类杯芳烃孔穴桥联双芘分子开关化合物

doi:10.7503/cjcu20150445

摘要/Abstract

摘要：

利用构型可变的分子开关类杯芳烃孔穴化合物(Cavitand)作为母体, 合成了2种具有不同臂长的双芘Cavitand化合物. 在室温及中性状态下, 2种双芘Cavitand化合物均可检验出分子内激基复合物荧光, 其中短臂双芘Cavitand化合物的荧光明显强于长臂Cavitand化合物. 经三氟乙酸酸化后, 2种双芘化合物的分子内激基复合物荧光消失; 而继续使用碱中和至中性, 则荧光恢复. 这个荧光出现-消失-出现的过程验证了Cavitand母体化合物分子构型闭合-打开-闭合可有效调控分子激基复合物荧光开关过程. 此外, 通过高斯计算模拟了2种化合物的理论分子构型, 发现长臂双芘化合物在Cavitand母体构型处于闭合状态时2个芘基团重叠部分较少是其分子内激基复合物荧光较弱的关键原因.

关键词: 分子开关, 类杯芳烃孔穴化合物, 荧光, 双芘Cavitand化合物

Abstract:

Two kinds of di-py-cavitand compounds with different arm lengths were synthesized using molecular switch which configurations are variable-class calixarene cavities(Cavitand) as the parent compounds. In the neutral state of room temperature, the two kinds of di-py-cavitand compounds can detect intramolecular exciplex fluorescence and the compounds with short arm is obviously more stronger than the long arm one in the fluorescence intensity. However, intramolecular exciplex fluorescence disappears after acidification by trifluoroacetic acid and appears again when continuing to add alkali so as to neutralize to neutral state. The process of fluorescence appearing-disappearing-appearing powerfully verified that the process of closing-opening-closing of the molecular configuration of cavitand parent compounds can efficiently control intramolecular exciplex fluorescence’s opening and closing processes. In addition, the molecular configurations of di-py-cavitand compounds in theory with different arm length were simulated through Gaussian calculation module, finding that two pyrene groups of di-py-cavitand compound with long arm were less overlaped when the cavitand parent configuration was in the closing state, which is the key cause of the corresponding weak intramolecular exciplex fluorescence intensity.

Key words: Molecular switch, Class calixarene cavities compounds(Cavitand), Fluorescence, Di-py-cavitand compound

中图分类号:

O626

TrendMD:

徐海, 赵斯祺, 任扬, 蔡健峰, 汪翔, 林雨霖. 类杯芳烃孔穴桥联双芘分子开关化合物. 高等学校化学学报, 2015, 36(12): 2421.

XU Hai, ZHAO Siqi, REN Yang, CAI Jianfeng, WANG Xiang, LIN Yulin. Bridged Di-py-cavitand Compounds as Molecular Switch^†. Chem. J. Chinese Universities, 2015, 36(12): 2421.

图/表 7

Fig.1 Molecular configurations of Cavitand compounds in different conditions

Scheme 1 Synthetic process of bridged di-py-cavitand compounds

Table 1 Appearance, yields, melting points, HRMS and IR data of compounds 3, 4, 6a and 6b

Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd.), m/z[M+H]⁺	IR(KBr), $ν ˙$ /cm^-1
3	Yellow solid	100	194—195	498.1804	3039, 2920, 2851, 2360, 2206, 2106, 1922, 1794, 1738, 1674,
				(498.1795)	1600, 1516, 1463, 1435, 1407, 1298, 1243, 1181, 1103, 1018,
					971, 836, 757, 716, 681, 647, 613
4	Green solid	100	228—229	426.1409	3272, 3036, 2360, 2207, 2105, 1917, 1794, 1662, 1598, 1516,
				(426.1398)	1406, 1264, 1104, 965, 899, 832, 761, 717, 661, 632
6a	Yellow solid	34	>300	2022.7986	3044, 2924, 2852, 2202, 1738, 1583, 1483, 1412, 1361, 1260,
				(2022.7934)	1157, 1108, 843, 800, 752
6b	Yellow solid	17	>300	2422.9210	3038, 2955, 2922, 2852, 2360, 2210, 2160, 1738, 1600, 1482,
				(2422.9238)	1412, 1364, 1260, 1202, 1158, 1068, 840, 763, 717

Table 1 Appearance, yields, melting points, HRMS and IR data of compounds 3, 4, 6a and 6b

Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd.), m/z[M+H]⁺	IR(KBr), $ν ˙$ /cm^-1
3	Yellow solid	100	194—195	498.1804	3039, 2920, 2851, 2360, 2206, 2106, 1922, 1794, 1738, 1674,
				(498.1795)	1600, 1516, 1463, 1435, 1407, 1298, 1243, 1181, 1103, 1018,
					971, 836, 757, 716, 681, 647, 613
4	Green solid	100	228—229	426.1409	3272, 3036, 2360, 2207, 2105, 1917, 1794, 1662, 1598, 1516,
				(426.1398)	1406, 1264, 1104, 965, 899, 832, 761, 717, 661, 632
6a	Yellow solid	34	>300	2022.7986	3044, 2924, 2852, 2202, 1738, 1583, 1483, 1412, 1361, 1260,
				(2022.7934)	1157, 1108, 843, 800, 752
6b	Yellow solid	17	>300	2422.9210	3038, 2955, 2922, 2852, 2360, 2210, 2160, 1738, 1600, 1482,
				(2422.9238)	1412, 1364, 1260, 1202, 1158, 1068, 840, 763, 717

Table 2 1H NMR and 13C NMR data of compounds 2—4, 6a, 6b

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(75 MHz, CDCl₃), δ
2	0.26(s, 9H, CH₃), 7.24(m, 2H, apparent AA'BB' ArH), 7.44(s, 1H, ArH), 7.79(m, 2H, apparent AA'BB' ArH)	0.04, 90.30, 94.36, 96.43, 104.44, 122.39, 122.81, 123.07, 128.34, 131.24, 131.80, 132.93, 137.43
3	0.26(s, 9H, CH₃), 7.58—7.78(q, 4H, ArH), 7.50(s, 4H, ArH), 8.02—8.75(m, 9H, PyH)	0.04, 90.30, 94.36, 96.43, 104.44, 122.39, 122.81, 123.07, 128.34, 131.24, 131.80, 132.93, 137.43
4	3.20(s, 1H, CH), 7.58—7.73(q, 4H, J=8.4 Hz, ArH), 7.50(d, 4H, ArH), 8.04—8.67(m, 9H, J=0.9 Hz, PyH)	132.00, 131.83, 131.57, 131.52, 131.39, 131.14, 130.94, 129.54, 128.26, 128.21, 127.14, 126.19, 125.62, 125.58, 125.34, 124.46, 123.54, 123.42, 122.70, 121.99, 117.33, 94.74, 91.11, 90.75, 83.21, 79.03
6a	0.91—0.97(m, 12H, CH₃), 1.24—1.59(m, 40H), 2.05—2.30(m, 12H), 5.60—5.81(m, 4H, methane CH) 7.36(s, 4H ArH), 7.43—7.45(q, 4H, J=3.4 Hz, ArH), 7.58(d, 4H, J=9.0 Hz, ArH) 8.15(s, 4H, ArH), 7.64—8.45(m, 22H, ArH and PyH)	14.25, 18.34, 18.49, 22.85, 28.13, 29.55, 29.88, 32.06, 32.37, 32.81, 34.35, 90.50, 94.13, 117.23, 119.02, 123.97, 12.24, 124.50, 124.64, 125.33, 125.68, 125.87, 125.95, 126.25, 127.23, 128.59, 128.66, 128.97, 129.83, 130.96, 131.18, 131.63, 132.14, 132.385, 135.91, 136.32, 137.06, 137.71, 140.00, 141.74, 152.11, 152.27, 152.48, 153.27, 159.06, 161.69
6b	0.91—0.97(m, 12H, CH₃), 1.24—1.56(m, 40H), 2.05—2.30(m, 12H), 5.60—5.81(m, 4H, methane CH), 7.27(s, 4H, ArH), 7.49(s, 4H, ArH), 7.30—7.34(q, 4H, J=3.3 Hz, ArH), 7.61(s, 8H, ArH), 7.64—8.45(m, 16H, PyH), 8.20—8.30(m, 16H, ArH), 8.66—8.70(d, 2H, J=9.3 Hz, PyH)	14.26, 14.31, 17.87, 17.99, 18.22, 18.29, 22.86, 28.14, 28.17, 29.56, 29.91, 32.07, 32.37, 32.89, 34.39, 34.49, 90.50, 90.82, 91.05, 91.24, 91.57, 95.05, 96.72, 117.70, 119.00, 123.10, 123.60, 123.97, 124.58, 124.80, 125.40, 125.70, 125.97, 126.53, 127.49, 128.54, 128.61, 128.71, 128.98, 129.13, 129.61, 129.90, 131.32, 131.51, 131.63, 131.71, 131.89, 131.92, 131.95, 131.98, 132.22, 132.43, 135.92, 136.21, 137.06, 137.09, 137.61, 138.04, 138.43, 139.34, 140.02, 141.63, 141.70, 141.76, 152.24, 152.26, 152.45, 153.30, 159.08, 161.51, 161.64

