Excited states of poly

Quenching of the excited state of poly(acrylic acid-co vinylbipyridine)-pendant [Ru(bpy)3]2 + 19) by methyl viologen in alkaline aqueous medium has been studied and the effect of the polymer has been discussed 99). Among the three different molecular weight samples used (MW 2100, 4400, 13 300), the quenching of the lowest molecular weight polymer is explained to occur through a dynamic process, while the... 

The Excited States of Poly(vinyl cinnamate) and their Photochemical Reactivities. The photochemical reaction of PVCi is believed to be Intermolecular crosslinking of the polymer chains by the formation of the four-membered ring from the central double bonds of cinnamoyl-oxy groups( ), and it is known that many experimental results from the photochemical reaction are interpreted well(6) if we can postulate that the reaction is the concerted cycloaddition according to the Woodward-Hoffmann s rule(lB). This means that the four-membered ring... 

In addition, Tsuda and Oikawa carried out molecular orbital calculations of the electronic structures in the excited states of poly(vinyl cinnamate) [131, 132], They based their calculations on the reaction of intermolecular concerted cycloaddition that take place according to the Woodward-Hoffmann s rule. This means that the cyclobutane ring formation takes place if a nodal plane exists at the central double bond in the lowest unoccupied MO(LLUMO) and not in the highest occupied MO (HOMO) of the grotmd state cinnamoyloxy group. This is within the picture of Huckel MO or Extended Huckel MO theory. The conclusion is that the cmicerted cycloadditions occur favorably in the lowest triplet state Ti and in the second excited singlet state S2 [132]. 

Kim and Webber studied delayed emission spectra of poly(vinyl carbazole) that was doped with dimethylterephthalate and pyrene [252]. On the basis of their results, they concluded that at room temperature dimethylterephthalate does not completely quench the triplet excitation state of poly (vinyl carbazole). They also concluded that phosphorescent states of poly(vinyl carbazole)-dimethylterephthalate are similar, implying a significant charge-transfer character in the former. 

Lochmuller and coworkers used the formation of excimer species to answer a distance between site question related to the organization and distribution of molecules bound to the surface of silica xerogels such as those used for chromatography bound phases. Pyrene is a flat, poly aromatic molecule whose excited state is more pi-acidic than the ground state. An excited state of pyrene that can approach a ground state pyrene within 7A will form an excimer Pyr +Pyr (Pyr)2. Monomer pyrene emits at a wavelength shorter than the excimer and so isolated versus near-neighbor estimates can be made. In order to do this quantitatively, these researchers turned to measure lifetime because the monomer and excimer are known to have different lifetimes in solution. This is also a way to introduce the concept of excited state lifetime. 

The emissive counterpart to CD is circularly polarized photoluminescence (CPPL). Where the fluorophore is chiral, then the photo-excited state can return to the ground state with emission of circularly polarized light, the direction of polarization of which depends on the relative intensities of the right-handed and left-handed emissions (/r and /L, respectively), which in turn depends on the chirality of the material, or more accurately, the chirality of the photo-excited state of the material. CPPL studies on poly silanes are extremely rare, however, due to the low CPPL intensity and rapid sample degradation in solution, and problems due to artifacts in the solid state. 

A two-photon allowed absorption of poly(dihexylsilane) has been observed at 0.9 eV above the one-photon excitation63 -65, in contrast to the two-photon absorption of linear polyenes, which is about 0.5 eV below the intense one-photon absorption. Absorption spectra and the dynamics of other high-lying excited states of the polysilane have been investigated by means of femtosecond time-resolved excited-state absorption spectroscopy66. 

The spectroscopic signatures of excited states of derivatives of the conjugated polymer poly (p-phenylene vinylene) have been widely investigated both... 

