Isosorbide

The itaconic acid (99%) (IA), succinic acid (99%) (SA), propylene glycol (99%) (PG), neopentyl glycol (99%) (NPG), isosorbide (98%) (IS), methyl ethyl ketone peroxide (MEKPO), cobalt octoate, hydroquinone (pro analysis) (HQ), ethanol (99%) and toluene (99%) were supplied from Acros Organics, Geel, Belgium. Isopropanol and tetrahydrofuran were purchased from Macron Fine Chemicals, Center Valley, Pennsylvania, USA, and Fisher Chemical, Waltham, MA, USA, respectively. Zinc acetate (99.99%) (ZnAc) and dimethyl itaconate (99%) (DMI) were purchased from Sigma-Aldrich, St. Louis, MI, USA. All chemicals were used as received.

Isosorbide (98%) and levulinic acid (98%) were
obtained from Acros Organics, vinyl methacrylate (98%) was obtained
from Sigma-Aldrich, vinyl acetate (99%) was obtained from Fluka, adipic
dihydrazide (adh, 97%) was obtained from Alfa Aesar,
malonic dihydrazide (mdh, 99%) was obtained from Thermo
Scientific, and methyl methacrylate (MMA, 99%) was obtained
from Fisher Chemicals. All used solvents were HPLC grade. All reagents
and solvents were used without further purification if not mentioned
otherwise. Reactions were monitored by thin-layer chromatography (TLC),
and TLC plates were visualized either by UV detection or by staining
with phosphomolybdic acid (PMA) solution. The reaction products were
purified by flash chromatography using silica gel 60 (0.040–0.063
mm, 230–400 mesh).

Isosorbide, 4-nitrobenzoyl chloride, (N-ethyl-N-hydroxyethyl)aniline and cholesteryl chloroformate were purchased from Alfa Aesar Co. The concentrated sulfuric acid, glacial acetic acid, dichloromethane (DCM) and N,N-dimethylformamide (DMF) were purchased from commercial sources as analytical pure products. The deionized water (resistivity > 18.0 MΩ cm) was obtained from a Milli-Q water purification system. The reagents and solvents mentioned above and others were commercially available products and used as received without further purification. The PDMS molds with the periodic holes in the hexagonal lattice alignment, where the depth and diameter of the holes were 800 and 500 nm, were purchased from GD-nano Co. Ltd. The azo molecular glass (IA-Chol) was synthesized according to the method reported by us previously^{56 (link)}, which is also presented in detail in the Supplementary.

Isosorbide was purchased from Alfa Aesar (Karleshrue, Germany), Isomannide and Isoidide were purchased from Sigma Aldrich (Milwaukee, WI, USA), previously crystallized from acetone and dried under high vacuum. 1-fluoro-4-benzonitrile (99%), 1,4,7,10,13,16-hexaoxacyclooctadecane (18-Crown-6), activated palladium supported on charcoal (10%), and thionyl chloride were purchased from Sigma-Aldrich (St Louis, MO, USA). KOH (Normapur) was purchased from Prolabo (Paris, France). Unless otherwise mentioned, all the reactants were used as received. The solvents were distilled over CaH₂ and placed on molecular sieves.
1D and 2D NMR techniques were recorded at 300 and 500 MHz (Bruker WP 250). The chemical shifts are given in ppm. Differential Scanning Calorimetric data were obtained using DSC131 (SETARAM). DSC measurements were conducted with a heating and cooling rate at 10 °C/min. The first heating cycle was conducted from room temperature to 150 °C. Then samples were cooled down to room temperature. Then, a second heating scan was conducted (RT to 500 °C for the diacid) (RT to 300 °C for the AB monomers) (RT to 250 °C for the polymer). The T_m and T_g values were determined from the second DSC heating scan. Sample weights of about 10−15 mg were used in these experiments.