Cd2cl2

All bio-polyol syntheses were carried out on a double manifold Schlenk vacuum line under a nitrogen atmosphere according to the literature [18 (link)]. Epoxidized linseed oil (ELO) with approximately 6.4 epoxy groups per triglyceride and M_n equal to 1182 g/mol was kindly supplied by Hallstar (Chicago, IL, USA). 1,4-diazabicyclo[2.2.2]octane (DABCO, 98%), toluene-2,4-diisocyanate (TDI, tech. 80%, remainder 2,6-diisocyanate) glycerol (≥99%) and triethylamine (TEA, 98%) were purchased from Fisher Scientific Company (Hampton, NH, USA). Caprylic acid (CA, ≥99%) was purchased from Carlo Erba (Milan, Italy). Niax Silicone L-537 XF (Momentive, NY, USA) was kindly supplied by Eigenmann & Veronelli SpA (Milan, Italy) and used as silicone surfactant. Polypropylene glycol (PPG, Mn ~4600 g/mol from SEC analysis), all the terpenes, dibutyltin dilaurate (DBT) and Irgasan^® were purchased from Merck KGaA (Darmstadt, Germany). Deuterated solvent, CD₂Cl₂, and hexamethyldisilane (HMDS) for NMR measurements were used as received from Merck KgaA (Darmstadt, Germany).

All bio-polyol syntheses were carried out on a double manifold Schlenk vacuum line under nitrogen atmosphere. Epoxidized linseed oil (ELO) with approximately 6.4 epoxy groups per triglyceride and M_n equal to 1182 g/mol, and epoxidized soybean oil (ESO) with approximately 4.3 epoxy groups per triglyceride and M_n equal to 1168 g/mol, were supplied by Hallstar (Chicago, IL, USA) and Tecnosintesi Spa (Bergamo, Italy), respectively. Caprylic acid (CA, ≥99%) and 3-phenyl butyric acid (3PBA, 99%) were purchased from Carlo Erba (Milan, Italy). Partially bio-based diisocyanate (Tolonate™ X FLO 100) was kindly provided by Vencorex Chemicals (Saint-Priest, France). Niax Silicone L-537 XF (Momentive, NY, USA) was kindly supplied by Eigenmann and Veronelli SpA (Milan, Italy) and used as silicone surfactant. Polypropylene glycol (PPG, M_n ~3000 g/mol) was purchased from Merck KGaA (Darmstadt, Germany) and glycerol (≥99%) and triethylamine (TEA, 98%) from Fisher Scientific Company (Hampton, NH, USA). Deuterated solvent, CD₂Cl₂, and hexamethyldisilane (HMDS) for NMR measurements were used as received from Merck KGaA (Darmstadt, Germany).

Chemicals were obtained from the following suppliers: diisopropylamine, 2.5 M n-butyl lithium in hexanes (Acros); EDTA, AgOTf, 4,4′-dimethyl-2,2′-bipyridine, sodium sulfide, celite 512 medium, Et₃N, 2-chloro-methylpyridinium iodide, triethanolamine, anhydrous DMF, methyl chloroformate, copper(ii) acetate (Aldrich); 3-picoline (BDH Chemicals); CO₂ – CP-grade with 5% CH₄ (or 1% CH₄) (BOC); Na₂SO₄, Na₂CO₃, NaHCO₃, NaOH, HCl, KOH, ammonium hydroxide (Fisher); Zn(OAc)₂·H₂O, CH₃CO₂Na (Fisons).
Solvents for general use were obtained from Fisher. Solvents were dried by refluxing over sodium wire (C₆H₆, THF, toluene) or over CaH₂ (CH₂Cl₂). DMF was dried using a Pure Solv 400-3-MD (Innovative Technology). For TRIR experiments, CH₂Cl₂ (99.9%, Merck) was distilled under an inert atmosphere of Ar from calcium hydride and anhydrous THF (≥99.9%, inhibitor-free, Sigma Aldrich) was used as supplied and stored in a glove box.
CD₂Cl₂, CD₃OD, DMSO-d₆ and CDCl₃ were used as obtained (Aldrich) and THF-d₈ was dried over potassium. Diisopropylamine was distilled from sodium hydroxide. Methyl chloroformate was distilled prior to use. n-BuLi was titrated against n-benzylbenzamide prior to use. Routine separation of porphyrins by flash chromatography was performed on a CombiFlash Rf system using 24 g RediSep Rf silica columns (Teledyne Isco), and dry-loading the samples on silica (Fluka).