(dr. maxim a. shcherbina) · effect of the shape of mesogenic group on structure and phase...

Effect of the Shape of Mesogenic Group on Structure and Phase Behaviour of 2,3,4-tris(dodecyloxy) benzenesulfonates with Alkaline Cations Maxim A. Shcherbina*a,b, Artem V. Bakirovb, Andrei N. Yakuninc, Uwe Beginnd, Linglong Yane, Martin Möllere and Sergei N. Chvalunab

a Enikolopov Institute of Synthetic Polymer Materials RAS. 70, Profsoyuznaya street, Moscow, 117393 Russian Federation. b Kurchatov Institute. 1, Kurchatov sq., Moscow, 123098 Russian Federation. c Karpov Institute of Physical Chemistry. 10, Vorontsovo Pole, Moscow, 105064 Russian Federation. d Universität Osnabrück, Institut für Chemie, OMC. Barbarastraße 7, D-49076 Osnabrück, Deutschland. e DWI / RWTH Aachen University. Building 5293 / DWI Erweiterungsbau, Forckenbeckstraße 50. 52056 Aachen. e-mail: [email protected] (Dr. Maxim A. Shcherbina)

Electronic Supplementary Material (ESI) for Soft MatterThis journal is © The Royal Society of Chemistry 2013

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Structure and Phase Behaviour of Lithium 2,3,4-tris(dodecyloxy)benzenesulfonate Figure S1. 1H spectrum (300 MHz, CDCl3, 20°C, TMS, δ, ppm) of lithium 2,3,4-tris(dodecyloxy)benzene sulfonate.

Figure S2. 13C spectrum (75 MHz, CDCl3, 20°C, TMS, δ, ppm) of lithium 2,3,4-tris(dodecyloxy)benzene sulfonate.


Table S1. Crystallographic data for as-received samples of lithium 2,3,4-tris(dodecyloxy)benzenesulfonate (Figure 2, curve 1). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for two different layer structures with interlayer distance of L1 = 3.64 nm and L2 = 3.27 nm, and their corresponding indices.

N qN dN(obs) i dN

(calc) hk 1 1.72 3.64 61 3.64 10 2 1.92 3.27 100 3.27 10* 3 3.49 1.80 1.4 1.82 20 4 3.86 1.63 4.3 1.63 20* 5 5.22 1.20 1.8 1.21 30

Table S2. Crystallographic data for lithium 2,3,4-tris(dodecyloxy)benzenesulfonate at 90ºC (Figure 2, curve 2). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for 2-D orthogonal unit cell (a = 3.58 nm, b = 3.30 nm) and their corresponding indices.

N qN dN(obs) i dN

(calc) hk 1 1.77 3.54 100 3.58 10 2 3.56 1.76 2.5 1.79 20 3 3.96 1.59 0.04 1.65 20* 4 5.37 1.17 2.4 1.19 30

Table S3. Crystallographic data for lithium 2,3,4-tris(dodecyloxy)benzenesulfonate at 130ºC (Figure 2, curve 3). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for Pm3n cubic lattice (a = 5.95 nm).

N qN dN(obs) i dN

(calc) hkl 1 1.48 4.25 0.23 4.21 110 2 2.10 3.00 24.1 2.98 200 3 2.36 2.66 100 2.66 210 4 2.59 2.42 58.3 2.43 211 5 2.99 2.10 0.5 2.10 220 6 3.34 1.88 0.25 1.88 310 7 3.66 1.72 0.15 1.72 222 8 3.81 1.65 0.08 1.65 320 9 3.96 1.59 0.19 1.59 321

10 4.38 1.44 0.21 1.44 410


Table S4. Crystallographic data for lithium 2,3,4-tris(dodecyloxy)benzene sulfonate at 170ºC (Figure 2, curve 4). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for primitive cubic lattice (a = 2.585 nm).

N qN dN(obs) i dN

(calc) hkl 1 2.42 2.59 100 2.585 100 2 3.44 1.83 1.5 1.83 110 3 4.23 1.49 0.07 1.49 111

Table S5. Crystallographic data for lithium 2,3,4-tris(dodecyloxy)benzene sulfonate at 220ºC (Figure 2, curve 5). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for primitive cubic lattice (a = 2.56 nm).

N qN dN(obs) i dN

(calc) hkl 1 2.44 2.57 100 2.56 100 2 3.46 1.82 1.3 1.82 110 3 4.25 1.48 0.07 1.48 111

Figure S3. TGA analysis of lithium 2,3,4-tris(dodecyloxy)benzene sulfonate in nitrogen atmosphere (heating rate is 20ºC/min).


Structure and Phase Behaviour of Sodium 2,3,4-tris(dodecyloxy)benzenesulfonate Figure S4. 1H spectrum (300 MHz, CDCl3, 20°C, TMS, δ, ppm) of sodium 2,3,4-tris(dodecyloxy)benzene sulfonate.

Figure S5. 13C spectrum (75 MHz, CDCl3, 20°C, TMS, δ, ppm) of sodium 2,3,4-tris(dodecyloxy)benzene sulfonate.


Table S6. Crystallographic data for as-received samples of sodium 2,3,4-tris(dodecyloxy)benzene sulfonate (Figure 6). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for I23 cubic unit cell (a = 6.18 nm) and their corresponding indices.

