Triplet state, definition

The comparatively small size of the simplest carbene (methylene) ensures that it has a definite mobility in frozen inert matrices, which leads to the formation of dimerization products under these conditions. It became possible only in 1981 to detect in the spectra of the diazomethane photolysis products bands at 1115 cm (Ar matrix) and 1109 cm (Xe matrix) which were attributed to the deformation vibration of methylene in its ground triplet state (Lee and Pimentel, 1981). 

As seen in the previous section, one characteristic of the triplet state is its paramagnetism. This alone would of course not suffice as a definition of the triplet since there are many odd-electron species that also exhibit paramagnetism but do not exist as triplets. Thus we might state that a triplet is a paramagnetic even-electron species. This still does not constitute a limiting definition since compounds containing even numbers of electrons may exhibit two, three, or even five distinct electronic levels. For example, when in a biradical the radical centers are separated by several carbon atoms as below, no interaction between the electron spins occurs and the radicals appear as two doublet states ... 

Since we have two unpaired electrons, 5=1, and the number of states is three. If we should have other even numbers of unpaired electrons, such as four or six, we could have three, five, or even as many as seven states. Thus we arrive at a definition for the triplet as a paramagnetic species possessing an even number of unpaired electrons and existing in a set of three energetically similar electronic levels which result from interaction of the electronic spin. Generally these three distinct electronic levels, between which transitions may be observed under certain conditions, are collectively referred to as the triplet state. 

The results of EPR studies of photoezcited triplets of model systems show that it is not possible to give generally applicable rules for the interpretation of the spectroscopic data. In a number of cases there appears to be a well-understood relationship between dimerization effects and dimer geometry. In most of the systems considered here that is not the case. It is not clear to what difference in make-up of the dimers this discrepancy must be attributed and this is an interesting point of further investigation. Evidently, as long as the data on fairly well characterized model systems are not fully understood it will be impossible to derive definitive conclusions concerning the structure of the special pair from data on its photoexcited triplet state. 

Schenck and Steinmetz [26] have found that the addition of maleic anhydride to benzene can be photosensitized by benzophenone. The photosensitized reaction also works with toluene, o-xylene, and chlorobenzene. Hardham and Hammond [27,28] have also studied the photosensitized addition and they obtained definitive evidence that this reaction proceeds via the triplet state. They also proposed an ortho adduct as intermediate but were unable to isolate it. Bryce-Smith and Vickery [29] found that phenanthrene reacts with maleic anhydride at the 9,10-positions to give an adduct that does not further react with a molecule of maleic anhydride. This reaction can also be sensitized by benzophenone. 

Time-resolved CIDEP and optical emission studies provide further definitive characterization of the triplet and excited singlet states followed by their primary photochemical reactions producing transient radicals in individual mechanistic steps in the photolysis of a-guaiacoxylacetoveratrone. Both fluorescence and phosphorescence are observed and CIDEP measurements confirm the mainly n,n character of the lowest triplet state. The results indicate a photo triplet mechanism involving the formation of the ketyl radical prior to the P-ether cleavage to form phenacyl radicals and phenols. Indirect evidence of excited singlet photo decomposition mechanism is observed in the photolysis at 77 K. 

The triplet state of the unpaired electrons of oxygen play a key role in both the photon excitation and the potential relaxation mode of the excited chromophores of vision. The paramagnetic properties of oxygen provide a definitive method of determining whether oxygen is present in the chromophores of vision, a condition that would eliminate the Shiff-base theory of retinol reaction with opsin to form rhodopsin. The evaluation of the electron paramagnetic resonance of the chromophores of vision is discussed in Chapter 7. 

By using the above definitions, one gets the following expression for the repulsion energy of the triplet state (9, in Scheme 3.4) ... 

A mechanism below 325 nm must definitely invoke the radical process (22) in addition to the mechanism for the 325 to 360-nm region just described above. Here, it is possible that the triplet state (T ) may dissipate directly by the H + HCO channel as justified by the potential-energy-surface calculations of Hayes and Morokuma (104) and Jaffe and Morokuma (123). However, it is not possible to rule out the intermediacy of hydroxycarbene. It is apparent from Table 5 that the ratio of levels off at... 

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