Springer Online Journal Archives 1860-2000
Chemistry and Pharmacology
Abstract An analysis has been made of π-π* -electronic excitations of carbonium and dicarbonium ions obtained by the interaction of concentrated sulfuric or fluoboric acid with alcohols or glycols containing a heterocyclic bridge structure, i.e., nuclei of dibenzofuran, dibenzothiophene, carbazole, and N-methylcarbazole; this analysis has been aimed at establishing a correlation of their structure and spectral characteristics. From an analysis of experimental data, calculated results, and indexes quantitatively characterizing the structure of the π-π* -electronic excitations, it has been established that there are four electronic transitions in the visible region of the electronic absorption spectrum of the carbonium ions. The long-wave, intense band of the spectrum is due to superposition of intense (p-type) and weak (α-type) transitions proceeding from corresponding excitations of the heterocyclic fragment. In the electronic spectra of the dicarbonium ions, a doublet of p-transitions is clearly manifested. It has been shown that the interaction of chromophores through the bridge structure increases by a factor of approximately 1.8 when the change is made from dibenzofuran to dibenzothiophene, carbazole, and Nmethylcarbazole; in comparison with the corresponding dihydroxycarbonium ions, the degree of interaction of the chromophores is greater by a factor of approximately 1.5.
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