Study of photopolymer. XVII. Synthesis of novel photosensitive polymers with pendant photosensitive group and photosensitizer groups

Novel photosensitive polymers with pendant photosensitive group, such as cinnamic ester, and photosensitizer groups, such as N-carbamoyl-p-nitroaniline and N-carbamoly-4-nitro-1-naphthylamine, were synthesized from radical copolymerizations of (2-cinnamoyloxy)ethylmethacrylate with photosensitizer monomers, such as p-nitrophenylmethacrylamide and 4-nitro-1-na-phthylmethacrylamide, by using asobisisobutyronitrile (AIBN) in benzene and from the copolymerizations of (2-hydroxy)ethylmethacrylate or (2-hydroxy)ethylacrylate with photosensitizer monomers by using AIBN in DMF. This procedure was followed by condensation reactions of the copolymers with cinnamoyl chloride with pyridine as HCL acceptor in the same reaction flask. The photoreactivities of the polymers obtained were influenced by the concentration of photosensitive group and photosensitizer groups and their ratio in the polymer matrix. In addition, the photosensitivity of cinnamic ester groups attached to a soft polymer segment was higher than that of cinnamic ester group attached to a hard polymer segment when these polymers had the same pendant N-carbamoyl-p-nitroaniline group as photosensitizer. Furthermore, the spacer length between the polymer chain and photosensitizer group was important for increasing the photoreactivity of the photosensitive group in the polymers with pendant cinnamic ester and N-carbamoyl-p-nitroaniline groups.     

Chemical reactivities of the cation and anion of M@C82 (M = Y, La, and Ce)

The chemical reduction and oxidation of M@C82 (M = Y, La, and Ce) afford the corresponding anion and cation, respectively, which show unique and interesting chemical reactivities. It is found that the successful reversible gain or loss of electrons by ionization is useful for controlling the stability and reactivity of M@C82 toward both nucleophiles and electrophiles.     

X-ray photoelectron spectra of ylide—TCNQ charge-transfer complexes

Charge-transfer complexes of TCNQ with ylides, new-type donors, were synthesized and the X-ray photoelectron spectra of these complexes were measured. A broad satellite caused by TCNQ radicals observed.