with a hot stage (linked to a Physitemp TS-4 ER temperature controller) and a Sony CCD-IRIS/RGB color video camera connected to a Sony video monitor CMA-D2.
DSC Analyses: Thermal analyses were performed on a Mettler Toledo DSC820, and thermogravimetric measurements on a Mettler Toledo TGA850 coupled with a FTIR spectrophotometer Nicolet Nexus.
Dynamic Light Scattering: Malvern Instruments Zetasizer 3000. Preparation of Co-crystal 4a: Neat 1,8-diiodoperfluorooctane (3a, 0.4 mmol, 262 mg) was added to a solution of 1,3-di(4-pyridyl)propane (1a, 0.4 mmol, 80 mg) in chloroform (4 mL) at room temperature and in a clear borosilicate vial. The open vial was placed in a closed cylindrical wide-mouth bottle (50 mL) containing hydrocarbon oil. Volatiles were allowed to diffuse at room temperature and after 2 h the non-covalent co-crystal 4a precipitated as a white solid. The crystals were filtered and washed with cold dichloromethane. MPs: 1a: 58ยฑ60 C, 3a: 75ยฑ76 C, 4a: 110ยฑ112 C. The product 4a was recrystallized in acetone for X-ray diffraction. 19 F-NMR (CDCl 3 , 0.05 M solution): d = ยฑ59.57 ppm (CF 2 I in 3a), ยฑ62.37 (CF 2 I in 4a; Dd = d free ยฑd 4a = 2.80; (0.1 M solution: d = ยฑ64.37 ppm; Dd = 4.80)). Preparation of Co-crystal 4b: Starting from 1,6-diiodoperfluorohexane (3b, 0.4 mmol, 222 mg) and 1,3-di(4-pyridyl)propane (1a, 0.4 mmol, 80 mg), 4b was obtained as a white solid following the procedure described above. MPs: 3b: 25 C, 4b: 115 C. Preparation of Comblike Complexes 5: Complex 5a: To a clear solution of P4VP (2a, 300 mg) in chloroform (250 mL), neat 1,8-diiodoperfluorooctane (3a, 934 mg) was added. The solvent was evaporated at room temperature to dryness. MP 2a: 115 C, 3a: 75ยฑ76 C, 5a: 77 C. 19 F-NMR data (CDCl 3 , 0.001 M solution) d = ยฑ59.69 ppm (CF 2 I in 5a; Dd = d free ยฑd 5a = 0.12). Comblike Complex 5b:
To a clear solution of P4VP (2a, 300 mg) in chloroform (250 mL), liquid 1,6diiodoperfluoroexane (3b, 791 mg) was added. The solvent was evaporated at room temperature to dryness to give a colourless and dense oil. Comblike Complex 5c: To a clear solution of P4VP (2a, 300 mg) in chloroform (250 mL), neat 1,2-diiodotetrafluoroethane (3c, 0.50 g) was added. The solvent was evaporated at room temperature to dryness to give a colorless dense oil. Complexes 6aยฑc were prepared similarly, as described in the text.