Stilbene Lasers

A theoretical study of the excited states of stilbene and stilbenoid donor-acceptor dye systems as potential laser was performed [4]. Semiempirical calculations within the CNDO/S framework were used to characterize the nature of the phantom-singlet excited state P (double-bond twisted geometry) of stilbene and stilbenoid donor-acceptor dye systems including 4-(dimethylamino)styrylpyridylmethylium and DCM laser dyes. It was shown that for stilbene, a slight geometric symmetry reduction is 

Stiibmes. Applications in Chemistiy, Life Sciences and Materials Science. Gerlz Likhtenshtein Copyright 2010 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 978-3-527-32388-3 

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Coupling tetra2o (7) with o-cresol has been reported to give a dye (19) which is less alkah-sensitive than Direct Yellow 4 (Cl 24890) and to have better cold-water solubiUty than Direct Yellow 12 (Cl 24895) (18). One reference is made to a stilbene laser dye (10) and two each to dyes for 1ight-po1ari2ing films (34,35) and reprographic inks (36,37). 

According to Kramers model, for flat barrier tops associated with predominantly small barriers, the transition from the low- to the high-damping regime is expected to occur in low-density fluids. This expectation is home out by an extensively studied model reaction, the photoisomerization of tran.s-stilbene and similar compounds [70, 71] involving a small energy barrier in the first excited singlet state whose decay after photoexcitation is directly related to the rate coefficient of tran.s-c/.s-photoisomerization and can be conveniently measured by ultrafast laser spectroscopic teclmiques. 

The easiest method for creating many vibrational excitations is to use convenient pulsed visible or near-UV lasers to pump electronic transitions of molecules which undergo fast nonradiative processes such as internal conversion (e.g. porjDhyrin [64, 65] or near-IR dyes [66, 62, 68 and 62]), photoisomerization (e.g. stilbene [12] or photodissociation (e.g. Hgl2 [8]). Creating a specific vibrational excitation D in a controlled way requires more finesse. The easiest method is to use visible or near-UV pulses to resonantly pump a vibronic transition (e.g. 

Fig. 10. Tuning curves (41) for a continuous argon laser pumped dye laser, where A represents polyphenyl 2 B, stilbene 1 [74758-59-1] C, stilbene 3...

Organic colors caused by this mechanism are present in most biological colorations and in the triumphs of the dye industry (see Azinedyes Azo dyes Eluorescent whitening agents Cyanine dyes Dye carriers Dyes and dye intert diates Dyes, anthraquinone Dyes, application and evaluation Dyes, natural Dyes, reactive Polymethine dyes Stilbene dyes and Xanthenedyes). Both fluorescence and phosphorescence occur widely and many organic compounds are used in tunable dye lasers such as thodamine B [81-88-9], which operates from 580 to 655 nm. 

The characterization of the laser pulse widths can be done with commercial autocorrelators or by a variety of other methods that can be found in the ultrafast laser literature. " For example, we have found it convenient to find time zero delay between the pump and probe laser beams in picosecond TR experiments by using fluorescence depletion of trans-stilbene. In this method, the time zero was ascertained by varying the optical delay between the pump and probe beams to a position where the depletion of the stilbene fluorescence was halfway to the maximum fluorescence depletion by the probe laser. The accuracy of the time zero measurement was estimated to be +0.5ps for 1.5ps laser pulses. A typical cross correlation time between the pump and probe pulses can also be measured by the fluorescence depletion method. 

Fig. 3 Transient spectra obtained upon the application of a 200-fs laser pulse to a solution of stilbene (S) and chloranil (Q) in dioxane. (a) The fast decay ( 20 ps) of the contact ion-radical pair S+ , Q generated by direct charge-transfer excitation (CT path), (b) The slow growth ( 1.6 ns) of the ion pair S+ Q due to the diffusional quenching of triplet chloranil (A path) as described in Scheme 13. Reproduced with permission from Ref. 55.

Figure 1. Time-dependent absorption spectra obtained after laser excitation (248 nm, 20 ns) of benzophenone (frans-2,3-diphenylaziridin-l -yljimine (134d) in oxygen-saturated TFE.64 Inset influence of the laser dose on the yields of stilbene (monophotonic) and diphenylmethyl cation (biphotonic).

