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UV/VIS and ESR spectra of electron transfer reaction products in aprotic (c H⊕  &lt; 0,1 ppm) solution can be measured in an especially designed and sealed glass apparatus and provide information on unknown facets of the microscopic pathway through the network of interdependent equilibria. For tetraphenyl-p-benzoquinone in tetrahydrofuran, single-electron reduction by a sodium metal mirror produces a red solution and, unexpectedly, after addition of 2.2.2. cryptand, contact with a potassium metal mirror generates a green (!) one. For both, ESR/ENDOR spectra prove the presence of tetraphenyl-p-benzoquinone radical anion. UV/VIS measurements provide the clue: In the equilibrium revealed by repetetive spectra recording, M ·⊖  solv  + Me ⊕  solv  ⇄ [M ·⊖ ···Me ⊖ ] solv , the radical anion is green (v m  = 16900 cm -1 ) and the contact ion pair red (v m =18900 cm -1  ). On ion pair formation, therefore, the excitation energy of the radical anion increases by 0.25 eV.

zeitschrift für naturforschung b

Elektronentransfer und Ionenpaar-Bildung, 48 [1] Titrationen von Tetraphenyl-p-benzochinon mit Natrium- und Kaliummetall in aprotischen Lösungen / Electron Transfer and Ion Pair Formation, 48 [ 1 ] Titrations of Tetraphenyl-p-benzoquinone with Sodium and Potassium Metals in Aprotic Solutions