Table 2 1H NMR and 13C NMR data of compounds 2—4, 6a, 6b

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(75 MHz, CDCl₃), δ
2	0.26(s, 9H, CH₃), 7.24(m, 2H, apparent AA'BB' ArH), 7.44(s, 1H, ArH), 7.79(m, 2H, apparent AA'BB' ArH)	0.04, 90.30, 94.36, 96.43, 104.44, 122.39, 122.81, 123.07, 128.34, 131.24, 131.80, 132.93, 137.43
3	0.26(s, 9H, CH₃), 7.58—7.78(q, 4H, ArH), 7.50(s, 4H, ArH), 8.02—8.75(m, 9H, PyH)	0.04, 90.30, 94.36, 96.43, 104.44, 122.39, 122.81, 123.07, 128.34, 131.24, 131.80, 132.93, 137.43
4	3.20(s, 1H, CH), 7.58—7.73(q, 4H, J=8.4 Hz, ArH), 7.50(d, 4H, ArH), 8.04—8.67(m, 9H, J=0.9 Hz, PyH)	132.00, 131.83, 131.57, 131.52, 131.39, 131.14, 130.94, 129.54, 128.26, 128.21, 127.14, 126.19, 125.62, 125.58, 125.34, 124.46, 123.54, 123.42, 122.70, 121.99, 117.33, 94.74, 91.11, 90.75, 83.21, 79.03
6a	0.91—0.97(m, 12H, CH₃), 1.24—1.59(m, 40H), 2.05—2.30(m, 12H), 5.60—5.81(m, 4H, methane CH) 7.36(s, 4H ArH), 7.43—7.45(q, 4H, J=3.4 Hz, ArH), 7.58(d, 4H, J=9.0 Hz, ArH) 8.15(s, 4H, ArH), 7.64—8.45(m, 22H, ArH and PyH)	14.25, 18.34, 18.49, 22.85, 28.13, 29.55, 29.88, 32.06, 32.37, 32.81, 34.35, 90.50, 94.13, 117.23, 119.02, 123.97, 12.24, 124.50, 124.64, 125.33, 125.68, 125.87, 125.95, 126.25, 127.23, 128.59, 128.66, 128.97, 129.83, 130.96, 131.18, 131.63, 132.14, 132.385, 135.91, 136.32, 137.06, 137.71, 140.00, 141.74, 152.11, 152.27, 152.48, 153.27, 159.06, 161.69
6b	0.91—0.97(m, 12H, CH₃), 1.24—1.56(m, 40H), 2.05—2.30(m, 12H), 5.60—5.81(m, 4H, methane CH), 7.27(s, 4H, ArH), 7.49(s, 4H, ArH), 7.30—7.34(q, 4H, J=3.3 Hz, ArH), 7.61(s, 8H, ArH), 7.64—8.45(m, 16H, PyH), 8.20—8.30(m, 16H, ArH), 8.66—8.70(d, 2H, J=9.3 Hz, PyH)	14.26, 14.31, 17.87, 17.99, 18.22, 18.29, 22.86, 28.14, 28.17, 29.56, 29.91, 32.07, 32.37, 32.89, 34.39, 34.49, 90.50, 90.82, 91.05, 91.24, 91.57, 95.05, 96.72, 117.70, 119.00, 123.10, 123.60, 123.97, 124.58, 124.80, 125.40, 125.70, 125.97, 126.53, 127.49, 128.54, 128.61, 128.71, 128.98, 129.13, 129.61, 129.90, 131.32, 131.51, 131.63, 131.71, 131.89, 131.92, 131.95, 131.98, 132.22, 132.43, 135.92, 136.21, 137.06, 137.09, 137.61, 138.04, 138.43, 139.34, 140.02, 141.63, 141.70, 141.76, 152.24, 152.26, 152.45, 153.30, 159.08, 161.51, 161.64

Table 3 Chemical shift of di-py-cavitand compounds

Compound 6a				Compound 6b
System	Pyrene shift	T/℃	Pyrene shift	System	Pyrene shift	T/℃	Pyrene shift
NaOD	8.46	35	8.47	NaOD	8.69	35	8.69
TFA-D	8.67	-20	8.47	TFA-D	8.69	-20	8.68
D₂O	8.46	-65	8.69	D₂O	8.72	-65	8.67

Fig.2 Fluorescence spectra of bridged di-py-cavitand compounds with short arm(A) and long arm(B) a. Neat; b. neutual with base; c. TFA.

Fig.3 Cis/trans isomer of structures of bridged di-py-cavtiand compounds with “bud” conformation (A) Dcc=0; (B) Dcc=0.39 nm; (C) Dcc=0.38 nm; (D) Dcc=0.38 nm.

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