Synthesis and Characterisation of Photo-Cross-Linkable Liquid ...

Hindawi Publishing CorporationJournal of SpectroscopyVolume 2013 Article ID 181485 13 pageshttpdxdoiorg1011552013181485

Research ArticleSynthesis and Characterisation of Photo-Cross-Linkable LiquidCrystalline Poly(n-[n1015840-flurobenzoylstyryloxy]alkylmethacrylate)sand Their Fluorescence Lifetime Properties

G Kumar1 K Subramanian1 and S Ganesan2

1 Department of Chemistry Anna University Chennai 600 025 India2Department of Medical Physics Anna University Chennai 600 025 India

Correspondence should be addressed to K Subramanian kathsubramanianyahoocom

Received 22 June 2012 Accepted 16 January 2013

Academic Editor Khalique Ahmed

Copyright copy 2013 G Kumar et alThis is an open access article distributed under theCreativeCommonsAttribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

This paper reports a study on photo-cross-linkable polymer containing pendant chalcone moiety exhibiting liquid crystallineas well as fluorescence lifetime properties in detail The photoresponsive polymers were prepared and their structure has beencharacterized by 1H-NMR 13C-NMR andUV-Visible spectroscopyThephoto-cross-linking behavior of polymers has been studiedbyUV-Visible and fluorescence spectroscopy UV spectral studies revealed that the polymers follow 2120587+2120587 cyclo addition reactionswhen they undergo photo-cross-linking under the influence of UV-light Number and weight average molecular weight of thepolymers were determined by Gel Permeation Chromatography (GPC) and polydispersity index value near to 15 The thermaland thermooxidative stability of the polymers were determined by Thermogravimetric Analysis (TGA) Thermal transitions werestudied by DSC and presence of mesophases was identified at 147 and 126∘C by hot stage polarized light optical microscopy(HPOM) Fluorescence lifetime measurements using the time-correlated single photon counting (TCSPC) method reveal that theaverage lifetime values decrease from 594 ns to 532 ns on UV-irradiation were discussed in detail

1 Introduction

Liquid crystalline polymers have generated considerableinterest in recent years and the photo-cross-linkable LCPshave driven special attention if they contain both mesogenand photoactive groups in their structure [1ndash5] The formerincorporates LC properties to the polymer and the laterfacilitates cross-linking of the chain under the influence ofUV radiationThese classes of polymers are very useful in fab-ricating anisotropic networks information storage devices [67] and nonlinear optical devices [8] Many research articlesreported photochemical and liquid crystalline behavioursof these polymers using UV-Visible spectral studies andpolarised optical microscopic characterisations In additionto these studies fluorescence lifetime measurement has beenused as a new instrumental technique to support photore-active behaviour of photo-cross-linkable liquid crystallinepolymers

Fluorescence lifetime measurements encompass tremen-dously large fields of science Since the mid-19th centurynearly every great breakthrough in chemistry and physics hasaided the development of fluorescence lifetime techniquesand a growing number of discoveries in biology andmedicineowe their existence to fluorescence lifetime A variety offluorescence detection methods are available for lifetimemeasurements but the advent of time-correlated single pho-ton counting (TCSPC) [9 10] has simplified data collectionand enhanced quantitative photon counting

This paper reports newer root for the synthesis of poly(n-[n1015840-flurobenzoylstyryloxy] alkylmethacrylate)s the photo-cross-linking and liquid crystalline behaviour of polymershave been well characterised by UV and HPOM studies Webelieve that there is no report in recent years on fluorescencelifetime study in combination with UV and liquid crystallinemesophase transition studies about photo-cross-linkable liq-uid crystalline polymer containing pendant chalcone moiety

2 Journal of Spectroscopy

O

F

O

OH

OH

+

F

C

O

H3C10ndash15∘C

EthanolNaOH

Scheme 1 Synthesis of HPFSK

This research work may kindle significant scientific workand practical contribution with respect to the developmentof unique photo-cross-linkable liquid crystalline polymericmaterials

