Supporting Information

Crystal-to-Crystal Synthesis of Helically Ordered Polymers of

Trehalose by Topochemical Polymerization
Kuntrapakam Hema, Rajesh G. Gonnade, and Kana M. Sureshan*

anie_201914164_sm_miscellaneous_information.pdf
Author Contributions

R.G.G. contributed to this paper by refining the crystal structures.

S.No. Table of Contents Page No.

1 Materials and methods S2

2 Synthesis of monomer 1 S3

3 Crystallization of monomer 1 S6
1
4 H NMR spectrum of form II crystals in DMSO-d6 S6

5 ORTEP diagrams of form I and form II S7

6 Crystal structures of form I and form II S7

7 Topochemical azide-alkyne cycloaddition (TAAC) of form I and form II S7

8 Time-dependent FT-IR during TAAC reaction of form I and form II S7

9 Kinetics of TAAC reactions of form I and form II S8

10 Thermogravimetric analysis of form II crystals after heating for 36 h S8

11 Isolation of dimer S9

12 Molten state azide-alkyne cycloaddition reaction of 1 S11

13 Gel permeation chromatography (GPC) analysis S12

14 MALDI-TOF analysis of polymers obtained from form I and form II S12

15 Circular dichroism (CD) spectroscopic analysis of form I and form II crystals S12

16 Circular dichroism (CD) spectroscopic analysis of the random polymers S12

17 Circular dichroism (CD) spectroscopic analysis of the polymer in solution S13

state

18 Crystal data of form I and form II S13

19 Unit cell determination of the heated crystal of form II S14
20 Non-covalent interactions in form I and form II S14

21 References S16

22 Spectral information S17

S1
1. Materials and methods
All the chemicals and solvents were purchased from commercial suppliers and were used without
further purification. Reactions were monitored by thin layer chromatography (TLC) using Merck pre-
coated silica plates. TLC plates were visualized under ultraviolet light at 254 nm and also by charring
after dipping in ceric ammonium molybdate solution. Column chromatography was performed using
silica gel (200-400 mesh) as the stationery phase. 1H, 13C NMR spectra were recorded using 500 MHz
and 125 MHz NMR spectrometers, respectively. Proton chemical shifts (δ) are relative to
tetramethylsilane (TMS, δ = 0.0) as internal standard and expressed in parts per million (ppm). Spin
multiplicities were represented as s (singlet), d (doublet), t (triplet), dd (doublet of doublet), and m
(multiplet). Coupling constants (J) are given in Hertz. The protons and carbons were assigned by using
two-dimensional NMR spectroscopic techniques such as COSY, HMQC and HMBC. Melting points
were determined a Stanford Research Systems (EZ-Melt) melting point apparatus. Specific rotations
were recorded on a Rudolph Autopol III automatic polarimeter. Elemental analyses were done on
Elementar, vario MICRO cube elemental analyzer. X-ray intensity data measurements of freshly grown
crystals were done on a Bruker-KAPPA APEX II CCD diffractometer with graphite-monochromatized
(MoK = 0.71073Å) radiation. Refinement was carried out with SHELXL-2014. The microscopic
images were taken using Leica Microsystems (Leica M80). The solid-state reactions of the monomers
to polymers were studied by various time-dependent techniques. Time-dependent 1H NMR spectra were
recorded after dissolving the solid samples in CDCl3. 1H NMR spectra were overlaid using MestreNova.
FT-IR spectra were recorded using a IR Prestige-21 (Shimadzu) spectrometer using KBr pellet method.
DSC analyses were done using a DSC Q2000 differential scanning calorimeter with a nitrogen flow
rate of 100 mL/min. and at a heating rate of 5 oC/min. TGA analyses were done using a TGA Q50
thermogravimetric analyzer with a nitrogen flow rate of 100 mL/min. and at a heating rate of 5 oC/min.
The PXRD experiments were conducted using slow and continuous scan rate mode using Cu as the
anode material (Kα1 = 1.540598Å). Gel permeation chromatography analyses were carried out on an
Agilent 1260 Infinity GPC/SEC (PLgel column) using chloroform as mobile phase (flow rate
1mL/min.) using RI detector and polystyrene as the standard. MALDI-TOF mass spectrum of sample
was recorded on a Bruker Daltonics flex Analysis mass spectrometer using 2,5-dihydroxybenzoic acid
as the matrix. CD spectra of solid samples were recorded on a JASCO (J-815) CD spectrometer by KBr
pellet method with a bandwidth of 10 nm and scanning speed of 200 nm/min.

