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

doi:10.7503/cjcu20170708

Abstract

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

CLC Number:

O626.2

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 889.

Figures/Tables 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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