Cage mechanism photochemistry

Cadmium, tris[4,4,4-trinuoro-l-(2-furyl)-l,3-butanedione]-structure, 65 Cadmium complexes equilibrium constant solvent effect, 516 Cage compounds in gravimetry, 525 Cage mechanism photochemistry, 393 Cages, 135 formation... 

In addition, because thiols are often used to remove the initially formed 2-nitrosoacetophenone (45) byproduct, the photochemistry of the caged ATP was examined in both the absence and the presence of dithiothreitol (46). With the aid of TRIR experiments, the ultimate products and mechanisms of their formation were elucidated for the first time. In the absence of added thiol 45 mainly dimerizes in the presence of 46, however, 45 reacts through a series of intermediates to form 3-methylanthranil (47) (Scheme 2.22). 

The photochemistry of nitrophenylacetates has been investigated by UV-pump/IR-probe spectroscopy, combined with quantum chemical calculations. For the meta and para isomers, decarboxylation proceeds via a triplet state with subnanosecond lifetime. In the case of the ortho derivative, photodecarboxylation is nearly suppressed by excited state proton or hydrogen atom transfer, but it can still be investigated due to the isolated spectral position of the CO2 band. Data analysis reveals that a weak ultrafast release channel represents the main photodecarboxylation pathway for this compound. Understanding CO2 uncaging mechanisms can be useful for the design of improved nitrobenzyl cages. 

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