S2
2. Synthesis of the azide- and alkyne-functionalized monomer 1

Scheme S1. Synthesis of the monomer 1.

Synthesis of compound 3
Anhydrous α,α-D-trehalose (5.18 g, 15.13 mmol) was taken in an RB flask and kept in an oven at 110
o
C for 4 h. To this, suspension of trehalose in anhydrous DMF (50 mL), CSA (1.05 g, 4.54 mmol) and
p-anisaldehyde dimethylacetal (5.93 mL, 34.80 mmol) were added under N2 atmosphere and heated at
80 oC. The reaction was monitored by TLC analysis. After 1h, the starting material was consumed
completely. Then the reaction was quenched by adding Et3N (6 mL, pH>7) and the solvents were
evaporated in a rotary evaporator. The obtained crude residue was purified by column chromatography
using ethyl acetate/petroleum ether (8:2; v/v) as eluent to afford compound 3 (8.5 g, 97%) as a white
solid (m.p. 239-241 oC). 1H NMR of the compound matched with the reported data.1

Synthesis of compound 4
To a solution of compound 3 (8.0 g, 13.83 mmol) in dry DMF (60 mL), NaH (60% in oil; 4.41 g, 110.62
mmol) was added in small portions at 0 oC under N2 atmosphere. To this, PMBCl (14.97 mL, 110.62
mmol) was added at 0 oC. Upon completion of the starting material (40 min.), the reaction was quenched
by the slow dropwise addition of ice cold water (4 mL). The reaction mixture was taken in EtOAc, and
was washed with water and brine successively, dried over anhydrous Na2SO4 and the solvents were
evaporated in a rotary evaporator. The residue obtained was purified by column chromatography using
ethyl acetate/petroleum ether (4:6; v/v) as eluent to obtain compound 4 (14.05 g, 96%) as a sticky syrup.
1
H NMR of the compound matched with the reported data.1

