文摘
Cationic arene ruthenium assemblies of the general formulas [Ru6(p-cymene)6(tris-pvb)2(渭2-Cl)6]6+, [Ru6(p-cymene)6(tris-pvb)2(OO鈭㎡O)3]6+ (tris-pvb = 1,3,5-tris{2-(pyridin-4-yl)vinyl}benzene), and [Ru8(p-cymene)8(NN鈭㎞N)2(OO鈭㎡O)4]8+ (NN鈭㎞N = 1,2,4,5-tetrakis{2-(pyridin-4-yl)vinyl}benzene, 1,2,4,5-tetrakis{2-(pyridin-4-yl)ethynyl}benzene) have been obtained from the corresponding dinuclear arene ruthenium complexes [Ru2(p-cymene)2(渭-Cl)2Cl2] and [Ru2(p-cymene)2(OO鈭㎡O)Cl2] (OO鈭㎡O = oxalato, 2,5-dioxido-1,4-benzoquinonato, 2,5-dichloro-1,4-benzoquinonato, 5,8-dioxido-1,4-naphthoquinonato, 5,8-dioxido-1,4-anthraquinonato, 6,11-dioxido-5,12-naphthacenedionato) by reaction with the multidentate ligands and silver trifluoromethanesulfonate. These cationic hexa- and octanuclear cages have been isolated and characterized as their triflate salts. Addition of coronene during the synthesis of the large hexanuclear assemblies leads to the direct encapsulation of coronene in the cavity of the trigonal-prismatic complexes. Photosensitizers such as porphin, phthalocyanine, and Zn-phthalocyanine present during the synthesis of these metalla-cages are encapsulated in five of these arene ruthenium complexes to give photosensitizer-encapsulated systems. The host鈥揼uest properties of these systems were studied in solution by DOSY, 2D NOESY and 2D ROESY NMR spectroscopy. The H路路路H distances between guests and selected metalla-cages were estimated by 2D ROESY NMR spectroscopy and modelization. NMR analyzes indicate that the guest photosensitizers are completely encapsulated in two of these metalla-cages, while in the three other ruthenium cages NMR spectra reveal an equilibrium between empty and filled cages.
