Synthesis and Mesocrystalline Properties of Glassy Liquid Crystal Compounds Based on Tetrathiofuvalene and Cyanobenzene†

doi:10.7503/cjcu20180116

Abstract

Abstract:

Mesocrystalline cyanodiphenyl moiety was introduced to the periphery of tetrathiofuvalene(TTF) to successfully synthesize three new liquid crystal compounds. Their structures were fully characterized by means of NMR, FTIR and MALDI-TOF-MS methods. The liquid crystal phase state of the compounds was studied by differential scanning calorimetry(DSC), hot stage polarizing microscopy(HS-POM) and small angle X-ray scattering(SAXS) experiment. The results demonstrated that the synthesized compounds in the wide range of temperature displayed a single liquid crystal phase and in the cooling process did not appear crystallization phenomenon, but transformed into the glass state. The change of linker length had significant influence on the phase state of liquid crystal compounds. The results illustrated that compound with shorter linker represented smectic A phase(SmA), while compound with longer spacer(1c) presented hexagonal columnar mesophase. The density functional theory(DFT) was used to calculate the electron structure and the electron density distribution of molecular frontier orbital of compound 1a. The results showed that the electron cloud density of the HOMO orbital of compound 1a was concentrated on TTF, and that of LUMO was concentrated on cyanobenzene, indicating that such liquid crystal molecules were typical D-σ-A molecules.

Key words: Tetrathiofuvalene(TTF), Cyanobiphenyl, Glassy liquid crystal, Density functional theory

CLC Number:

TrendMD:

WEI Fuzhi, FENG Wei, XIA Yan, LI Dongfeng, HOU Ruibin. Synthesis and Mesocrystalline Properties of Glassy Liquid Crystal Compounds Based on Tetrathiofuvalene and Cyanobenzene^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1549.

Figures/Tables 9

Scheme 1 Synthetic route of compounds 1a—1c

Table 1 Appearance, yields, IR and MALDI-TOF-MS data of compounds 1a—1c

Compd.	Appearance	Yield(%)	IR(KBr), $ν ˙$ /cm^-1	MALDI-TOF-MS[M⁺+H](calcd.)
1a	Orange solid	23.5	2916, 2851, 2227, 1603, 1493, 1291, 1249, 1181, 1030, 824	1553(1554)
1b	Orange solid	25.6	2921, 2851, 2227, 1603, 1493, 1293, 1248, 1178, 1039, 824	1665(1666)
1c	Orange solid	22.8	2921, 2851, 2227, 1603, 1493, 1293, 1248, 1178, 1028, 825	1777(1778)

Table 1 Appearance, yields, IR and MALDI-TOF-MS data of compounds 1a—1c

Compd.	Appearance	Yield(%)	IR(KBr), $ν ˙$ /cm^-1	MALDI-TOF-MS[M⁺+H](calcd.)
1a	Orange solid	23.5	2916, 2851, 2227, 1603, 1493, 1291, 1249, 1181, 1030, 824	1553(1554)
1b	Orange solid	25.6	2921, 2851, 2227, 1603, 1493, 1293, 1248, 1178, 1039, 824	1665(1666)
1c	Orange solid	22.8	2921, 2851, 2227, 1603, 1493, 1293, 1248, 1178, 1028, 825	1777(1778)

Table 2 NMR data of compounds 1a—1c

Compd.	¹H NMR(CDCl₃, 400 MHz), δ	¹³C NMR(CDCl₃, 100 MHz), δ
1a	7.69(d, J=8.0 Hz, 8H), 7.63(d, J= 8.0 Hz, 8H), 7.52(d, J=8.0 Hz, 8H), 6.99(d, J=8.0 Hz, 8H), 4.00(t, J=6.1 Hz, 8H), 2.82(t, J=8.0 Hz, 8H), 1.84—1.77(m, 8H), 1.68—1.61(m, 8H), 1.57(m, 8H), 1.52—1.32(m, 32H)	159.77, 145.23, 132.6—57, 131.31, 128.33, 127.77, 127.06, 119.08, 115.09, 110.10, 109.95, 68.10, 36.23, 29.68, 29.22, 29.00, 28.39, 25.98
1b	7.68(d, J=8.1 Hz, 8H), 7.63(d, J=8.2 Hz, 8H), 7.52(d, J=8.4 Hz, 8H), 6.98(d, J=8.5 Hz, 8H), 3.99(t, J=6.2 Hz, 8H), 2.81(t , 8H), 1.80(m, 8H), 1.63(m, 8H), 1.46(s, 8H), 1.41—1.26(m, 48H)	159.84, 145.29, 132.32, 128.36, 127.10, 119.13, 115.13, 110.12, 68.20, 36.23, 29.76, 29.52, 29.46, 29.40, 29.28, 29.12, 28.52, 26.09
1c	7.69(d, J=8.1 Hz, 8H), 7.64(d, J=8.2 Hz, 8H), 7.52(d, J=8.4 Hz, 8H), 7.00(d, J=8.5 Hz, 8H), 4.01(t, J=6.2 Hz, 8H), 2.82(s, 8H), 1.85—1.78(m, 8H), 1.68—1.60(m, 8H), 1.48—1.43(m, 8H), 1.43—1.27(m, 62H)	159.65, 145.09, 132.40, 131.08, 128.15, 126.89, 118.93, 114.93,109.90, 68.02, 36.13, 29.58, 29.41, 29.34, 29.25, 29.09, 28.95, 28.35, 25.90

Fig.1 DSC thermograms of glassy liquid crystal 1b

Table 3 DSC and TGA measurement results of target compounds

Compd.	Second heating process			Second cooling process			$T f d$ /℃
Compd.	$T a g$ /℃	$T b S A$ /℃	ΔH^c(J/mol)	ΔH^d(J/mol)	$T e S A$ /℃	$T a g$ /℃	$T f d$ /℃
1a	11.54	101.21	5.53	-5.16	98.48	8.32	284
1b	9.86	108.40	7.86	-7.75	104.43	2.96	292
1c	8.50	108.56	2.46	-11.09	105.07	5.98	278

Table 3 DSC and TGA measurement results of target compounds

Compd.	Second heating process			Second cooling process			$T f d$ /℃
Compd.	$T a g$ /℃	$T b S A$ /℃	ΔH^c(J/mol)	ΔH^d(J/mol)	$T e S A$ /℃	$T a g$ /℃	$T f d$ /℃
1a	11.54	101.21	5.53	-5.16	98.48	8.32	284
1b	9.86	108.40	7.86	-7.75	104.43	2.96	292
1c	8.50	108.56	2.46	-11.09	105.07	5.98	278

Fig.2 Optical polarized micrograph(50×) of compounds 1a(A), 1b(B) and 1c(C) at 60 ℃

Fig.3 Small-angle X-ray scattering patterns of compounds 1a(A), 1b(B) and 1c(C) after being cooled to 60 ℃

Fig.4 Cyclic voltammograms of compounds 1a—1c(a—c) in DMF(1×10-3 mol/L) and DPV(inset)

Fig.5 Quantum calculation of target compound 1a

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