Absorption and Fluorescence Spectra of Polydiacetylenes (4BCMU and 3BCMU) in Solution

Kanetake, T.; Tokura, Y.; Koda, T.; Kotaka, Tadao; Ohnuma, Hiroshi

doi:10.1143/jpsj.54.4014

Cited by 39 publications

(13 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From a comparison of experimental and calculated bond lengths in TCDU crystal, it is observed that the C2-C3 bond length by EL [ 1.17 ( 1 ) A] is considerably smaller than the predicted value for the butatriene structure (1.248 A). It is the shortest C-C bond length in Table V (9) CIO-C9-C8 121.2(6) 124.6(7) C8-C 13-C 12 119.1 (6) 119.0 (7) FIG. 1.…”

Section: Resultsmentioning

confidence: 99%

“…The exciton absorption peak of this form is located at about 1.9 eV (about 1.S X 10 4 cm -1) which is similar in energy and shape to those of the blue-form films and solutions of PDAs. 5 , 6 We shall therefore refer to this golden TCDU crystal as the blue form. According to a previous x-ray study by Enkelmann and Lando (cited hereafter as EL), 7 the blueform TCDU crystal has been assigned to the acetylene structure (=RC-C=C-CR=), while the red form one to the butatriene structure ( [RC=C=C=CR]).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Crystal structure of polydiacethylene TCDU revisited

Kobayashi

Tokura

et al. 1987

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Exciton self-trapping and formation of diradical intermediates in 5,7-dodecadiyne-1,12-diol bis[phenyl carbamate] (TCDU) crystals at low temperaturesThe crystal structure of the as-prepared form ofpoly(S,7-dodecadiyne-l,12-diyl-bisphenylurethane), customarily called TCDU, has been reexamined by an x-ray analysis. Bond lengths of the conjugated polymer backbone chain presently determined indicate that the structure of the as-prepared form of TCDU crystal is more close to that predicted for the acetylenic structure than the hitherto presumed butatrienic one.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Crystal structure of polydiacethylene TCDU revisited

Kobayashi

Tokura

et al. 1987

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…The characteristic spectral change of P-(3BCMU) solution was explained by Kanetake et al 17 It is reported that the color change is due to the conformation change of the backbone from rod-like to coil-like accompanied by the change of the conjugation length. The 630 nm wavelength light was used to monitor the color change.…”

Section: Ultraviolet and Visible Light Spectra And Colormentioning

confidence: 97%

“…where [17] is the intrinsic viscosity. Using eq 1, we estimated C* of this system to be 0.45% from the data of [17] in chloroform (CHC1 3 ) Polym.…”

Section: Estimation Of Ionic Conductivity In Gel Phasementioning

confidence: 99%

Electric Conductivity and Phase Transition of a Polydiacetylene Gel: Poly[4,6-decadiyn-1,10-diol-bis(n-butoxy-carbonylmethyl urethane)] P(3BCMU)

Chen

Adachi

Kotaka

1992

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:Electric conductivity and sol-gel transition behavior were studied for gels of a polydiacetylene poly[ 4,6-decadiyn-1, I 0-diol-bis(n-butoxy-carbonylmethyl urethane)] abbreviated to P(3BCMU). Two solvents with different dielectric constant were used, i.e., a-dichlorobenzene (o-DCB) and a mixed solvent of p-dichlorobenzene (p-DCB) and toluene (TOL). Temperature dependence of the shear moduli G' was measured to determine the gel-to-sol transition temperatures T, at which the moduli decreased steeply. The T, was 378 Kin o-DCB and 387 Kin p-DCBITOL (62138). Both direct current (DC) conductivity o-d, and alternating current (AC) conductivity 0"30 at I kHz exhibited a maximum around 368 and 362 K in o-DCB and p-DCBITOL, respectively. Dopant effects of an electron acceptor iodine and a donor tetrathiafulvalene TTF on o-do and o-" were also studied. o-" was enhanced approximately by 100 times with iodine but only by 5 times with TTF. The pronounced dopant effect indicates that the conduction in the gel state is partly due to electronic conduction through the P(3BCMU) chains. We also observed an appreciable strength of ionic conductivity in the sol and gel phases. The ionic conductivity in the gel phase was estimated from o-30 of the solvent containing the ions extracted from the gel phase. Then observed o-a, and o-d, were separated into the contributions of ionic and electronic conductions. Electronic conductivity increased with increasing dielectric constant of the solvent. Transition temperature T, where the color changed from blue to yellow was also determined by measuring the transmittance at 630 nm wave length. The temperature dependence of the transmittance indicated a hysteresis.KEY WORDS Electric Conductivity I Sol-Gel Transition I Polydiacetylene I Gel I Poly[ 4,6-decadiyn-1,10-diol-bis(n-butoxycarbonylmethyl urethane)] I P(3BCMU) I Among conducting polymers, derivatives of polydiacetylene with a relatively long side group are unique in a sense that they are soluble in a variety of organic solvents and form gel in poor solvents. 1 -4 In our previous papers, 1 • 2 we reported behavior of the reversible sol-gel transition and electric conduction in toluene (TOL) solution of poly[5,7-dodecadiyn-1,12-diol-bis(n-butoxy carbonyl methylurethane)] abbreviated to P(4BCMU). The alternating current (AC) conductivity O'ac at 1kHz and the direct current (DC) conductivity O'dc of P(4BCMU)/TOL gel exhibited a broad maximum around 336 K. Above this temperature, the() ac and() de decreased steeply with increasing temperature and reached to a level of an insulator. The O'ac and O'dc were enhanced approximately 20 times by doping with iodine.

