Irene SANCHEZ MOLINA, Mine INCE, Giovanni BOTTARI, Christian Georges CLAESSENS

Encapsulation of phthalocyanine-C60 fullerene conjugates into metallosupramolecular subphthalocyanine capsules: a turn of the screw

In this communication, encapsulation studies between metallosupramolecular capsule 1, formed by 2 subphthalocyanines (SubPcs) coordinated to 3 metallic centers, and phthalocyanine (Pc)-C60 fullerene conjugates 2--5 have been carried out. It was shown that the encapsulation of the C60 moiety by the SubPc cage occurred exclusively for dyads 2--4, whereas it was not observed in the case of triad 5. The rigidity of the linker between the Pc and the fullerene unit proved to have an important impact in the complex formation. Complex formation was tested in 2 different solvents, where the importance of solvophobic effects was highlighted. The resulting multicomponent supramolecular systems represent a unique combination of photoactive moieties where covalent and supramolecular chemistry coexist.

Anahtar Kelimeler:

Phthalocyanines, subphthalocyanines, C60 fullerene, metallosupramolecular chemistry, host--guest complexes

Encapsulation of phthalocyanine-C60 fullerene conjugates into metallosupramolecular subphthalocyanine capsules: a turn of the screw

Keywords:

Phthalocyanines, subphthalocyanines, C60 fullerene, metallosupramolecular chemistry, host--guest complexes,

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Pc dimer 7
To a solution of Pc 6
(50 mg, 0.029 mmol) and malonyl chloride (1.4 µ L, 0.014 mmol) in THF (5 mL), a solution of Et3N (4.04 µ L, 0.029 mmol) in THF (2 mL) was added dropwise. The mixture was stirred at room temperature overnight, and then evaporated to dryness. Purification of the solid residue by column chromatography (toluene/THF 10:1) afforded pure compound 7 (25 mg, 49%). 1H NMR ( d
) = 2928, 2847, 1738, 1603, 1464, 1342, 1234, 1103, 1090, 870; UV/Vis (THF): λmax(log ε) = 678 (5.28), 632 (5.03), 343 (5.15); MS (MALDI, dithranol), m/z: 3469.5 (M-H)+; HRMS (MALDI-TOF, dithranol): calc. for C223H344N16O6Zn2: [M]+: m/z: 3470.5682, found 3470.5236. 3.3. (Pc)2C605
1H NMR ( d-THF, 300 MHz): δ = 9.06 (m, 2H, ArH), 9.17–8.90 (m, 4H, ArH), 8.82–8.34 (m, 10H, 8-THF, 300 MHz): δ = 9.06 (m, 2H, ArH), 9.17–8.90 (m, 4H, ArH), 8.82–8.34 (m, 10H, ArH), 7.58 (m, 2H, ArH), 4.94–4.84 (m, 2H, OCH2) 4.81–4.54 (m, 6H, OCH2) , 3.59–3.32 (m, 12H, alkylH), 3.31–3.02 (m, 12H, alkylH), 2.24–1.3 (m, 256H, alkylH), 1.1–0.9 (m, 36H, alkylH); IR (KBr): ν (cm −1
) = 3442, 2956, 2920, 2851, 1750, 1646, 1609, 1466, 1432, 1339, 1105; UV/Vis (THF): λmax(log ε) = 679 (5.2), 632 (5.0), 339 (5.1); MS (MALDI, dithranol), m/z: 4188.6 (M)+; HRMS (MALDI-TOF, dithranol): calc. for C283H342N16O6Zn2: [M]+: m/z: 4188.5526, found 4188.5649.
Samples for31P NMR study
Capsule 1 (2 mg, 0.45 mmol), and the corresponding Pc-C60conjugate (0.45 mmol) were dissolved in CDCl3 or d8-THF. An aliquot from each of these mixtures was taken after 1 h to ensure equilibrium conditions and a 31P NMR spectrum was recorded.