S3
Synthesis of compound 5
To a solution of compound 4 (10 g, 9.44 mmol) in dry DCM (200 mL), 1.5 M DIBAL (25 wt% in
toluene; 37.8 mL, 56.64 mmol) was added dropwise at -15 oC under N2 atmosphere and stirred at the
same temperature for 10 h. After the consumption of the starting material, the reaction was quenched
by slow addition of methanol (10 mL) at -15 oC followed by aq. KOH (10%, 10 mL) at rt. The reaction
mixture was then diluted with DCM and the organic layer was then washed successively with water and
brine. The organic layer was dried over anhydrous Na2SO4 and evaporated under reduced pressure. The
crude mass was purified by column chromatography using ethyl acetate/petroleum ether (7:3; v/v) as
eluent to obtain diol 5 as a white solid (7.62 g, 76%; m.p. 110-112 oC). The 1H NMR of the compound
matched with the reported data.1
Synthesis of compound 6
To a solution of diol 5 (7 g, 6.59 mmol) in dry pyridine (70 mL), mesyl chloride (0.46 mL, 5.93 mmol)
was added at 0 oC. The reaction mixture was then stirred for 3 h. Then the reaction mixture was diluted
with EtOAc and washed with sat. aq. NaHCO3, water and brine successively. The organic layer was
dried over anhydrous Na2SO4 and the solvents were evaporated under reduced pressure. The crude
residue was purified by column chromatography using ethyl acetate/petroleum ether (6:4; v/v) as eluent
to obtain 6 (5.05 g, 67%) as a colorless sticky liquid.
[α]D 25 = 83.5° (c 0.2, CHCl3); Rf = 0.3 (ethyl acetate/ petroleum ether, 6:4; v/v); 1H NMR (500 MHz,
CDCl3) δ: 7.21 (dd, J = 5.3 Hz, 8.5 Hz, 4H, ArH), 7.17-7.11 (m, 8H, ArH), 6.82-6.78 (m, 8H, ArH),
6.74 (dd, J = 6.4 Hz, 8.5 Hz, 4H, ArH), 4.96 (t, J = 3.8 Hz, 2H, H-1, H-7), 4.83 (dd, J = 6.5 Hz, 10.4
Hz, 2H, ArCH2), 4.76-4.70 (m, 4H, 2 X ArCH2), 4.62 (d, J = 11.5 Hz, 1H, ArCH2A/ ArCH2B), 4.52-
4.50 (m, 3H, ArCH2, ArCH2B/ ArCH2A), 4.46 (dd, J = 2.7 Hz, 11.7 Hz, 2H, ArCH2), 4.10-4.04 (m, 2H,
H-5, H-6A/H-6B), 3.96 (m, 1H, H-11), 3.93-3.84 (m, 3H, H-3, H-9, H-6B/H-6A), 3.73 (s, 6H, 2 X
CH3), 3.71 (s, 3H, CH3), 3.70 (s, 9H, 3 X CH3), 3.55 (brm, 2H, H-12A, H-12B), 3.47-3.36 (m, 4H, H-
2, H-4, H-8, H-10), 2.82 (s, 3H, CH3), 1.43 (t, J = 6.1 Hz, 1H, OH); 13C NMR (125 MHz, CDCl3) δ:
159.46, 159. 41, 159.3, 159.26, 159.20, 130.9, 130.8, 130.3, 130.2, 130.1, 130.0, 129.8, 129.7, 129.5,
129.4, 129.2, 129.1, 113.96, 113.95, 113.90, 113.85, 113.82, 94.5 (C-1/C-7), 94.1 (C-7/C-1), 81.5 (C-
3/C-9), 81.2 (C-9/C-3), 79.4, 78.9, 76.6, 75.3 (ArCH2), 74.8 (ArCH2), 74.7 (ArCH2), 73.1 (ArCH2),
72.6 (ArCH2), 71.4 (C-11), 68.9 (C-5), 68.1 (C-6), 61.7 (C-12), 55.32 (OCH3), 55.30 (OCH3), 55.2
(OCH3), 37.3 (CH3). Elemental analysis calcd for C61H72O19S: C, 64.20; H, 6.36; S, 2.81. Found: C,
64.54; H, 6.45; S, 2.64.
Synthesis of compound 7
To a solution of compound 6 (5.0 g, 4.38 mmol) in anhydrous DMF (40 mL), sodium azide (0.60 g,
9.20 mmol) was added under N2 atmosphere. The reaction mixture was then heated at 80 oC. Upon
completion of the starting material (3 h), the reaction mixture was then dissolved in EtOAc and washed
with water and brine successively. The organic layer was dried over anhydrous Na2SO4 and solvents
were evaporated under reduced pressure. The residue obtained was purified by column chromatography
using ethyl acetate/petroleum ether (1:1; v/v) as eluent to obtain 7 (4.14 g, 87%) as a colourless sticky
liquid.
[α]D 25 = 102.5° (c 0.2, CHCl3); Rf = 0.7 (ethyl acetate/ petroleum ether, 1:1; v/v); 1H NMR (500 MHz,
CDCl3) δ: 7.20 (dd, J = 4.2 Hz, 8.5 Hz, 4H, ArH), 7.16-7.11 (m, 8H, ArH), 6.79 (t, J = 8.5 Hz, 8H,
ArH), 6.73 (d, J = 8.5 Hz, 4H, ArH), 5.03 (d, J = 3.5 Hz, 1H, H-1/H-7), 5.02 (d, J = 3.5 Hz, 1H, H-7/H-
1), 4.82 (dd, J = 3.6 Hz, 10.7 Hz, 2H, ArCH2), 4.76-4.68 (m, 4H, 2 X ArCH2), 4.59-4.56 (m, 2H,
ArCH2), 4.53 (brs, 2H, ArCH2), 4.50 (d, J = 10.6 Hz, 1H, ArCH2A/ArCH2B), 4.42 (d, J = 10.6 Hz, 1H,
ArCH2B/ArCH2A), 4.06 (m, 1H, H-5), 3.96 (m, 1H, H-11), 3.94-3.88 (m, 2H, H-3, H-9), 3.73 (s, 3H, 1
X CH3), 3.72 (s, 3H, 1 X CH3), 3.71 (s, 6H, 2 X CH3), 3.70 (s, 6H, 2 X CH3),3.54 (brm, 2H, H-12A, H-
12B), 3.46-3.40 (m, 3H, H-2, H-8, H-10), 3.35 (t, J = 9.5 Hz, 1H, H-4), 3.13 (brm, 2H, H-6A, H-6B),

