Photophysical properties and photoinduced electron transfer within host-guest complexes of 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin with water-soluble calixarenes and cyclodextrins.
We report the formation of host-guest complexes between water-soluble calix[n]arene-p-tetrasulfonates (n = 4, 6, 8) or 2-hydroxypropyl-cyclodextrins (alpha-, beta-, gamma-) and the tetratosylate salt of 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP). The binding constants ranging between 10(2) and 10(5) M-1 were calculated from the absorption and fluorescence changes. Calix[4]arene-p-tetrasulfonate has a high binding affinity and forms with TMPyP a 1:1 complex, whereas other calixarenes bind two molecules of TMPyP. Electrostatic attraction is the dominating binding mode. Binding to calixarenes leads to a considerable decrease of the quantum yields of the triplet and excited singlet states and to shortening of the singlet and triplet lifetimes of TMPyP. The quenching mechanism is attributed to electron transfer between calixarene phenolates and excited TMPyP. Photoinduced electron transfer within a novel supramolecular complex calixarene/TMPyP (electron donor)/methyl viologen (electron acceptor) has been proven by absorption and fluorescence measurements. Electrostatic attraction between the cationic donor and cationic acceptor, on the one hand, and the anionic host, on the other, overcomes the electrostatic repulsion forces. In contrast, the interaction of cyclodextrin with TMPyP is hydrophobic in nature and only slightly influences the photophysical properties of TMPyP. The different behavior of TMPyP bound to either of the hosts has been assigned to the specific effects of the dominant binding modes, viz. the electrostatic attraction for calixarenes and the hydrophobic interactions for inclusion complexes with cyclodextrins.
Lang
K
K
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, 250 68 Rez, Czech Republic. lang@iic.cas.cz
Kubát
P
P
Lhoták
P
P
Mosinger
J
J
Wagnerová
D M
DM
D047250:Calixarenes; D003505:Cyclodextrins / Q000737:chemistry*; D004563:Electrochemistry; D046911:Macromolecular Substances; D008956:Models, Chemical; D015394:Molecular Structure; D010777:Photochemistry; D011166:Porphyrins / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013054:Spectrophotometry, Atomic; D013056:Spectrophotometry, Ultraviolet
D003505:Cyclodextrins; D046911:Macromolecular Substances; D011166:Porphyrins; D047250:Calixarenes; C021096:tetra(4-N-methylpyridyl)porphine