• Title/Summary/Keyword: Quinolinium salts

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Synthesis and Characterization of Substituted Quinoline Complexes of Molybdenum (I). Substituted Quinolinium Salts of Pentachlorooxomolybdate (V) (몰리브덴(V)의 퀴놀린계 착물합성과 그 성질 (제2보). 오클로로옥소몰리브덴(V) 산의 치환퀴놀린윰염)

  • Kwang Lee;Sang-Oh Oh
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.482-489
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    • 1985
  • The substituted quinolinium salts of pentachlorooxomolybdate (V) have been synthesized and characterized by means of the investigation of elemental analysis, infrared spectra, electron spectra, electric conductivity. The results of elemental analysis were well coincided with the theoretical value and all prepared salts were mononuclear complexes. The complexes were binary univalent electrolytes and analyzed d-d transition and charge transfer transition.

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The Mechanism of the Photocyclization of N-(2-Haloarylmethyl)Pyridinium and N-(arylmethyl)-2-Halopyridinium Salts

  • Yong-Tae Park;Chang-Han Joo;Chung-Do Choi;Kum-Soo Park
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.163-169
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    • 1991
  • The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.