S4
1.44 (t, J = 6.4 Hz, 1H, OH); 13C NMR (125 MHz, CDCl3) δ: 158.35, 158.34, 158.19, 158.18, 158.15,
158.13, 130.0, 129.9, 129.4, 129.28, 129.23, 129.1, 128.7, 128.6, 128.5, 128.4, 128.1, 128.0, 112.89,
112.87, 112.7, 93.1 (C-1/C-7), 92.8 (C-7/C-1), 80.3 (C-3/C-9), 80.1 (C-9/C-3), 78.17 (C-2/C-8), 78.11
(C-8/C-2), 77.0 (C-4), 74.2 (ArCH2), 73.7 (ArCH2), 73.6 (ArCH2), 71.66 (ArCH2), 71.60 (ArCH2), 70.2
(C-11), 69.4 (C-5), 60.7 (C-12), 54.26 (OCH3), 54.24 (OCH3), 50.2 (C-6). Elemental analysis calcd for
C60H69N3O16: C, 66.22; H, 6.39; N, 3.86. Found: C, 66.35; H, 6.38; N, 4.13.

Synthesis of compound 8
To a solution of compound 7 (4.0 g, 3.67 mmol) in dry DMF (30 mL), NaH (60% in oil; 0.29 g, 7.34
mmol) was added in small portions at 0 oC under N2 atmosphere. To this, propargyl bromide (0.65 mL,
7.34 mmol) was added at 0 oC. Upon completion of the starting material (30 min), the reaction was
quenched by the slow dropwise addition of ice cold water (1 mL). The reaction mixture was diluted
with EtOAc, and the organic layer was washed with water and brine successively. The organic layer
was dried over anhydrous Na2SO4 and the solvents were evaporated in a rotary evaporator. The residue
obtained was purified by column chromatography using ethyl acetate/petroleum ether (3:7; v/v) as
eluent to obtain compound 8 (3.52 g, 85%) as a sticky liquid.
[α]D 25 = 84.5° (c 0.4, CHCl3); Rf = 0.4 (ethyl acetate/ petroleum ether, 3:7; v/v); 1H NMR (500 MHz,
CDCl3) δ: 7.20 (d, J = 8.4 Hz, 4H, ArH), 7.16-7.10 (m, 8H, ArH), 6.80-6.77 (m, 8H, ArH), 6.73 (dd, J
= 8.5 Hz, 13.7 Hz, 4H, ArH), 5.05 (d, J = 2.4 Hz, 2H, H-1, H-7), 4.83-4.79 (m, 2H, ArCH2), 4.75-4.68
(m, 4H, 2 X ArCH2), 4.57-4.51 (m, 5H, 2 X ArCH2, ArCH2A/ArCH2B ), 4.42 (d, J = 10.7 Hz, 1H,
ArCH2B/ArCH2A), 4.11-4.05 (m, 3H, H-5, H-11, H-13A/H-13B), 3.98 (dd, J = 2.1 Hz, 15.9 Hz, 1H,
H-13B/H-13A), 3.88 (t, J = 9.3 Hz, 2H, H-3, H-9), 3.72 (s, 6H, 2 X CH3), 3.70 (s, 9H, 3 X CH3), 3.69
(s, 3H, CH3), 3.60 (dd, J = 3.1 Hz, 10.5 Hz, 1H, H-12A/H-12B), 3.51 (t, J = 9.6 Hz, 1H, H-4/H-10),
3.44 (m, 2H, H-2, H-8), 3.35 (m, 2H, H-12B/H-12A, H-10/H-4), 3.13 (d, J = 3.2 Hz, 2H, H-6A, H-6B),
2.30 (t, J = 2.3 Hz, 1H, H-15); 13C NMR (125 MHz, CDCl3) δ: 159.3, 159. 23, 159.21, 159.20, 159.1,
131.2, 131.0, 130.7, 130.3, 130.2, 1129.6, 129.5, 129.4,129.19, 129.14, 113.9, 113.83, 113.80, 94.5 (C-
1/C-7), 94.1 (C-7/C-1), 81.5 (C-3/C-9), 81.2 (C-9/C-3), 79.5 (C-14), 79.2 (C-2/C-8), 79.0 (C-8/C-2),
78.1 (C-4/C-10), 75.26 (ArCH2), 75.23 (ArCH2), 74.9 (C-15), 74.8 (ArCH2), 74.7 (ArCH2), 72.66
(ArCH2), 72.61 (ArCH2), 70.5 (C-4/C-11), 70.4 (C-11/C-4), 68.0 (C-12), 58.5 (C-13), 55.3 (OCH3),
55.28 (OCH3), 55.26 (OCH3), 51.2 (C-6). Elemental analysis calcd for C63H71N3O16: C, 67.19; H, 6.35;
N, 3.73. Found: C, 66.92; H, 6.42; N, 3.54.
Synthesis of monomer 1
To a solution of compound 8 (3 g, 2.66 mmol) in MeCN/H2O (4:1; 100 mL), ceric ammonium nitrate
(CAN, 14.58 g, 26.6 mmol) was added and stirred for 5 h. After completion of the reaction, solvents
were evaporated and the crude compound was adsorbed on silica and passed through a short column of
silica using MeOH/EtOAc (2:8, v/v) as eluent. The solvents were evaporated to obtain the PMB
deprotected compound as a white solid with some impurities. This white solid was dissolved in pyridine
(20 mL) and acetic anhydride (5.6 mL, 50 mmol) was added to this solution at 0 oC and stirred for 3 h.
After the completion of the reaction, the solvents were evaporated under reduced pressure. The residue
thus obtained was dissolved in EtOAc, and washed with sat. aq. NaHCO3, water and brine successively.
The mixture was dried over anhydrous Na2SO4 and the solvents were evaporated in a rotary evaporator.
The crude product thus obtained was purified by column chromatography using ethyl acetate/petroleum
ether (1:1; v/v) as eluent to obtain compound 1 (1.43 g, 82% for two steps) as a white solid.
[α]D 25 = 153.0 (c 0.2, CHCl3); Rf = 0.5 (ethyl acetate/ petroleum ether, 1:1; v/v); 1H NMR (500 MHz,
CDCl3) δ: 5.48 (m, 2H, H-3, H-9), 5.31 (d, J = 3.9 Hz, 1H, H-1/H-7), 5.29 (d, J = 3.9 Hz, 1H, H-7/H-
1), 5.08-5.05 (m, 3H, H-2, H-4/H-10, H-8), 4.99 (t, J = 9.7 Hz, 1H, H-10/H-4), 4.18-4.07 (m, 4H, H-5,
H-11, H-13A, H-13B), 3.56 (m, 2H, H-12A, H-12B), 3.35 (dd, J = 7.3 Hz, 13.3 Hz, 1H, H-6A/H-6B),
3.15 (dd, J = 2.4 Hz, 13.3 Hz, 1H, H-6B/H-6A), 2.41 (t, J = 2.3 Hz, 1H, H-15), 2.11 (s, 3H, CH3), 2.10

