Near-UV light

Other early work, which continues to this day, involved vibronic relaxation [6] of large colored molecules such as chrysene [19], pyrene [20] and perylene [21], due to the relative ease of using visible or near-UV light to pump and probe these systems (see example C3.5.6.5 below). 

The primary photochemical act, subsequent to near-uv light (wavelengths <400 nm) absorption by Ti02 particles, is generation of electron—hole pairs where the separation (eq. 3) into conduction band electrons (e g ) and valence band holes (/lyB ) faciUtated by the electric field gradient in the space charge region. Chemically, the hole associated with valence band levels is constrained at... 

The same products are obtained (though in different proportions) when Na or K is omitted but the solution is irradiated with near-UV light.In either case other leaving groups can be used instead of halogens (e.g., NR3, SAr) and the mechanism is the SrnI mechanism. Iron(II) salts have also been used to initiate this reaction. The reaction can also take place without an added initiator Enolate ions of ketones react with Phi in the dark. " In this case, it has been suggested that initiation... 

It is practical to place a washing bottle or scrubber in the gas line just before the manifold. The aqueous solution in this bottle contains a reductant for traces of molecular oxygen and at the same time wets the gas which will minimize a concentrating effect on the sample by drying. A practical solution is 1 mM zinc acetate, 1 pM TMP (meso-tctra(/V-methyl-4-pyridyl)porphinc-tetra-tosylate), 100 mM Na2EDTA, 100 mM Tris-HCl buffer at pH 10. The porphyrin complexates the Zn2+ and forms a light-sensitive compound that can be excited by near UV light from an 18 watt TL-tube. 

The molecule [ReI(MQ+)(CO)3(dmb)]2+ has been a model system for studying intramolecular electron transfer over the last two decades. Here, MQ+ is the monodentate ligand Af-methyl-4,4/-bipyridinium, dmb is the bidentate ligand 4,4r-dimethyl-2,2r-bipyridine, and the three CO ligands are facially coordinated. Irradiation of this complex at room temperature in solution with near-UV light leads to a sequence of intramolecular electron-transfer events as shown in Fig. 7. 

Fujishima and Honda reported the splitting of water by the use of a semiconductor electrode of titanium dioxide (rutile) connected through an electrical load to a platinum black counter-electrode. Irradiation of the Ti02 electrode with near-UV light caused electrons to flow from it to the platinum counter-electrode via the external circuit. 

If di-arylethylenes are used as electrochromic substances (in media capable of conducting electric current), applying a 10- to 12-V cyclically changing voltage enhances the optical absorption as described earlier. These changes are readily registered and remain constant for at least 2 years. In order to return to the initial state of the system, it is sufficient to apply a near-UV light impulse for just a few seconds. The record-erase cycles can be repeated more than 1000 times with the same capacity. 

Since chemistry of pterines and purines has been already reviewed (42,48,491), only recent studies will be described here. Guanine (93) was prepared by reaction of 4-hydroxy-2,5,6-triaminopyrimidine sulfate (588 see Scheme 73) with HCONH2 with removal of H2O from the reaction system in an excellent yield (492). Also, irradiation of oxygenated aqueous solutions of 6-mercaptopurine with near-UV light gave hypoxanthine (92) as a minor product (< 10%) together with purine-6-sulfinate (589). It also arises from degradation of purine-6-sulfonate obtained from photooxidation of the sulfinate (589) (493). 

The molecule spiropyran and its derivatives are one of the most widely used photochromic systems. The starting material is colourless, hence near UV light is needed for the photochromic action. The coloured species is a tautomer which reverts to the starting material thermally in the dark (Figure 6.23). 

Semiconductor systems have other advantages in that the visible and near uv light can be absorbed effeciently and the electrons and holes in the semiconductor in general have much higher mobilities than ions in solution. In the present chapter, the basic properties of the semiconductor/soiution interface are described followed by discussion of some recent topics of photoelectrochemistry at this interface. 

The possibility of solar photoelectrolysis was demonstrated for the first time with a system in which an n-type Ti02 semiconductor electrode, which was connected through an electrical load to a platinum black counter electrode, was exposed to near-UV light (Fig 2.2).l9) When the surface of the Ti02 electrode was... 

Brunow and Sivonen (34) obtained similar results on a lignin model system, ethylguaiacylcarbinol. This compound did not undergo any oxidation when irradiated with near-uv light until p-methoxyacetophenone, a triplet sensitizer, was added to the solution. As the molar ratio of p-methoxyacetophenone to ethylguaiacylcarbinol was increased to 0.32 the rate of photooxidation of this benzyl alcohol increased. This result is consistent with the mechanism of light-induced yellowing shown in Scheme 3. 

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