2 Experimental

21 Materials 4-Fluorobenzaldehyde and 4-hydroxyaceto-phe none were purchased from Spectrochem Chemicals4-bromobutanols 6-bromoheaxnol methacryloyl chlor-ide were purchased from Aldrich Chemicals Ethanoltetrahydrofuran ethylacetate chloroform and diethyletherwere purchased from Merck and all the solvents weredistilled as per standard methods Thin Layer Chroma-tography (TLC) technique was carried out on Merckaluminium plates with 02mm silica gel Anhydrous sodiumsulphate was used to dry all organic extracts AIBN wasrecrystallised using 1 1 methanol and chloroform

22 Measurements The FT-IR spectra of the polymers wererecorded on Perkin Elmer FT-IR Spectrometer RXI Thespecimen was prepared in the pellet form using KBr 1H-NMR spectroscopic measurement was recorded with BrukerMSC 300 spectrometer Thermal stability of polymers wasinvestigated by TGA using NETZSCH STA 409CCD Thenumber average and weight average molecular weight ofthe polymer were determined by PL-GPC 650 Glass tran-sition temperature of polymer was measured from Dif-ferential Scanning Calorimeter (DSC) NETZSCHDSC204The photo-cross-linking studies have been done by PerkinElmer Lambda 35 UV-Visible SpectrometerThe fluorescencespectrum of the polymer has been recorded in FluroMax 20The texture of the prepared sample was studied by Euromaxpolarizingmicroscope equippedwith a LinkenHFS91 heatingstage The sample was prepared by a small quantity of thematerial beingmelted between two thin glass cover slips to getuniformfilm and anisotropic behavior observed by heating aswell as cooling with Toshiba digital camera

221 Fluorescence Lifetime Measurements Lifetime mea-surements were made using time-correlated single photoncounting system (TCSPC HORIBA JOBIN YUVON IBHUK) by exciting the sample using 280 nm Nano-LED (pulsewidth lt1 ns) and 460 nm Nano-LED (pulse width gt1 ns)a fast response red sensitive PMT (Hamamatsu PhotonicsJapan) detectorThefluorescence emissionwas collected to 90degree from the path of the light source The electrical signalwas amplified by a TB-02 pulse amplifier (Horiba) fed to the

constant fraction discriminator (CFD Phillips The Nether-lands) The first detected photon was used as a start signalby a time-to-amplitude converter (TAC) and the excitationpulse triggered the stop signal The multichannel analyzer(MCA) recorded repetitive start-stop signals from the TACand generated a histogram of photons as a function of time-calibrated channels (557 pschannel) until the peak signalreached 1000 counts The instrument response function wasobtained using a Rayleigh scatter of Ludox-40 (40wtsuspension in water Sigma-Aldrich) in a quartz cuvette at280 nm excitation and 460 nm excitation Decay analysissoftware (DAS6 v60 Horiba) was used to extract the lifetimecomponents The goodness of fit was judged by the chi-square values Durbin-Watson parameters as well as visualobservations of fitted line residuals and autocorrelationfunctions

23 Synthesis of Pendant Chalcone (Scheme 1) The pendantchalcone compound HPFSK was synthesized according tothe reported literatures [11 12] The obtained products werepurified by recrystallisation in ethanol and then identifiedusing 1H 13C-NMR and FT-IR spectra

24 Hydroxyphenyl-41015840-flurostyryl Ketone (HPFSK) In athree-necked flask equipped with a mechanical stirrer anddropping funnel a solution of NaOH (8 g) in distilledwater (40mL) was added to 4-hydroxyacetophenone(680 g 005mol) in 50mL of ethyl alcohol The reactionwas cooled using an ice bath (10ndash15∘C) A solution of 4-fluorobenzaldehyde in 50mL of ethyl alcohol was then addeddropwise with constant stirring and the temperature was notallowed to exceed 25∘C After 12 h the reaction mixture wasneutralized with 2M HCl to isolate the product The yellowcoloured solid product was filtered and washed several timeswith ice-cold water The crude product was recrystallizedfrom methanol into a yellow crystalline product HPFSK(Scheme 1)