S5
(s, 3H, CH3), 2.06 (s, 6H, 2 X CH3), 2.03 (s, 6H, 2 X CH3); 13C NMR (125 MHz, CDCl3) δ: 169.0 (CO),
168.9 (CO), 168.7 (CO), 168.69 (CO), 168.64 (CO), 168.62 (CO), 92.1 (C-1/C-7), 91.8 (C-7/C-1), 77.8
(C-14), 74.0 (C-15), 69.1, 68.87, 68.82, 68.7, 68.6, 68.4, 68.2, 67.0 (C-12), 57.7 (C-13), 49.9 (C-6),
19.69 (CH3), 19.66 (CH3), 19.65 (CH3), 19.63 (CH3), 19.60 (CH3). Elemental analysis calcd for
C27H35N3O16: C, 49.32; H, 5.36; N, 6.39. Found: C, 49.20; H, 5.52; N, 6.13.
3. Crystallization of the monomer 1
Compound 1 was dissolved in EtOAC under slight heating and n-hexane was added to this solution
slowly till the solution became cloudy. Colourless rod-shaped crystals (form-I) were obtained from the
solution upon natural evaporation; m. p. 119-120 oC .
Compound 1 was dissolved in CHCl3 under slight heating and n-hexane was added to this solution
slowly till the solution became cloudy. Colourless rectangular-block shaped crystals (form-II) were
obtained from the solution upon natural evaporation; m. p. 123-125 oC.
1
4. H NMR spectrum of form II crystals in DMSO-d6

Figure S1. 1H NMR spectrum on form II crystals recorded in DMSO-d6 showing the presence of peak
corresponding to chloroform (8.32 ppm).