Laser flash photolysis (30 ns, 50 mj, 347 nm) of 4-nitrostilbene, 4,4 -dinitro-stilbene, 4-nitro-4 -methoxystilbene and 4-dimethyl-amino-4 -nitrostilbene permits the observation of transients 133) por the latter two compounds, the lifetime and the absorption spectra of the transients vary strongly with the polarity of the solvent used. First order decay rate constants are given in Table 4. 

While much has been learned about S near the geometry of tS in solution, there have been no reports on the spectroscopic detection of the twisted excited singlet state of stUbene. Information about the twisted excited singlet state of tetrapheny-lethene will be described in this chapter in Section 2.3. Interesting photochemistry also occurs following the excitation of cw-stilbene however, because of the much shorter lifetime of c -stilbene, femtosecond-pulsed lasers must be used." ... 

Fig. 3 Charge transfer in DNA hairpins after photoexcitation of stilbene linker (St) by a laser pulse [45]. A hole, first, undergoes a transition from photoexcited St to the adjacent GC pair as shown by the solid arrow. Then it can either hop to next GC pairs (dot-dashed arrow) or return to St with the subsequent electron-hole recombination (dotted arrow)...

Spectroscopic evidence for the transient formation of the trans-stilbene radical cation could be obtained when colloidal TiOj suspended in an acetonitrile solution containing trans-stilbene (a species which should also be exothermically oxidized by a TiO valence band hole) was excited with a laser pulse The observed transient was identical in spectroscopic features and in lifetime with an authentic sample of the stilbene cation radical generated in the same medium via pulse radiolytic techniques. That the surface influences the subsequent chemistry of this species can be seen in the distribution of products observed under steady state illumination, Eq. (4) 2 . ... 

The present work comprises of a first step towards this goal and involves measured photoelectron spectra of trans-Stilbene following the excitation with tuneable femtosecond UV laser pulses. The ionization process occurs in a (1+1) REMPI scheme, using the first excited singlet state (Si) of trans-Stilbene as an intermediate resonance. 

In conclusion, we present a spectroscopic study of nn excitation in trans-Stilbene in a molecular beam experiment. The excitation involves a 1+1 REMPI scheme following the interaction of the molecule with femtosecond UV laser pulses. When the excitation is resonant with the origin of the intermediate Si state, the measured photoelectron distribution reveals a maximum probability for the 0-0 transition. For higher photon energies (266nm) the photoelectron spectrum exhibits a rather complex distribution, due to the excitation of an alternate (C-C) stretching mode. 

Platinum porphyrin complexes can be prepared by reaction with PtCl2(PhCN)2. Purification of the final complex is by medium pressure liquid chromatography on alumina. The strongly phosphorescent platinum(II) porphyrin complexes are efficient sensitizers for stilbene isomerization. The quantum yields for the cis to trans process are greater than unity because of a quantum chain process in which the metalloporphyrin serves both as an energy donor and an acceptor.1110 Picosecond laser spectroscopy has been used to obtain time-resolved excited-state spectra of platinum octaethylporphyrin complexes, and to probe the excited-state energy levels.1111 Tetrabenzoporphyrin complexes have been prepared for platinum in both the divalent and tetravalent oxidation states. The divalent complex shows strong phosphorescence at 745 nm.1112... 

Fig. 3.4. A set of SORS spectra collected from a two-layer system consisting of 1 mm thick layer of PMMA made of 20 im diameter spheres followed by a 2 mm layer of trans-stilbene powder measured using 514 nm as the probe wavelength. The spectra are shown for different spatial offsets. The top and bottom spectra are those of the individual layers obtained in separate measurements. The spectra are offset for clarity. The acquisition time was 100 s for each spectrum and the average laser power 12 mW (reprinted with permission from [18]. Copyright (2005) The Society for Applied Spectroscopy)...

Let us mention the rotational beats which have recently been observed (with a trans-stilbene molecule in a gasodynamic jet) and interpreted by Felker and Zewail [54, 145]. The essence of this interesting phenomenon may be described in a simplified way as follows. Let a picosecond laser pulse be capable of coherently exciting from some rotational state J f of a... 

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