FT-IR (KBr pellet cmminus1) 1497 (aromatic C=C) 1590(olefinicCH=CH) 1650 (ketoC=O) 3550 (Ar-OH)1H-NMR(CDCl

3 120597 in ppm) (Figure 1) 68ndash8 (2d 8H Ar-H) 75 78

(2d 2H olefinic ndashCH=CHndash) and 64 (S 1H ndashOH)

25 4-[41015840-Flurobenzoylstyryloxy]butyl Methacrylate(FBSOBMA) (M1) (Scheme 2) In a two-necked roundbottom flask chalcone (HPFSK) (3 g 00123mol) wasdissolved in 100mL of DMF and stirred well and K

2CO3

(339 g 00246mol) and a pinch of KI were added intothe above solution and allowed stiring for 30 minutes in

Journal of Spectroscopy 3

F

C

+

F

C

O

O

O+

O

F

C

O

O OC

O

F

C

O

O OC

O

Chalcone

DMFKIK2CO3

90∘C 24 hRefluxing

119899

119899

119899

119899

119899

Ethylmethylketone

OH

OH

Cl

OHBr

minus5 to 0∘CTEA

Monomers (M1-M2)

Dry THFAIBN 70∘C48 hrs

Polymers (P1-P2)

119899 = 4 6

119899 = 4 6

Scheme 2 Synthesis of monomers and polymers

an oil bath The prepared 4-bromobutanol (16mL) wasadded dropwise into the above mixture and allowed stirringfor 24 h at 90∘C The product yellow solid formed waspoured into water filtered and dried The crude product4-hydroxybutyloxystyryl-41015840-flurophenyl ketone obtainedwas recrystallised from ethanol-water mixture (50 50) (yield65 25 g)

4-Hydroxybutyloxystyryl-4-flurophenyl ketone (2 g63mmol) and 15mL of triethylamine were dissolved inethylmethylketone (150mL) The above mixture was cooledbetween 0 to minus5∘C and methacryloyl chloride (2mL in20mL of EMK) was added drop wise for an hour withconstant stirring and cooling The reaction mixture wasstirred for another 6 hours at room temperature and theprecipitated ammonium salt was filtered off After drying

over anhydrous sodium sulphate EMKwas evaporated usingrotary evaporator The crude monomer product was purifiedby column chromatography using ethyl acetaten-hexane(2 8 vv) as eluent The monomer FBSOBMA (Figure 2)obtained was pale yellow coloured solid (yield 75)1H-NMR (Figure 2) (CDCl

3 120597 in ppm) 7ndash83 (aromatic

protons m 8H) 75 and 79 (olefinic double bond 2d 2H)13ndash17 and 33ndash43 (spacer ethylenic protons m 8H) 58 and65 (vinylic protons d 2H) 21 (methyl protons t 3H)

26 6-[41015840-Flurobenzoylstyryloxy]hexyl Methacrylate(FBSOHMA) (M2) (Scheme 2) The monomer 6-[41015840-flurobenzoylstyryloxy] hexyl methacrylate (FBSOHMA)(Figure 3) was synthesised followed by analogous procedurediscussed in the above monomer synthesis using 6-bromo


10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

2 099

204

106

198

2 084

084

Figure 1 1H-NMR spectrum of 4-hydroxyphenyl-41015840-flurostyrylketone (HPFSK)

1011 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

Figure 2 1H-NMRspectrumof (4-[41015840-flurobenzoylstyryloxy] butylmethacrylate) (FBSOBMA) (M1)

hexanol instead of 4-bromobutanol The monomer obtainedwas pale yellow coloured solid (yield 67)1H-NMR (Figure 3) (CDCl


protons m 8H) 75 and 79 (olefinic double bond 2d 2H)09ndash19 (spacer ethylenic protons m 12H) 58 and 63 (vinylicprotons d 2H) 2 (Methyl protons t 3H)