S6
5. ORTEP diagrams of form I and form II

Figure S2. ORTEP diagrams of form I (a) and form II (b) drawn with ellipsoids at 40% probability
level using Mercury 4.1.0.
6. Crystal structures of form I and form II

Figure S3. Crystal structures of form I (a) and form II (b) showing positional disorders of azide and
alkyne groups. Azide, alkyne and chloroform are represented in a ball and stick model. Hydrogen atoms
are omitted for clarity.
7. Topochemical azide-alkyne cycloaddition (TAAC) of form I and form II
The crystals of form-I and form-II were taken in separate test-tubes and placed in a pre-heated oil bath
at a constant temperature of 90 oC. The progress of the reaction was monitored by withdrawing small
fractions at different times and then by recording their 1H NMR (CDCl3), FT-IR, PXRD and DSC. Both
form I and form II underwent topochemical reaction to give the corresponding triazole-linked polymers.
8. Time-dependent FT-IR during TAAC reaction of form I and form II
The FT-IR analysis was carried out at different times during the TAAC reaction. The FT-IR of form I
and form II (at 0 h) showed a signal for azide at 2108 cm-1. Reduction in the intensity of azide signal
was observed with time indicating the progress of TAAC reaction. The persistence of azide signal by
the end of the TAAC reaction indicates the formation of linear oligomers.

S7
Figure S4. Time-dependent FT-IR of form I (a) and form II (b).
9. Kinetics of TAAC reactions of form I and form II
The kinetics of TAAC reactions of form I and form II were monitored using 1H NMR spectra recorded
in CDCl3. Plots of percentage of conversion against time have resulted in sigmoidal graphs, indicative
of the topochemical nature of these reactions.

Figure S5. Plots of percentage conversion against time of form I (a) and form II (b) showing sigmoidal
kinetics.

10. Thermogravimetric analysis of form II crystals after heating for 36 h

While the crystals of form II showed a weight loss of 12% (Figure 2 of manuscript), crysals heated for
36 h showed no weight loss indicating the loss of chloroform during TAAC reaction.

S8
Figure S6. TGA analysis of form II crystals heated at 90 oC for 36 h.

11. Isolation of dimer

The crystals of form I were heated for 48 h at 90 oC. Then the TAAC reaction was halted and the heated
sample was purified through column chromatography using EtOAC/petroleum ether (9:1; v/v) as eluent
to obtain pure 1,5-triazole-linked dimer. The regiochemistry of the product was confirmed using 2D-
NMR spectroscopic techniques.
1
H NMR of pure dimer (500 MHz, CDCl3) δ: 7.47 (s, 1H, triazole CH), 5.48 (t, J = 9.7 Hz, 1H), 5.39
(t, J = 9.8 Hz, 2H), 5.34 (t, J = 9.8 Hz, 1H), 5.27 (t, J = 3.6 Hz, 2H), 5.13 (d, J = 3.7 Hz, 1H), 5.02-4.97
(m, 2H), 4.95-4.87 (m, 6H), 4.59 (d, J = 3.8 Hz, 1H), 4.46 (s, 2H, OCH2C), 4.43-4.36 (m, 2H, N-CH2C),
4.07-4.02 (m, 4H), 3.94-3.88 (m, 2H, CH2), 3.46-3.35 (m, 4H), 3.29 (dd, J = 7.0 Hz, 13.3 Hz, 1H,
CH2N3), 3.12 (dd, J = 2.1 Hz, 13.3 Hz, 1H, CH2N3), 2.33 (t, J = 2.2 Hz, 1H, alkyne CH), 2.14 (s, 3H,
CH3), 2.05 (s, 3H, CH3), 2.04 (s, 3H, CH3), 2.02 (s, 3H, CH3), 1.99 (s, 3H, CH3), 1.97-1.95 (broad, 15H,
5 X CH3), 1.93 (s, 3H, CH3), 1.82 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ: 169.0, 168.99, 168.95,
168.88, 168.84, 168.7, 168.68, 168.66, 168.62, 168.5, 132.8, 132.6, 92.2, 91.7, 91.1, 90.3, 77.8, 74.0,
69.29, 69.23, 69.0, 68.9, 68.7, 68.68, 68.64, 68.62, 68.5, 68.4, 68.3, 68.1, 67.9, 67.73, 67.70, 66.9, 60.5,
57.5, 49.9, 47.7, 20.0, 19.8, 19.65, 19.63, 19.61, 19.40.

