基于四硫富瓦烯和氰基联苯单元的玻璃态液晶化合物的合成及介晶性能

doi:10.7503/cjcu20180116

摘要/Abstract

摘要：

将性能优良的介晶单元氰基联苯基元引入到四硫富瓦烯(TTF)的外围, 成功合成了3种新型的液晶化合物. 通过核磁共振波谱(NMR)、傅里叶变换红外光谱(FTIR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)对其结构进行了表征. 利用示差扫描量热分析(DSC)、热台偏光显微镜(HS-POM)和小角X射线散射(SAXS)实验对3种化合物的液晶相态进行了研究. 结果表明: 合成的3种化合物在宽的温度范围呈现单一液晶相, 在冷却过程中并没有出现结晶现象, 而是转化为玻璃态. 间隔基长度的变化对液晶化合物相态的影响显著, 间隔基较短的化合物呈近晶A相(SmA), 而具有较长间隔基的化合物(1c)呈现六方柱状相. 采用密度泛函(DFT)方法计算了化合物1a的电子结构和前线分子轨道密度分布, 化合物1a的HOMO轨道上的电子云密度集中在TTF上, LUMO集中在氰基联苯上, 说明此类液晶分子为典型的D-σ-A分子.

关键词: 四硫富瓦烯(TTF), 氰基联苯, 玻璃态液晶, 密度泛函理论

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

中图分类号:

TrendMD:

魏福志, 冯微, 夏艳, 李东风, 侯瑞斌. 基于四硫富瓦烯和氰基联苯单元的玻璃态液晶化合物的合成及介晶性能. 高等学校化学学报, 2018, 39(7): 1549.

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

图/表 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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