27 Synthesis of Polymers (Scheme 2) The polymerspoly(4-[41015840-flurobenzoylstyryloxy] butyl methacrylate) (P1)and poly(6-[41015840-flurobenzoylstyryloxy] hexyl methacrylate)(P2) were synthesised by free radical polymerisation Thefree radical polymerizations of monomer M1 and M2 werecarried out using AIBN as initiator as shown in the schematicrepresentation (Figure 2) The predetermined quantities ofmonomers were taken with AIBN (5 weight of monomer)in polymerization tube and dissolved with 20mL of drytetrahydrofuran (THF) The above solutions were degassedby N2gas atmosphere for 10ndash15 minutes Then the polymer-

ization tubes were kept at 70∘C for 48 hours and subsequentlythen poured into methanol to precipitate the polymer Thepolymers obtained were separated by filtration and purified

10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

Figure 3 1H-NMR spectrum of (6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate) (FBSOHMA) (M2)

by repeated reprecipitation from chloroform into methanoland then dried in vacuumThe yield obtained was 70

3 Photoreactive Measurements

Thephotoreactivity of polymers was studied by dissolving thesamples in chloroform irradiated with UV-light at 254 nmusing photoreactor and kept at a distance of 10 cm from thelight source for different time intervals After each irradiationperiod the UV spectra were recorded using Perkin Elmerscanning spectrometer The rate of disappearance of doublebond in photosensitive group was followed by the expression

Rate of conversion () =(119860119900minus 119860119905)

(119860119900minus 119860infin)

times 100 (1)

where 119860119900 119860119905 and 119860

infinare absorption intensities due to the

gtC=Clt group after the irradiation time 119905 = 0 119905 = 119879 and119905 = infin (maximum irradiation time) respectively

4 Results and Discussions

41 Synthesis andCharacterization Thephoto-cross-linkableliquid crystalline monomers and polymers were preparedas shown in Scheme 2 The photoreactive chalcone HPFSKwas prepared by reacting 4-Fluorobenzaldehyde with 4-hydroxyacetophenone in the presence of NaOH as base TheFT-IR spectrum of HPFSK showed absorption bands at 14971590 and 3550 cmminus1 corresponding to aromatic olefinic andalcoholic group respectively The 1H-NMR spectrum (Fig-ure 1) showed resonance signals at 68ndash8 75 78 and 64 ppmcorresponding to aromatic olefinic and alcoholic protonsrespectively The monomers were synthesised by reacting theintermediate (formed by O-alkylation of chalcone in DMFin the presence of K

2CO3) with methacryloyl chloride in the

presence of triethylamine at 0ndash5∘C (Scheme 2)The 1H-NMR(Figure 2) spectrum of M1 showed characteristic peaks at 58and 65 ppm due to vinyl and methyl protons The aliphaticethoxy protons showed signals between 13 and 43 ppmThe


F H O

O H

O

CO

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

10

10

9

9

8

8

7

7

6

6

5

5

4

4

119899

3

3

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

Figure 4 13C-NMR spectrum of poly(4-[41015840-flurobenzoylstyrylox-y]butyl methacrylate) (FBSOBMA) (P1)

pendent olefinic double bond was shown by signals at 75 and79 ppmThe appearance of multiplet signals between 70 and83 ppm is due to aromatic protons The above same trendswere exhibited by M2 (Figure 3) with slight deviations Thephotoresponsive liquid crystalline polymers P1 and P2 weresynthesized by predetermined amount of monomers in THFat 70∘C the polymerization was carried out for 48 hours(Scheme 2) The above mixture was precipitated in methanoland filtered off The precipitated polymer was separatedby filtration and purified by repeated reprecipitation fromchloroform into methanol The polymers synthesized wereidentified using 13C-NMR spectra The 13C-NMR of P1 isshown in Figure 4 The methyl vinyl and tertiary carbonsresonate between 235 and 70 ppm The ester and olefiniccarbons were identified by the signals at 1746 122 and1445 ppm respectively The signals between 118 and 167 ppmwere due to aromatic double-bonded carbons 13C-NMRspectra polymer P2 is shown in Figure 5 The methyl vinyland tertiary carbons resonate 255ndash69 ppm The ester andolefinic carbons were identified by the signals at 1755 1215and 1435 ppm respectively The signals 116ndash170 ppm weredue to aromatic double-bonded carbons The solubility ofboth the polymers P1 and P2 was tested in various organicsolvents They were soluble in polar aprotic solvents such asDMF DMSO Dioxane and THF and in chlorinated solventssuch as chloroform dichloromethane It was insoluble inmethanol 2-propanol and hydrocarbon solvents such astoluene benzene and n-hexane

