Synthesis and Properties of Barbituric Acid Based Taper Shaped Rodlike Liquid Crystal Compound and Hydrogen Bonded Complex with Triazine Derivative†

doi:10.7503/cjcu20160877

Abstract

Abstract:

A new kind of barbituric acid based taper shaped rodlike compound 4-{[2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene]methyl}phenyl-3,4,5-tris(dodecyloxy)benzoate(BA³/12), consisting of a styrene conjugate rodlike core with the barbituric acid at one end, and benzoate wedge unit with triple alkyl chain at the other end was synthesized. The properties were investigated with polarising optical microscopy(POM), differential scanning calorimetry(DSC), X-ray diffraction(XRD), scanning electron microscope(SEM), infrared spectrum(IR), nuclear magnetic resonance(NMR) spectroscopy and fluorescence emission spectrum. Compound BA³/12 can self-assemble into columnar liquid crystalline(LC) phase with c2mm lattice. The structure of complex BA/T between BA³/12 and triazine 6-[5-(4-{[3,4-bis(dodecyloxy)benzyl]oxy}phenyl)thiophen-2-yl]-1,3,5-triazine-2,4-diamine(1T²/12) was initially identified via IR and ¹H NMR. This complex BA/T showed both liquid crystalline property in its pure state and supramolecular organogels with three-dimensional networks in organic solvents.

Key words: Barbituric acid, H-Bonding, Liquid crystal, Organogel, Fluorescence quenching

CLC Number:

O626.41

TrendMD:

XIA Meng, PENG Xiongwei, GAO Hongfei, YAN Chao, CHEN Huiru, CHENG Xiaohong. Synthesis and Properties of Barbituric Acid Based Taper Shaped Rodlike Liquid Crystal Compound and Hydrogen Bonded Complex with Triazine Derivative^†[J]. Chem. J. Chinese Universities, 2017, 38(7): 1203.

Figures/Tables 10

Scheme 1 Synthesis route of compound BA3/12a. n-C12H25Br, K2CO3, DMF, reflux 24 h, 90 ℃(yield 96.2%); b. KOH, C2H5OH, 60 ℃, reflux 15 h(yield 92.3%); c. 4-hydroxybenzaldehyde, DCC, DMAP, dry CH2Cl2, 25 ℃, 20 h(yield 87.5%); d. C2H5OH, barbituri-cacid, 60 ℃, reflux 4 h(yield 85.4%).

Table 1 Phase transition temperatures and associated enthalpy values of compounds BA3/12, 1T2/12 and BA/Ta

Compd.	Transition temperature/℃[Enthalpy change/(kJ·mol^-1)]
Compd.	C $r 1 b$	C $r 2 b$	Co $l rec b$	I^b	I^c	Co $l rec c$	C $r 1 c$
BA³/12	108.2(40.4)			137.3(30.0)	136.7(0.5)	124.9(13.8)	114.6(0.4)
1T²/12	67.0(3.76)	133.2(9.4)	172.1(22.9)	184.5(0.8)	182(1.1)	154.0(21.0)
BA/T^d			121	191	181	134

Table 1 Phase transition temperatures and associated enthalpy values of compounds BA3/12, 1T2/12 and BA/Ta

Compd.	Transition temperature/℃[Enthalpy change/(kJ·mol^-1)]
Compd.	C $r 1 b$	C $r 2 b$	Co $l rec b$	I^b	I^c	Co $l rec c$	C $r 1 c$
BA³/12	108.2(40.4)			137.3(30.0)	136.7(0.5)	124.9(13.8)	114.6(0.4)
1T²/12	67.0(3.76)	133.2(9.4)	172.1(22.9)	184.5(0.8)	182(1.1)	154.0(21.0)
BA/T^d			121	191	181	134

Fig.1 Texture of columnar phase at 123 ℃(A), SAXS diffractogram at 130 ℃(B), electron density map as reconstructed from the diffraction pattern of (B)(C) and molecular model the Colrec phase(D) of BA3/12

Fig.2 FTIR spectra of BA3/12(a), 1T2/12(b) and complex BA/T(c)

Fig.3 Schematic representation of hydrogen bonding between 1T2/12 and BA3/12

Fig.4 Fluorescence spectra of 1T2/12(4 μmol/L) in DCM with increasing concentration of BA3/12c(BA3/12)/(μmol·L-1)= 0, 0.4, 0.8, 1.6, 2.4, 3.2, 4.0, 4.8, 5.6, 6.4, 7.2; λex=386 nm. Inset: the fluorescence of 1T2/12 and BA3/12, respectively in DCM solution under UV irradiation at 365 nm.

Fig.5 Stern-volmer plots of the fluorescence quenching of 1T2/12 by compound BA3/12F0 is the fluorescence intensity of 1T2/12 without BA3/12; F is the fluorescence intensity of 1T2/12 with different concentrations of BA3/12.

Fig.6 Texture of columnar phase of BA3/12 at 123 ℃(A), 1T2/12 at 169 ℃(B) and BA/T at 154 ℃(C)

Fig.7 Reversible thermo- and mechano-responsive gels of binary mixture BA/T in ethylacetate

Fig.8 SEM image of xerogel formed by binary mixture BA/T in ethyl acetate

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