Bridged Di-py-cavitand Compounds as Molecular Switch†

doi:10.7503/cjcu20150445

Abstract

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

CLC Number:

O626

TrendMD:

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

Figures/Tables 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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