42 Molecular Weight The number average and weight aver-agemolecular weight of polymers P1 and P2 were determinedby PL-GPC650 The number average molecular weight (119872

119899)

and weight average molecular weight (119872119908) of the polymer P1

were 87 times 104 and 1305 times 104 The molar mass distributionof polymer is given by polydispersity index (PDI) value 150For the polymer P2 the 119872

119899and 119872

119908were 892 times 104 and

C

CF O O O

O

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

21

21

20

20

10

10

9

9

8

8

7

7

6

6

5

5

4

3

3

4

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

119899

Figure 5 13C-NMR spectrum of poly(6-[41015840-flurobenzoylstyrylox-y]hexyl methacrylate) (FBSOHMA) (P2)

100 200 300 400 500 600 700 8000

20

40

60

80

100W

eigh

t los

s (

)

Temperature (∘C)

Poly(FBSOBMA) (P7)Poly(FBSOBMA) (P8)

Figure 6 Thermogravimetric Analysis of poly(4-[41015840-flurobenzoylstyryloxy] butyl methacrylate) (P1) and poly(6-[41015840-flurobenzoylstyryloxy] hexyl methacrylate) (P2)

1346 times 104 respectively and polydispersity index (PDI) valuewas 151 The theoretical values of PDI for polymer producedvia radical combination and disproportionation are 15 and20 respectively The PDI values of polymers P1 and P2 were150 and 151 respectively Both polymers P1 and P2 show thetendency of chain termination by radical combination ratherthan disproportionation

43 Thermal Properties The Thermogravimetric Analysis(TGA) of prepared polymers was measured under nitrogenatmosphere in the temperature ranges 30ndash700∘C in order toinvestigate the thermal stability The TGA data are illustratedin Table 1 The data in Table 1 and Figure 6 indicate that thehomopolymers decompose at higher temperature and they


Table 1 Thermogravimetric Analysis (TGA) and liquid crystalline properties data of polymers (P1 and P2)

S no Polymer Temperature (∘C) at weight loss ()119879119892(∘C) 119879

119898(∘C) 119879

119894(∘C) Δ119879 = 119879

119894minus 119879119872(∘C) Mesophase

IDT (∘C) 50P1 Poly(FBSOBMA) 160 287 Nil 105 147 42 NematicP2 Poly(FBSOHMA) 194 310 Nil 97 126 29 Nematic

show single-stage decomposition with good thermal stabilityThe initial decomposition temperature (IDT) of the polymersP1 and P2 were slightly different from each other due tosmaller difference in molecular mass Both P1 and P2 show50 weight loss at temperatures 287 and 310∘C respectivelyproving the flame retardancy and stability of polymersThesethermal studies have shown that the polymers possess verygood thermal and thermooxidative stability required for thenegative photoresist polymers

44 Photo-Cross-Linking Studies The photo-cross-linkingstudies were carried out to study the changes which occurredin the polymer during UV irradiation to confirm photoresistnature of polymer The polymer solution was prepared in theconcentration range of 10ndash20mgL using chloroform It wasirradiated with UV-light of 254 nm the photo-cross-linkingability of the polymer was followed by the rate of disap-pearance of the C=C bond of photosensitive group in theUV spectrum When the polymers irradiated with UV lightof 254 nm they undergo 2120587 + 2120587 cycloaddition and formphotodimers as shown in Scheme 3The absorption intensitydecreases rapidly with increasing irradiation time and banddisappears almost completely within three minutes of irradi-ationThe decrease in the UV absorption intensity due to thecross-linking of polymer through 2120587+2120587 cyclodimerisationof CH=CHndash group of 4-flurobenzoylstyryloxy group leads toformation of cyclobutane ring The rate of disappearance ofdouble bond in photosensitive group was calculated by theexpression [13]