Figure S7. 1H NMR of the 1,5-triazole-linked dimer.

S9
The HMBC spectrum of the dimer showed coupling between triazole carbon (CH) and O-CH2 protons
and not with N-CH2 protons (Figure S7).
The NOESY spectrum of the dimer showed spatial interaction between the protons of triazole (CH) and
O-CH2 and not between protons of triazole (CH) with N-CH2 protons (Figure S8).
Hence the dimer is identified as 1,5-triazole-linked dimer.

Figure S8. HMBC of the 1,5-triazole-linked dimer.

S10
Figure S9. 1H NMR (CDCl3) of the pure 1,5-triazole-linked dimer.
12. Molten state azide-alkyne cycloaddition reaction of 1
3 mg of the monomer 1 was taken in a NMR sampling tube and placed in a pre-heated oil bath at 150
o
C for 20 min. Then the compound was dissolved in CDCl3 and 1H NMR was recorded.

Figure S10. 1H NMR (CDCl3) for molten-state azide-alkyne cycloaddition of 1.

S11
13. Gel permeation chromatography (GPC) analysis
The crystalline polymers obtained from form I and form II after TAAC reaction were dissolved in
CHCl3 (4.0 mg/mL) for GPC analysis.
Polymer formed from form I: Mw = 7,327 g/mol Mn = 2,513 g/mol PDI = 2.916
Polymer formed from form II: Mw = 6,870 g/mol Mn = 1,764 g/mol PDI = 3.894

Figure S11. GPC analysis of polymer obtained from form I (a) and polymer obtained from form II
(b).
14. MALDI-TOF analysis of polymers obtained from form I and form II
Polymers obtained from form I and form II were dissolved using 0.1% DMSO in acetonitrile and
used for MALDI-TOF analysis using 2,5-dihydroxybenzoic acid as the matrix.
15. Circular dichroism (CD) spectroscopic analysis of form I and form II crystals

Figure S12. CD spectra of the crystals of form I (a) and from form II (b).
16. Circular dichroism (CD) spectroscopic analysis of the random polymers
The TAAC-obtained polymers of form I and form II were dissolved in dichloromethane. Then, the
solvents were evaporated to obtain the randomly oriented polymers which were analysed by CD
spectroscopy.

S12
Figure S13. CD spectra of the random polymers obtained from TAAC polymers form I (a) and from
form II (b).
17. Circular dichroism (CD) spectroscopic analysis of the polymer in solution state
The TAAC polymer was dissolved in acetonitrile (2mg/mL) and analysed by CD spectroscopy. CD
spectra revealed the helical nature of the polymer in solution state.

Figure S14. CD spectra of the polymer recorded in acetonitrile.

18. Table S1. Crystal data of form I and form II
Parameters Form-I Form-II
CCDC No. 1963092 1963093
Empirical formula C27 H35 N3 O16 C28 H36 N3 O16 Cl3
Formula weight 657.58 776.95
Temperature 150(2) K 296(2) K
Wavelength 0.71073 Å 0.71073 Å
Crystal system Orthorhombic Orthorhombic
Space group P212121 P212121
Unit cell dimensions a = 12.376(3) Å, α = 90° a = 12.424(4) Å, α = 90°
b = 15.750(4) Å, β = 90° b = 16.447(6) Å, β = 90°
c = 18.272(4) Å, γ = 90° c = 18.446(6) Å, γ = 90°
Volume 3561.5(15) Å3 3769(2) Å3

Z 4 4

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 Density (calculated) 1.226 g/cm3 1.368 g/cm3
Absorption 0.102 mm-1 0.314 mm-1
coefficient
F(000) 1384 1616
Crystal size 0.25 x 0.05 x 0.05 mm3 0.18 x 0.08 x 0.05 mm3
Theta range for data 3.066 to 28.354° 2.054 to 26.372°
collection
-14<=h<=16, -15<=h<=12,
Index ranges -20<=k<=17, -20<=k<=20,
-24<=l<=20 -23<=l<=22
Reflections collected 8394 7513
Independent 3255 [R(int) = 0.1412] 1977 [R(int) = 0.2123]
reflections
Completeness to theta 99.1 % 99.4 %
= 25.242°
Absorption correction Semi-empirical from Semi-empirical from equivalents
equivalents
Max. and min. 0.995 and 0.975 0.9923 and 0.9733
transmission
Refinement method Full-matrix least-squares on
Full-matrix least-squares on F2
F2
Data / restraints / 8394 / 165 / 485 7513 / 298 / 531
parameters
Goodness-of-fit on F2 0.860 0.813
Final R indices R1 = 0.0783, wR2 = 0.1795 R1 = 0.1070, wR2 = 0.2644
[I>2sigma(I)]

