THE IMPORTANCE OF COMPLEX FORMATION IN THE SENSITIZATION OF Eu(III) EMISSION BY OROTIC ACID

Abstract

Orotic acid (I) and 3-methylorotic acid (11) are the only orotic acid derivitives which efficiently sensitire emission from Eu(II1) in D 2 0 solution. This emission is only weakly sensitized by I-methylorotic acid (III), 1,3-dimethylorotic acid (IV), the methyl and isopropyl esters of orotic acid (V) 6-acetyluracil (VI) and not sensitized at all by the bases uracil. thymine and their nucleosides. Substituent groups on either the carboxyl group or the N-l position of the ring thus prevent efficient energy transfer from the excited orotic acid to Eu(1II). These structural requirements for efficient energy transfer are the same as the structural requirements for formation of a stable. bidentate. ground state complex between Eu(II1) and orotic acid (VII) (Sarpotdar and Burr, 1978).We. therefore. propose that sensitization of Eu(ll1) emission by orotic acid at pH 5 is an example of energy transfer within the bidentate complex of Eu(II1) and orotic acid. We also propose that the complexed orotic acid is itself excited by eollisional energy transfer from free triplet excited orotic acid (since the concentration of complex measured to be present. 5-7"4,, is too low to account for the efficiency of the sensitization). We also propose that emission from the excited complexed Eu(Il1) can be either from the complexed ion or from free Eu(III)* resulting from dissociation of the complex during the lifetime of the excited ion.The efficiency of Eu(lI1) sensitized emission is shown to depend on the concentrations of Eu(1II). orotic acid and pH with relationships kinetically consistent with the above hypothesis.