(119860119900)

times 100 (2)

where119860119900and119860

119905are absorption intensities due to thegtC=Clt

group after the irradiation time 119905 = 0 and 119905 = 119879 respectivelyThe UV spectral changes during photo-cross-linking and

photoconversions of polymers are shown in Figures 7 and 8In the polymers P1 and P2 the pendant chalcone unit andpolymeric backbone are linked by flexible methylene spacerunits The photo-cross linking rate of P2 was slightly fasterthan P1 This rapid cross-linking may be attributed to thespacer unit between the photosensitive group and polymerbackbone which provide more flexibility and free movementfor the side chain which accelerate the increased rate of crosslinking [14]

The photolysis studies of various ethylene spacer contain-ing polymers imparted that the rate of photo-cross-linkingdepends on the length of the methylene chain so the polymerP7 and P8 follow this trend

Hexamethylene gt Butamethylene (3)

260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)

Figure 7 UV spectral changes during photo-cross-linking ofpoly(4-[41015840-flurobenzoylstyryloxy]butyl methacrylate) (P7) at vari-ous time intervals in chloroform solution

240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds

Figure 8 UV spectral changes during photo-cross-linking ofpoly(6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate) (P8) at vari-ous time intervals in chloroform solution

Figure 9 denotes that the rate of disappearance of the C=Cof photoreactive groups is slightly fast in P2 than P1 andshows 100 photoconversion since they have smaller sub-stituents in their pendant unit and there is no intramolecularcrosslinking can be formed by the dimerization of adjacentchalcone groups

45 Fluorescence Spectral Studies The existence of pho-toresponsive behaviour of polymers can be evidenced byfluorescence spectra The fluorescence intensity of polymer


CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899

UV 254 nmPhotodimerisation

119899 = 4 6

Scheme 3 Photodimerisation of polymers (P1 and P2)

0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()

Irradiation time (s)

P1P2

Figure 9 Photoconversions on UV-irradiation for polymers P1 andP2

decreases as the time of irradiation increases The decreasein intensity is due to 2120587 + 2120587 cycloaddition which leads tocyclobutane ring formation by destroying 120587 electron conju-gation From the figures it is noticed that P1 shows gradualdecrease in the intensity whereas P2 shows sudden decrease

Fluorescence spectral changes during photo-cross-linking of polymers P1 and P2 are shown in Figures 10 and 11Both polymers P1 and P2 were excited at the wavelength of348 nm and they were irradiated with UV-light of 254 nm atvarious time intervals The decrease in fluorescence intensity

350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds

Figure 10 Fluorescence spectral changes during photo-cross-linking of poly(4-[41015840-flurobenzoylstyryloxy] butyl methacrylate)(P1) at various time intervals in chloroform solution

was observed till the completion of photo-cross-linking ofpolymers which is noticed from their decrease in intensityor disappearance of emission peaks The emission of bothpolymers P7 and P8 occurred at 430 nm since they containsimilar functional groups and spacer units

46 Morphological Study of Photo-Cross-Linking PolymersThe SEM technique can give high resolution images whichenables the visualization of morphological information with-out losing any accuracy during analysis The synthesized


350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Figure 11 Fluorescence spectral changes during photo-cross-linking of poly(6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate)(P2) at various time intervals in chloroform solution

photo-cross-linkable liquid crystalline polymers were irra-diated with UV-light of 254 nm for 30 minutes The virginpolymers (P1 and P2) and photo-cross-linked polymers (P1and P8) were characterised by HITACHI Scanning ElectronMicroscope (SEM) S-3400N model to understand the mor-phology of both virgin and photo-cross-linked polymersTheSEM images of both virgin and photo-cross-linked polymersshown in Figures 12(a) and 13(b) As observed from theSEM images of Figures 12(b) and 13(b) the photo-cross-linked polymer sample confirms loosely held dispersion ofpolymeric materials while virgin polymer exhibits compactstringent dispersion of polymeric surface as described byMathur and Kumar [15]

