N.M.R. relaxation study of crystalline quinuclidine

Transient signals in the fluorescence intensity induced by microwaves can be used to acquire quantitative information on the molecular rates of populating and depopulating of the lowest triplet state of organic molecules. This method seems especially promising when the molecule emits no detectable phosphorescence.

Part of this paper concerns the introduction of an appropriate mathematical model for describing the fluorescence transients. The model is formulated in conjunction with a specific series of experiments from which one may evaluate the molecular quantities in a systematic way. The kinetics of the lowest triplet state of free base porphin (H₂P) are determined explicitly by this method.

In the discussion the results for H₂P are compared with those for Zn porphin. A satisfactory qualitative explanation based on the theory of radiationless transitions can be given for the great difference in behaviour of these two porphyrin molecules.

Short attention is given to effects due to the photochemical shift of the two H atoms in the centre of H₂P, which is proven to occur even at a temperature as low as 1·3 K.