Triplet state quenching

Consider a photoreactive molecule M. If the triplet state of M is involved in any photochemical reaction, then addition of triplet acceptors to the reaction solution should quench triplet state reactions by the diffusion controlled process... 

Subsequent work has shown that this class shows some ability to behave by the chain-breaking mechanism (11,21,22) and also to quench triplet states (16,20). However, there is little doubt that uv screen-Ing is one, and probably the most Important, of their functions so that they prevent or reduce the rate of formation of initiating free radicals in the polymer. 

Energy Transfer. In the Kautsky mechanism for quenching triplet state molecules, electronic excitation energy is transferred from Mi to the oxygen molecules, as follows (20) ... 

On the other hand, ferrocene forms charge-transfer complexes with nitrobenzenes [966], tetracyanoethylene (TCNE) [96, 96c, 96d] and 2,3-dichloro-5,6-dicyanoquinone. Mdssbauer spectroscopy indicates that the ferricenium ion is not present in the 1 1 TCNE ferrocene complex, and, as may also be the case with the nitrobenzene complexes, it is suggested that the complex is of benzenoid type with the TCNE placed above a r-CsHs ring, 4.4 [96c]. In this context it is noteworthy that the high efficiency of ferrocene in quenching triplet states in excited photosensitizers, e.g., benzophenone, may be due to a charge-transfer mechanism [96e]. 

Typical singlet lifetimes are measured in nanoseconds while triplet lifetimes of organic molecules in rigid solutions are usually measured in milliseconds or even seconds. In liquid media where drfifiision is rapid the triplet states are usually quenched, often by tire nearly iibiqitoiis molecular oxygen. Because of that, phosphorescence is seldom observed in liquid solutions. In the spectroscopy of molecules the tenn fluorescence is now usually used to refer to emission from an excited singlet state and phosphorescence to emission from a triplet state, regardless of the actual lifetimes. 

Goudsmit G H and Paul H 1993 Time-resolved EPR investigation of triplet state Cgg. Triplet-triplet annihilation, CIDEP, and quenching by nitroxide radicals Chem. Phys. Lett. 208 73-8... 

The mechanism of the Patemo-Biichi reaction is not well understood, and while a general pathway has been proposed and widely aceepted, it is apparent that it does not represent the full scope of reactions. Biichi originally proposed that the reaction occurred by light catalyzed stimulation of the carbonyl moiety 1 into an excited singlet state 4. Inter-system crossing then led to a triplet state diradical 5 which could be quenched by olefinic radical acceptors. Intermediate diradical 6 has been quenched or trapped by other radical acceptors and is generally felt to be on the reaction path of the large majority of Patemo-Biichi reactions. Diradical 6 then recombines to form product oxetane 3. 

Quenching of the Intersystem Crossing to the Triplet State 521 Photoinduced 1RAV Studies 522 Time-Resolved Photoinduced Studies 524 Sensitization of Photoconductivity 525 Magnetic Properties 526... 

Figure lb shows the transient absorption spectra of RF (i.e. the difference between the ground singlet and excited triplet states) obtained by laser-flash photolysis using a Nd Yag pulsed laser operating at 355 nm (10 ns pulse width) as excitation source. At short times after the laser pulse, the transient spectrum shows the characteristic absorption of the lowest vibrational triplet state transitions (0 <— 0) and (1 <— 0) at approximately 715 and 660 nm, respectively. In the absence of GA, the initial triplet state decays with a lifetime around 27 ps in deoxygenated solutions by dismutation reaction to form semi oxidized and semi reduced forms with characteristic absorption bands at 360 nm and 500-600 nm and (Melo et al., 1999). However, in the presence of GA, the SRF is efficiently quenched by the gum with a bimolecular rate constant = 1.6x10 M-is-i calculated... 

Scheme 30 represents the energy diagram for the photorearrangement shown in Scheme 29. Quenching of the triplet state of the sensitizer by the cis allyl phosphate, c/s-1, generates the triplet state, T , of the 1,2-biradical 2. The 1,2-biradical is trapped by the phosphorus atom to afford the triplet state, TP, of the spirophosphoranyl 1,3-biradical 3. Then, inter-system crossing generates the...

Both energy and electron transfer quenchers have been employed to show that the quenching rates of the fullerene triplet state are decreased as a function of the size of the dendrimer shell [36]. These results further demonstrate that fullerene is an excellent functional group to probe the accessibility of a dendrimer core by external molecules. 

As can be seen in these reactions, carotenoids may protect photosynthetic bacteria at various levels by quenching the singlet-excited state of O2 or the tiiplet-excited state of chlorophyll. The ground states of oxygen would be 3O2 and for CHL the triplet state. The carotenoids may be the preferred substrates for oxidation or may act in quenching reactive species. ... 

A rather important aspeet that should be eonsidered is that interfaeial quenching of dyes does not neeessarily imply an eleetron-transfer step. Indeed, many photoehemieal reactions involving anthracene oeeur via energy transfer rather than ET [128]. A way to discern between both kinds of meehanisms is via monitoring the accumulation of photoproducts at the interfaee. Eor instance, heterogeneous quenehing of water-soluble porphyrins by TCNQ at the water-toluene interfaee showed a elear accumulation of the radical TCNQ under illumination [129]. This system was also analyzed within the framework of the exeited-state diffusion model where time-resolved absorption of the porphyrin triplet state provided a quenehing rate eonstant of the order of 92M ems. ... 

Zinc is also used in biological studies to gain information about non-zinc containing systems. It can be a convenient redox inactive replacement for the study of complex systems with multiple redox centers. For example, the mechanism of quenching the triplet state of zinc cytochrome c by iron(II) and iron(III) cytochrome c has been studied. Zinc insertion has been used to get around the difficulty of studying two heme proteins with the same absorption spectra and provides rate constants for iron and iron-free cytochrome c quenching.991... 

---