A Sequential Photoinduced Electron Relay Accelerated by Fullerene in a Porphyrin-Pyromellitimide-C60 Triad

✍ Scribed by Dr. Hiroshi Imahori; Koji Yamada; Masato Hasegawa; Seiji Taniguchi; Prof. Tadashi Okada; Prof. Yoshiteru Sakata

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 485 KB
• Volume: 36
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.199726261

✦ Synopsis

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([D,]

benzene) shows a number of resonance signals at room temperature that split into two signals in the ratio 1:2 at 70°C. This spectrum can be unequivocally attributed to the cluster structure. The 'H NMR spectra of the (R)(R')NAIF,.THF compounds have both the expected resonance signals. No differentiation between coordinated THF and free THF is observed at -90 "C on addition of further amounts of THF to the samples. This confirms the rapid exchange of the THF molecules.

The possibility of a partial hydrolysis was ruled out by the controlled hydrolysis of a sample of 4; the Me,SiF signal in the I9F NMR spectrum was of greater intensity after the hydrolysis. Thus, only the reaction with THF needs to be taken into consideration. Indeed, reactions of aliphatic ethers with halides of Group 13 have often been reported.['] The reaction of R,O with BC1, leads to the formation of RCI and ROBCI,. In contrast, the corresponding reaction with BF3 leads to alcohols (or water) and olefins.['I Investigations into analogous reactions of THF with BFJY] and AlC13['0] have also been reported; these always led to cleavage of the THF and opening of the ring. Thus, the aluminum-fluorine-oxygen clusters obtained are dependent on the substituents R and R' of (R)(R)NAlF,.THF. A molecular compound of oxygen in which the oxygen atom is surrounded by six main group elements was thus obtained for the first time. This type of structure was, until now, only known for the d-and f-block elements. [']