R indices (all data) R1 = 0.1895, wR2 = 0.2223 R1 = 0.2813, wR2 = 0.3574

Absolute structure -1.6(10) 0.8(4)
parameter
Extinction coefficient n/a 0.0028(19)
Largest diff. peak and 0.558 and -0.286 e.Å-3 0.411 and -0.438 e.Å-3
hole

19. Unit cell determination of the heated crystal of form II

a = 12.1130(14) Å; b = 15.4337(19) Å; c = 18.233(2) Å

α = 90°, β = 90°, γ = 90°
Volume = 3408.63 Å3

20. Table S2. Non-covalent interactions in form I and form II

Interaction D-H…A H…A (Å)/ vdW-d (Å) / D-H…A (o)/Symmetry code
Form I Form II
C-H… π C3-H3…C15 2.83/0.07/165.7/
1/2+x,1/2-y,2-z
C3-H3…C14 2.84/0.06/164.3/
1/2+x,1/2-y,2-z
C9-H9…C14 2.79/0.11/172.2/
1/2+x,1/2-y,2-z

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C-H…N C6- 2.59/0.15/140.1/
H6A…N3 1/2+x,-1/2-y,2-z
C6- 2.74/0.01/142.1/
H6A…N3 1/2+x,2.5-y,-z
C-H…Cl C19- 2.93/ 0.02/169.8/
H19B…Cl12 1-x,1/2+y,-1/2-z
C27- 2.85/0.10/127.4/
H27C…Cl1 x,y,z
C15- 1.67/1.27/112.9/
H15…Cl1 x,y,z
C15- 2.68/0.27/108.5/
H15…Cl2 x,y,z
C-H…O C2-H2…O7 2.65/0.07/158.6/
1.5-x,-y,1/2+z
C8-H8…O3 2.67/0.05/170.3/
1.5-x,-y,-1/2+z
C25- 2.65/0.07/154.9/
H25B…O11 1.5-x,-y,-1/2+z
C25- 2.64/0.08/146.7/
H25A…O11 1/2-x,2-y,1/2+z
C27- 2.58/0.14/160.7/
H27B…O11 1/2+x,1/2-y,2-z
2.67/0.05/141.6/
1/2+x,1.5-y,-z
C12- 2.57/0.15/158.2/
H12A…O12 -1/2+x,1/2-y,2-z
2.47/0.25/147.7/
-1/2+x,1.5-y,-z
C19- 2.58/0.14/158.7/
H19A…O16 1/2+x,1/2-y,2-z
C10- 2.72/0.002/148.7/
H10…O13 1.5-x,-y,-1/2+z
2.72/0.003/149.4/
1/2-x,2-y,1/2+z
C12- 2.71/0.005/134.1/
H12B…O13 1.5-x,-y,-1/2+z
2.71/0.01/134.2/
1/2-x,2-y,1/2+z
C21- 2.40/0.32/171.0/
H21C…O14 1/2+x,-1/2-y,2-z
C21- 2.71/0.01/142.3/
H21A…O14 1/2+x,2.5-y,-z
C19- 2.66/0.06/145.6/
H19C…O14 1.5-x,-y,1/2+z
2.58/0.14/149.8/
1/2-x,2-y,-1/2+z
C17- 2.25/0.47/172.3/
H17A…O15 -1/2+x,1/2-y,2-z
C17- 2.67/0.05/114.6/
H17B…O15 -1/2+x,1.5-y,-z
C27- 2.58/0.14/160.7/
H27B…O11 1/2+x,1/2-y,2-z
C13- 2.62/0.10/164.8/
H13A…O8 -1/2+x,1/2-y,2-z

S15
 C6- 2.32/0.40/159.5/
H6B…O16 1.5-x,-y,1/2+z
2.34/0.38/155.4/1/
2-x,2-y,-1/2+z
C28- 2.47/0.25/140.2/
H28…O9 1/2+x,1.5-y,-z

21. References

1. V. A. Sarpe, S. S. Kulakarni, Org. Biomol. Chem. 2013, 11, 6460–6465.

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