B. Kukliński

Photoluminescence Properties of trans–4,4'–Diamino–stilbene in Poly(vinyl alcohol) Films

Abstract Experimental studies have shown that the nonpolar molecule 4,4-diamino-stilbene (DAS) in poly(vinyl alcohol) film (PVA) at 296 K, apart from fluorescence displays phosphorescence whose intensity differs only slightly from that observed at 84 K. The overlapping of fluorescence and phosphorescence bands is the reason of the unusual behaviour of the emission anisotropy in the longwave absorption and photoluminescence bands. A distinct effect of direct irradiation on the intensity of these bands was observed.

Unusual Absorption and Fluorescence Properties of p-Substituted Stilbenes in Poly (vinyl alcohol) Films

Abstract The behaviour of absorbance, fluorescence and emission anisotropy of linear molecules with one double bond, i.e. 4-amino-4-nitrostilbene (ANS), 4-dimethylamino-4-nitrostilbene (DNS) and 4,4-diphenylstilbene (DPS), was examined in polyvinyl alcohol) (PVA) films at different temperatures (293-423 K). The unusual behaviour of absorption and fluorescence properties of the molecules in vestigated, similar to those of linear polyenes in PVA, was, however, less pronounced.

Absorption and Fluorescence Properties of p-Substituted Stilbenes in Poly (vinyl chloride) Film

Abstract Experimental studies have demonstrated that the absorption and fluorescence spectra of linear molecules with one double bond, i.e. 4-amino-4-nitrostilbene (ANS), 4-dimethylamino-4-nitro-stilbene (DNS) and 4,4-diphenylstilbene (DPS), contained in preheated to 393 K or nonheated polyvinyl chloride) (PVC) films are identical in shape and position, unlike those observed for ANS, DNS and DPS in polyvinyl alcohol) (PVA) films. For polar ANS and DNS molecules in PVC film a decrease in the emission anisotropy with growing wavelength of the fluorescence band was observed. This unusual behaviour of the emission anisotropy is accounted for by the overlap of two close emission bands from different luminescent centres, resulting from different microenvironments of the ANS and DNS molecules in PVC film. The emission anisotropy of nonpolar DPS molecule in PVC does not change within the fluorescence spectrum.

CAN TWISTED INTERNAL CHARGE-TRANSFER (TICT) STATE BE FORMED IN RIGID POLYMERS ?

Abstract Absorption, emission and emission anisotropy spectra of 4-cyano-N,N-dimethylaniline (CDMA) and 4-cyano-2,6,N,N-tetramethylaniline (CTMA) were investigated in polyvinyl alcohol) (PVA) films. It was found that the CDMA and CTMA molecules in PVA films at room temperature display phosphorescence, the emission band of which overlaps with the longwave fluorescence band a. The low value of the emission anisotropy shows that in the rigid PVA matrix there are microscopic defects in the form of empty spaces in which a certain fraction of the CDMA or CTMA molecules can attain twisted intramolecular charge-transfer states (TICT) due to rotational relaxation. The emission anisotropies in the shortwave, b, and longwave, a, fluorescence bands of CDMA in propylene glycol were found to be distinctly different, this indicating that the directions of the transition moments are not parallel.

Isomerization of Diphenyl Polyenes. Part VIII. Absorption and Fluorescence Properties of l-Phenyl-4-diphenylthiophosphinyl Butadiene in Poly (vinyl alcohol) Film

Abstract The effect of temperature (from 296 to 423 K) upon the absorption and fluorescence of l-phenyl-4-diphenylthiophosphinyl butadiene (PDPB) and of the direct irradiation on the absorbance were investigated in poly(vinyl alcohol) film. It was found that for PDPB in PVA film the transition from cis to trans configuration is only possible as a result of thermal isomerization due to the softening of PVA polymer, whereas photoisomerization results in both cis-to-trans and trans-to-cis transitions. Similar as with 1,4-diphenyl-1,3-butadiene in PVA, the luminescence is due to two, trans-trans and cis-trans, PDPB conformers.

