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キーワード:
Porphyrin-quinone cyclophanes; Photoinduced electron transfer; Porphyrin cyclophanes, conformational mobility of, crystal structures of
要旨:
In order to correlate photoinduced electron-transfer in porphyrin-quinone cyclophanes to specific molecular conformations, the internal mobility of single-and double-bridged porphyrin-quinone cyclophanes was studied by low-temperature 1H-NMR measurements. The dynamic processes observed are discussed in terms of N-H/N tautomerisation, of the rotation of the rings in the bridges, and of a specific “swinging bridge” process back and forth between two equivalent unsymmetrical conformations with a tilted orientation of the porphyrin and quinone ring planes. For comparison with the conformational situation in solution the results of X-ray structure analyses of 3(X[DOUBLE BOND]OMe) and 6, as representative examples of single-bridged quinone-porphyrin cyclophanes, and of the corresponding tetramethoxybenzene-bridged octamethylporphyrin cyclophane 4(X[DOUBLE BOND]OMe) are reported and discussed. In contrast to the previously solved crystal structure of the quinone-porphyrin-quinone cyclophane 1(X[DOUBLE BOND]H), all three X-ray structure analyses of the single-bridged porphyrin cyclophanes proved the existence of unsymmetrical, tilted-plane structures similar to those discussed as the stable conformations in the “swinging bridge” process.