N qN dN(obs) i dN

(calc) hkl 1 1.45 4.34 100.00 4.37 110 2 2.04 3.07 98.75 3.09 200 3 2.87 2.19 2.23 2.18 220 4 3.13 2.00 0.03 1.95 310 5 3.78 1.66 0.85 1.65 312 6 4.07 1.54 2.04 1.54 400 7 4.76 1.32 0.48 1.32 332 8 5.12 1.23 0.05 1.26 422 / 431 9 5.40 1.16 0.53 1.21 440 10 5.78 1.09 0.66 1.09 442 11 6.14 1.02 0.61 1.03 600 12 6.48 0.97 0.03 0.98 620 13 6.75 0.93 0.53 0.93 622 14

7.14 0.88 0.03 0.87 710 / 543 /

550 15 8.03 0.78 0.90 0.78 723, 651

Table S7. Crystallographic data for sodium 2,3,4-tris(dodecyloxy)benzene sulfonate at 100ºC (Figure 7, curve 1). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for 2-D hexagonal columnar lattice (a = 3.44 nm).

N qN dN(obs) i dN

(calc) hk 1 2.11 2.98 100 2.97 10 2 3.68 1.71 1.34 1.72 11 3 4.25 1.48 0.39 1.49 20

Table S8. Crystallographic data for sodium 2,3,4-tris(dodecyloxy)benzene sulfonate at 140ºC (Figure 7, curve 2). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for Pm3n cubic lattice (a = 6.51 nm).

N qN dN(obs) i dN

(calc) hkl 1 1.36 4.62 0.33 4.61 110 2 1.93 3.25 5.17 3.26 200 3 2.16 2.91 100.00 2.91 210 4 2.38 2.64 81.91 2.66 211 5 2.75 2.28 0.44 2.30 220 6 3.05 2.06 0.15 2.06 310 7 3.88 1.62 0.04 1.74 320 8 4.02 1.56 0.11 1.58 321


Structure and Phase Behaviour of Potassium 2,3,4-tris(dodecyloxy)benzenesulfonate

Figure S6. 1H spectrum (300 MHz, CDCl3, 20°C, TMS, δ, ppm) of potassium 2,3,4-tris(dodecyloxy)benzene sulfonate.

Figure S7. 13C spectrum (75 MHz, CDCl3, 20°C, TMS, δ, ppm) of potassium 2,3,4-tris(dodecyloxy)benzene sulfonate.


Table S9. Crystallographic data for as-received samples of potassium 2,3,4-tris(dodecyloxy)benzene sulfonate (Figure 10). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for I23 cubic unit cell (a = 6.39 nm) and their corresponding indices.

N qN dN(obs) i dN

(calc) hkl 1 1.84 3.42 0.56 3.20 200 2 2.41 2.61 100.00 2.61 211 3 2.71 2.32 1.51 2.26 220 4 3.25 1.94 23.47 1.85 222 5 3.50 1.80 6.32 1.71 321 6 4.20 1.49 0.21 1.51 420 7 4.69 1.34 2.15 1.31 422 8 4.89 1.29 1.67 1.25 431, 501 9 5.27 1.19 1.74 1.17 521

10 5.61 1.12 0.42 1.07 600, 422 11 7.05 0.89 0.42 0.85 642 12 7.81 0.80 0.83 0.79 820, 644

13 8.11 0.78 0.42 0.74 743, 750,

813 Table S10. Crystallographic data for potassium 2,3,4-tris(dodecyloxy)benzene sulfonate at 100ºC (Figure 11, curve 1). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for P6/mmm hexagonal unit cell (a = 3.67 nm, c = 4.83 nm,) and their corresponding indices.

N qN dN(obs) i dN

(calc) hkl 1 1.30 4.83 0.87 4.83 001 2 2.01 3.12 7.1 3.12 100 3 2.41 2.61 100 2.62 101 4 2.63 2.39 5.2 2.41 002 5 3.01 2.09 16.9 1.91 102 6 3.74 1.68 0.83 1.69 111 7 4.89 1.29 1.96 1.31 202

Table S11. Crystallographic data for potassium 2,3,4-tris(dodecyloxy)benzene sulfonate at 170ºC (Figure 11, curve 3). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for 2-D hexagonal columnar lattice (a = 3.37 nm).

N qN dN(obs) i dN

(calc) hk 1 2.15 2.92 100 2.92 10 2 3.78 1.66 1.15 1.69 11 3 4.37 1.44 0.29 1.46 20


Table S12. Crystallographic data for sodium 2,3,4-tris(dodecyloxy)benzene sulfonate at 200ºC (Figure 11, curve 4). Observed positions of X-Ray reflections (q-vector values, nm-1), corresponding d-spacings (nm) and their relative intensities; calculated d-spacings (nm) for Pm3n cubic lattice (a = 6.48 nm).

N qN dN(obs) i dN

(calc) hkl 1 1.37 4.58 0.08 4.58 110 2 1.93 3.26 2.5 3.24 200 3 2.18 2.88 100 2.90 210 4 2.38 2.64 35.2 2.65 211 5 2.78 2.26 0.17 2.29 220 6 3.07 2.04 0.16 2.05 310 7 4.02 1.56 0.12 1.57 410

Structure and Phase Behaviour of Caesium 2,3,4-tris(dodecyloxy)benzenesulfonate

Figure S8. 1H spectrum (300 MHz, CDCl3, 20°C, TMS, δ, ppm) of caesium 2,3,4-tris(dodecyloxy)benzene sulfonate.


Figure S9. 13C spectrum (75 MHz, CDCl3, 20°C, TMS, δ, ppm) of caesium 2,3,4-tris(dodecyloxy)benzene sulfonate.

Figure S10. TGA analysis of caesium 2,3,4-tris(dodecyloxy)benzenesulfonate in nitrogen atmosphere (heating rate is 20ºC/min).


(dr. maxim a. shcherbina) · effect of the shape of mesogenic group on structure and phase...

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