 2CpH), 4.69(t, J=1.6 Hz, 2H, CpH), 4.44(s, 5H, CpH), 3.95(s, 3H, CH₃)	145.2, 133.4, 132.1, 132.0, 131.3, 131.0, 130.1, 130.0, 129.0, 128.8, 125.7, 125.6, 118.6, 71.5, 70.7, 70.7, 66.6, 49.1, 35.3	-153.56, -153.61
4f	7.65(s, 2H, PhH), 7.36—7.40(m, 5H, PhH), 7.36(s, 2H, PhH), 7.31(s, 1H, PhH), 7.26(s, 1H, PhH), 7.22(d, J=7.2 Hz, 2H, PhH), 6.98(d, J=6.4 Hz, 2H, PhH), 5.72(s, 2H, CH₂), 4.96(s, 2H, CpH), 4.65(s, 2H, CpH), 4.48(s, 5H, CpH), 4.09(s, 3H, CH₃)	145.7, 135.0, 133.6, 132.3, 131.1, 131.0, 130.0, 129.9, 129.2, 129.0, 128.7, 128.2, 125.9, 125.6, 125.5, 71.6, 70.8, 70.7, 66.6, 50.4, 35.6	-153.56, -153.61

Fig.1 Molecular structure of compound 3a

Table 5 Cell parameters of compound 3a

Compound	3a	D_c/(g·cm^-3)	1.599
Empirical formula	C₂₇H₂₅FeIN₂	Abs. coeff./mm^-1	1.991
Formula weight	560.24	F(000)	1120
T/K	296(2)	Crystal size	0.50 mm×0.40 mm×0.20 mm
λ/nm	0.071073	Index ranges	-12≤h≤12; -7≤k≤4; -27≤l≤27
Crystal system	Monoclinic	Reflections collected	10136
Space group	P2₁/n	Independent reflections	2764 [R(int)=0.0226]
a/nm	1.1930(3)	Reflections observed	2428
b/nm	0.74519(18)	Data completeness	0.980
c/nm	2.6536(6)	Refinement method	Full-matrix least-squares on F²
α/(°)	90	Data/Restraints/Parameters	2764/0/282
β/(°)	99.420(4)	Goodness-of-fit on F²	1.043
γ/(°)	90	Final R indices[I>2σ(I)]	R₁=0.0231; wR₂=0.0546
V/nm³	2.3272(10)	R(all data)	R₁=0.0284; wR₂=0.0575
Z	4

Table 6 Selected bond lengths(nm) and angles(°) for compound 3a

N2—C5	0.1353(4)	N2—C8	0.1383(4)	N2—C12	0.1459(4)
C3—C34	0.1422(4)	C3—C34	0.1422(4)	N4—C5	0.1348(4)
N4—C9	0.1387(4)	N4—C9	0.1387(4)	C5—C20	0.1460(4)
C7—C18	0.1409(5)	C7—C18	0.1409(5)	C8—C9	0.1351(4)
C8—C10	0.1483(4)	C8—C10	0.1483(4)	C10—C30	0.1380(5)
C10—C31	0.1384(5)	C10—C31	0.1384(5)	C13—C23	0.1385(5)
C5—N2—C8	10.92(2)	C5—N2—C12	12.67(2)	C34—C3—C20	10.82(3)
C5—N4—C9	10.97(2)	C9—N4—C22	12.37(2)	N4—C5—C20	12.73(3)
C5—N4—C22	12.65(2)	N4—C5—N2	10.67(2)	N2—C5—C20	12.59(3)

Table 7 UV-Vis spectra data of compounds 1, 2a—2f, 3a—3f and 4a—4f

Compd.	λ_max/nm	Compd.	λ_max/nm	Compd.	λ_max/nm
1	296.0	3a	288.5	4a	288.3
2a	291.1	3b	285.1	4b	285.0
2b	289.4	3c	285.2	4c	285.3
2c	289.0	3d	284.5	4d	284.8
2d	289.2	3e	287.8	4e	288.0
2e	289.1	3f	288.0	4f	288.0
2f	289.0

Table 8 Electrochemistry data of compounds 1, 2a—2f and 4a—4f

Compd.	E_pa/V	E_pc/V	$E ˉ p a$ /V	Δ $E p b$ /V	Compd.	E_pa/V	E_pc/V	$E ˉ p a$ /V	Δ $E p b$ /V
1	0.673	0.600	0.6365	0.073	4a	0.995	0.916	0.9355	0.079
2a	0.686	0.611	0.6485	0.075	4b	0.976	0.902	0.9390	0.074
2b	0.686	0.610	0.6480	0.076	4c	0.972	0.901	0.9365	0.071
2c	0.682	0.609	0.6455	0.073	4d	0.980	0.906	0.9430	0.074
2d	0.686	0.612	0.6490	0.074	4e	1.002	0.925	0.9635	0.077
2e	0.695	0.622	0.6585	0.073	4f	0.979	0.908	0.9435	0.071
2f	0.683	0.613	0.6480	0.070

Table 8 Electrochemistry data of compounds 1, 2a—2f and 4a—4f

Compd.	E_pa/V	E_pc/V	$E ˉ p a$ /V	Δ $E p b$ /V	Compd.	E_pa/V	E_pc/V	$E ˉ p a$ /V	Δ $E p b$ /V
1	0.673	0.600	0.6365	0.073	4a	0.995	0.916	0.9355	0.079
2a	0.686	0.611	0.6485	0.075	4b	0.976	0.902	0.9390	0.074
2b	0.686	0.610	0.6480	0.076	4c	0.972	0.901	0.9365	0.071
2c	0.682	0.609	0.6455	0.073	4d	0.980	0.906	0.9430	0.074
2d	0.686	0.612	0.6490	0.074	4e	1.002	0.925	0.9635	0.077
2e	0.695	0.622	0.6585	0.073	4f	0.979	0.908	0.9435	0.071
2f	0.683	0.613	0.6480	0.070

Fig.2 DSC curves of compounds AP, AP+1 and AP+2a—AP+2f(A), AP+3a—AP+3f(B) and AP+4a—AP+4f(C)

Fig.3 TG curves of compounds AP, AP+1 and AP+2a—AP+2f(A), AP+3a—AP+3f(B) and AP+4a—AP+4f(C)

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2-茂铁基-4,5-二苯基咪唑离子液体的合成及对高氯酸铵热分解的催化作用

Synthesis of 2-Ferrocenyl-4,5-diphenylimidazolium Ionic Liquids and Their Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate^†

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2-茂铁基-4,5-二苯基咪唑离子液体的合成及对高氯酸铵热分解的催化作用

Synthesis of 2-Ferrocenyl-4,5-diphenylimidazolium Ionic Liquids and Their Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate†

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Synthesis of 2-Ferrocenyl-4,5-diphenylimidazolium Ionic Liquids and Their Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate^†