Isomerization of Diphenyl Polyenes. Part V. The Origin of Fluorescence of l,6-Diphenyl-1,3,5-hexatriene in Poly (vinyl alcohol) Films

Abstract The effect of temperature on the absorption and fluorescence spectra of l,6-diphenyl-1,3,5-hexatriene (DPH) was investigated in three different polymer films: polyvinyl chloride) (PVCh), polyvinyl formal) (PVF) and polyvinyl alcohol) (PVA) in the temperature range 296-423 K. Anomalous behaviour of the fluorescence intensity was observed only for DPH in non-heated PVA film. The intensity distribution in the fluorescence band of DPH in both non-heated and heated PVCh and PVF films was found to be independent of the excitation light wavelength, λexc . The behaviour of DPH is similar in the PVA film heated to 423 K. For these samples, single exponential fluorescence decay was observed. The behaviour of non-heated DPH samples in PVA is quite different, the intensity distribution and the fluorescence band position depending strongly on λexc and the fluorescence decay being double exponential. It can be inferred that the fluorescence of DPH in a non-heated PVA sample consists of two components, the first originating from the all-trans conformer and the second from the ground-state s-cis conformer.

Isomerization of Diphenyl Polyenes. Part VII. The effect of Daylight and Direct Irradiation on the Photoisomerization of Ph-(CH = CH)n-Ph for n = 2, 3, 4 in Poly(vinyl alcohol) Films

Abstract Photoisomerization of 1,4-diphenyl-1,3-butadiene (DPB), 1,6-diphenyl-1,3,5-hexatriene (DPH) and 1,8-diphenyl-1,3,5,7-octatetraene (DPO) in poly(vinyl alcohol) (PVA) films was studied unter daylight and direct irradiation. The most efficient photoisomerization occurs in the DPB molecule, the smallest among the compounds investigated. For the greatest, DPO, molecule no distinct isomerization was observed in daylight and only a temperature effect was noted. Therefore, the DPO molecule in the PVA film heated to 423 K may serve as a fluorescence standard.

Isomerization of Diphenyl Polyenes.Part IV. Evidence for Two Luminescent Conformers of 1,4-Diphenyl-1,3-butadiene in Poly(vinyl alcohol) Films

Abstract Investigations of the effect of the excitation light wavelength on the intensity distribution in the fluorescence band of 1,4-diphenyl-1,3-butadiene (DPB) in poly(vinyl alcohol) films (PVA) at 296 and 87 K for samples before and after heating to 423 K, and fluorescence lifetime measurements have shown that trans-trans and cis-trans conformers are responsible for the emission of fluorescence. The fluorescence properties of the DPB sample in PVA heated to 423 K were found to be similar to those of DBP in polyvinyl chloride and polyvinyl formal at 296 K.

Isomerization of Diphenyl Polyenes. Part VI. Properties of l,8-Diphenyl-l,3,5,7-octatetraene Fluorescence in Poly (vinyl alcohol) and other Polymer Films

Abstract Absorption, fluorescence and emission anisotropy spectra of l,8-diphenyl-l,3,5,7-octatetraene (DPO) in non-heated and heated polyvinyl alcohol) (PVA) films were measured at 296 and 87 K. Similar spectra to those of DPO in PVA heated to 423 K were observed for DPO in polymer films: polyvinyl chloride) (PVCh), polyvinyl formal) (PVF) and ethylacetate (EtA). Unusual photophysical properties of DPO fluorescence occur only in non-heated PVA. These are the increase in the absorbance and quantum yield at temperatures above 358 K and the change in the emission anisotropy, r, due to softening or stiffening of the PVA film. For DPO in PVCh and EtA, high values of r, close to 0.4, are observed (0.391 and 0.389, respectively), thus manifesting the stiffening of the microenvironment around the DPO molecule in these polymers. In the case of DPO in non-heated PVA film, strong temperature dependence of the intensity distribution in the fluorescence band and double exponential emission decay are observed. This proves that the fluorescence originates from two conformers: all-trans and s-eis.

Isomerization of Diphenyl Polyenes. Part III. Absorption and Fluorescence Properties of 1,4-Diphenyl-1,3-butadiene in Poly(vinyl alcohol) Film

The effect of temperature on the absorption and fluorescence properties of 1,4-diphenyl-1,3-butadiene (DPB) in polyvinyl alcohol) film (PVA) was investigated in the range from 293 to 423 K. Upon heating above 353 K, the optical density in the long wavelength region (at 339 nm) increases five times only, whereas for 1,6-diphenyl-1,3,5-hexatriene (DPH) and 1,8-diphenyl-1,3,5,7-octatetraene (DPO) ten and twenty times, respectively. However, the total quantum yield (ΦF = 0.68) at 293 K is greater than that for the trans-trans form (ΦF = 0.63) and decreases with growing temperature. Both this effect and broadening effect in the fluorescence band at 293 K evidence the existence of two emission centres, i.e. the trans-trans and cis-trans conformers.