It is inferred from the SEM images that all the virginpolymers P1ndashP8 have irregular-shaped flakes in their latticewhich packed on one over the other in nondirectionalmanner and they all have hard and crystal-like surface ButSEM images of photo-cross-linked polymers from P1 to P8show uniform size of polymer flakes which were arrangedregularly

It can be clearly observed from the SEM images thattheir surfaces after photo-cross-linking were smoothed welland all the irregular crystal with rough surface has beenchanged into brightened smooth surface The smoothnessin the polymer surface may be due to photodimerisation ofpolymers When two polymer molecules undergo cyclobu-tane ring formation during photo-cross-linking one polymermolecule bounds to the other through cyclobutane ringThisstructural interaction may lead to smoothness and regular orordered arrangement of polymer lattice after UV-treatment

47 Liquid Crystalline Properties of Polymers The develop-ment of photosensitive media based on liquid crystallinecompounds for data recording optical storage and repro-duction is one of the most rapidly developing areas in thephysical chemistry of lowmolecularmass and polymer liquidcrystals [16] The rigidity of the mesogenic core the flexiblespacer length and terminal units highly influence themolting

(a)

(b)

Figure 12 Scanning Electron Microscope image of (a) virginpolymer poly(FBSOBMA) (P1) and (b) photo-cross-linked polymerpoly(FBSOBMA) (P1)

temperature mesophase temperature and even moleculararrangement

In some polymers they are taking the effect of mesogenand spacer together a polymer having rigid mesogen andshorter spacer should show the higher transition temperature[17] The phase transition temperature and mesophase ofthe polymers are studied by traces of DSC thermogram andHPOM images Generally in the DSC thermogram at thehighest transition temperature there will be an endothermcorresponding to the transition from LC phase to isotropicphase The transition in some cases from crystal to liquidcrystal is marked by more than one endotherm When suchmultiple curves were observed the one having the highesttemperature is attributed to crystal-to-mesophase transition

The DSC thermograms of Polymers P1 and P2 are shownin the Figure 14 which shows two endotherms observed inthe heating scan and in the annealed samples In generalfor the first lowest transition temperature which occur justafter the glass transition temperature is melting endothermand the second highest transition temperature attributedto nematic phase to isotropic mesophase transition Thepolymers P1 and P2 show crystal-to-nematic phase transitionat temperatures at 105∘C and 97∘C respectivelyThe polymers


(a) (b)

Figure 13 Scanning Electron Microscope image of (a) virgin polymer poly (FBSOHMA) (P2) and (b) photo-cross-linked polymer poly(FBSOHMA) (P2)

50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2

∘C)Figure 14 Differential scanning calorimetric thermogram of poly-mers poly(FBSOBMA) (P1) and poly(FBSOHMA) (P2)

P1 and P2 show nematic-to-isotropic phase transition at thetemperature 147∘C and 126∘C respectively shown in Figures15 and 16 The liquid crystalline properties of polymer areshown in Table 1The liquid crystalline phases were observedin between the 119879

119898and 119879

119894 The mesophase duration (Δ119879 =

119879119894minus119879119898) was observed in between 42 and 29∘C this indicates

that they possess relatively good mesophase stability

48 Fluorescence Lifetime Studies The time-resolved fluores-cence decays of polymers P1 and P2 have been monitoredin chloroform The polymers P1 and P2 were excited at460 nm The fluorescence lifetimes of both polymers afterand before the UV-irradiation at wavelength of 254 nmhave been measured and plotted in Figures 17(a) and 18(c)The 1205942 values which are known as the fitting parametersdetermining the fine fit for triexponential decay are foundto be lt13 and average lifetime ⟨120591⟩ is calculated using thefollowing equation [18]