show abstract

“…Bands B and D were previously assigned to photo excited n~n* excitons along the extended rod-like chains for P(3BCMU) and P(4BCMU) molecules, respectively. 12 Bands A and C are due to the n~n * transition of the coiled chains.…”

Section: Uv Spectra and Color Changementioning

confidence: 99%

Electric Conductivity, Elasticity, and Optical Spectra in Blend Gels of Polydiacetylenes: P(3BCMU)/P(4BCMU)/Mixed Solvent System

Chen

Adachi

Kotaka

1993

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:Alternating current conductivity o-w shear moduli G', and ultraviolet-spectra (UV) were studied for gels consisting of two polydiacetylenes i.e., poly[ 4,6-decadiyn-1,10-diol-bis(nbutoxy-carbonylmethyl urethane)] abbreviated as P(3BCMU) and poly[5,7-dodecadiyn-1,12-diolbis(n-butoxy carbonyl methylurethane)] abbreviated as P(4BCMU). As a common solvent of these polydiacetylenes, a mixed solvent p-dichlorobenzene (p-DCB)/toluene (TOL) (62/38) was used. Shear moduli G' of blend gels decreased stepwise around 340 and 385 K which coincided with the gel-to-sol transition temperatures of pure P(4BCMU) and P(3BCMU) gels, respectively. At 385 K the blend gels transformed completely into sol. Observed G' of blend gels conformed approximately to the additivity law with respect to the weight fraction of P(3BCMU) and P(4BCMU). This indicates that in the range of T<340 the gel network is composed of both the P(4BCMU) and P(3BCMU) molecules but above 340 K the network is composed only of the P(3BCMU) molecules. Temperature dependence of o-"' at I kHz exhibited two maxima around 330 and 360 K. o-ac observed around 360 K was ca. ten times higher than O"ac expected from the additivity. The UV spectra of the blend gels exhibited abosorption bands not seen in pure gels of the components. It is speculated that the P(3BCMU) and P( 4BCMU) chains partially form a charge transfer complex in blend gels.KEY WORDS Gel / Electric Conductivity / Elasticity / UV Spectra / Blend / Polydiacetylene / P(3BCMU) / P(4BCMU) / Gel-to-Sol Transition In our previous papers, 1 -3 we reported the electric conductivity, sol-gel transition behavior and ultraviolet and visible (UV) spectra in gels of polydiacetylenes. Specifically they were poly[ 4,6-decadiyn-1, 10-diol-bis(nbutoxy-carbonylmethyl urethane)] abbreviated as P(3BCMU) and poly[5,7-dodecadiyn-1, 12-diol-bis(n-butoxy carbonyl methylurethane)] abbreviated as P(4BCMU). These polydiacetylens are soluble in a variety of solvents and form gels in poor solvents such as o-dichlorobenzene (a-DCB) and toluene (TOL) at concentration as low as 0.1 wt¾. 4 • 5 The electronic conduction in P(3BCMU) and P(4BCMU) cast films, 6 • 7 and that in the single crystal of P( 4BCMU) 8 were studied throughly but the conduction behavior and physical properties in the gel state have not been studied fully.Although the structures of the side groups of P(3BCMU) and P(4BCMU) are similar their properties differ greatly. 1 -3 , 9 For example, the color of P(4BCMU) gel is red but that of P(3BCMU) is blue indicating a different electronic state of the conjugated backbone. Gels of P(4BCMU) in p-DCB/TOL mixed solvent exhibit the gel-to-sol transition around 345 Kand those of P(3BCMU) around 387 K. 3 The transition temperatures of these gels are almost independent of polymer concentration and weakly depend on solvent quality and molecular weight. 1 -3

show abstract

Absorption and Fluorescence Spectra of Polydiacetylenes (4BCMU and 3BCMU) in Solution

Cited by 39 publications

References 23 publications

Crystal structure of polydiacethylene TCDU revisited

Crystal structure of polydiacethylene TCDU revisited

Electric Conductivity and Phase Transition of a Polydiacetylene Gel: Poly[4,6-decadiyn-1,10-diol-bis(n-butoxy-carbonylmethyl urethane)] P(3BCMU)

Electric Conductivity, Elasticity, and Optical Spectra in Blend Gels of Polydiacetylenes: P(3BCMU)/P(4BCMU)/Mixed Solvent System

Contact Info

Product

Resources

About