Fig. 11 Illustration of the excited state relaxation derived from experimental results obtained for poly(dA).poly(dT) by steady-state absorption and fluorescence spectroscopy, fluorescence upconversion and based on the modeling of the Franck-Condon excited states of (dA)io(dT)io. In red (full line) experimental absorption spectrum yellow circles arranged at thirty steps represent the eigenstates, each circle being associated with a different helix conformation and chromophore vibrations.

Polysilane-based nanostructured composites were synthesized by the inclusion of poly(di-w-hexylsilane) (Mw = 53,600) into mesoporous, Si-OH-rich silica with a pore size of 2.8 nm.81 Two PL bands are observed for the composite. A narrow band at 371 nm, assigned to a PDHS film on a quartz substrate is blue shifted by 20 nm, a shift attributed to the polymer being incorporated into the pores.82 The size of the monomeric unit of the PDHS is about 1.6 nm, so only one polymer chain can be incorporated into a mesopore with a diameter of 2.8 nm. The narrow PL band at 350 nm is due to the reduction of the intermolecular interactions between polymer chains. This narrow PL band at 350 nm is assigned to the excited state of the linear polymer chain.81 Also, a new broad band of visible fluorescence at 410 nm appeared, which is assigned to localized states induced by conformational changes of the polymer chains caused by its interaction with the silanol (Si-OH) covered pore surface. Visible luminescence in nanosize PDHS is observed only when the polymer was incorporated in hexagonal pores of 2.8 nm and is not seen for the polymer incorporated into cubic pores of 2.8 nm diameter or hexagonal pores of 5.8 nm diameter. 

Some polymers show discoloration as well as reduction of the mechanical properties (e.g. aromatic polyesters, aromatic polyamides, polycarbonate, polyurethanes, poly (phenylene oxide, polysulphone), others show only a deterioration of the mechanical properties (polypropylene, cotton) or mainly yellowing (wool, poly(vinyl chloride)). This degradation may be less pronounced when an ultraviolet absorber is incorporated into the polymer. The role of the UV-absorbers (usually o-hydroxybenzophenones or o-hydroxyphenylbenzotriazoles) is to absorb the radiation in the 300-400 nm region and dissipate the energy in a manner harmless to the material to be protected. UV-protection of polymers can be well achieved by the use of additives (e.g. nickel chelates) that, by a transfer of excitation energy, are capable of quenching electronically excited states of impurities (e.g. carbonyl groups) present in the polymer (e.g. polypropylene). 

Optically clear films of poly[(2-hydroxy-3-allyl-4,4 -dimethoxybenzophenone)-co-methyl methacrylate] having M 60000 and 83000 respectively were irradiated and both the character and rate of the decay of the excited state of attached... 

The character of the lowest excited state depends on the nature of the metal atom, the polypyridine ligand and the ancillary ligands. MLCT excited states are the lowest excited states of those complexes which contain easily-oxidized low-valent metal atoms Cr, Mo°, W°, Mn, Re Fe Ru Os, Pt and Cu These are the polypyridine complexes whose ground-state reduction and oxidation is predominantly localized on the metal atom and the polypyridine ligand, respectively (Section 5.3.1). MLCT electronic transitions are strongly allowed and usually occur in the visible spectral region. Hence, irradiation into MLCT absorption bands of poly-... 

Figure 26. Schematic representation of a sensory signal amplification upon formation of a poly-pseudorotaxane from a conjugated polymer with appended many fluorescent electron-donor macrocycles. Threading only one macrocycle by an electron acceptor can cause the quenching, by energy or electron transfer, of the fluorescent excited state of remote macrocycles [68b].

Poly(propyleneamine) dendrimers of generations 1 and 4 (89) functionalized with azobenzene groups were investigated as hosts for eosin Y (eosin = 2, 4, 5, 7 -tetrabromofluorescein dianion) in DMF solution [159]. The peripheral azobenzene groups can be switched by light excitation from the E to the Z form. The fluorescent excited state of eosin is reductively quenehed by the tertiary amine units present in the dendrimer structure. This electron transfer quenching takes place with a static... 

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