120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)

Figure 15 Polarised optical micrograph of poly(FBSOBMA) (P1)showing nematic mesophase at 147∘C

Figure 16 Polarised optical micrograph of poly(FBSOHMA) (P2)showing nematic mesophase at 126∘C

where 1205911 1205912 and 120591

3are the lifetime values of three emissive

states and 1205721 1205722 and 120572

3are called preexponential factors

which give abundance of emissive states The fluorescencelifetime values of photoresponsive polymers P1 and P2 were


100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)

Figure 17 (a) Lifetime decay of poly(4-[41015840-flurobenzoylstyryloxy]butyl methacrylate) (P1) before UV-irradiation (b) Lifetimedecay of poly(4-[41015840-flurobenzoylstyryloxy]butyl methacrylate) (P1) after 150 sec UV irradiation (c) Lifetime decay of poly(4-[41015840-flurobenzoylstyryloxy] butyl methacrylate) (P1) after infinite sec UV irradiation

given in Table 2 The polymer solutions were prepared inthe concentration range 10ndash20mgL using chloroform Thelifetime measurements of two polymers were determined atnonirradiative and UV-irradiative condition at different timeintervals Since the number of molecules with electron donororwithdrawing groups affects fluorescence only partially [19]the polymers show very little lifetime variations before andafter UV-irradiations In both polymers P1 and P2 lifetime

values are decreasing after UV-irradiation at different timeintervals 0 150 andinfin seconds

In general rotation of the part of the molecule par-ticipating in fluorescence is the most trivial process ofthe nonirradiative energy loss and typically occurs in theexcited state Considering the molecules of the bond orderin ground state equal to 2 upon excitation the electron fromthe bonding orbital is promoted to the excited state orbital


=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)

Figure 18 (a) Lifetime decay of poly(6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate) (P2) before UV-irradiation (b) Lifetimedecay of poly(6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate) (P2) after 150 sec UV irradiation (c) Lifetime decay of poly(6-[41015840-flurobenzoylstyryloxy] hexyl methacrylate) (P2) after infinite sec UV irradiation

Table 2 Fluorescence lifetime decay of polymers P1 and P2

Polymers 120582119860(nm) 120582

119864(nm) UV-irradiation time (sec) 120591

1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109


producing bond order 1 Such change in the bond ordertransforms the rigid frame work formed by the double bondto a flexible system of single bond leading to twisting ofmolecule around a C-C bond causing subsequent cistransisomerisation [20] Since rotation around the double bondscontributes to a decrease in lifetime it is logical to suggest thatany restriction of rotation such as rigid environment of themolecules would marginalize the role of nonradiative pathway and lead to subsequent increase of fluorescence lifetime

Molecules capable of undergoing an electron transfer pro-cess possess strong electron donating and occasionally elec-tron withdrawing group [21] Among withdrawing groupsonly nitro group has been used successfully as quenchersother withdrawing groups may affect a little fluorescencelifetime For example tetranitrofluorescence has lifetime of24 ns compared with 40 ns for fluorescence

The polymers poly(4-[41015840-flurobenzoylstyryloxy] butylmethacrylate) (P1) and poly(6-[41015840-flurobenzoylstyryloxy]hexyl methacrylate) (P2) fluorescence lifetime values beforeirradiation were 594 and 605 The molecules capableof undergoing an electron transfer possess strong elec-tron donating and occasionally electron withdrawing groupThe exceptions are however numerous and a number ofmolecules with electron donor or electron withdrawinggroup affect fluorescence lifetime partially So the electroneg-ative nature of flurogroup substitution at the 4th position ofboth polymers P1 and P2might not be affected by the fluores-cence lifetime values Nevertheless the two polymers showedrestriction to free rotation after photodimerisation andslight polarisation of ester linkage predominates into furtherdecrease of fluorescence lifetime up to infinite photodimeri-sation In the polymers P1 and P2 they show 1205942 values nearto 11 or 1 which indicate all the fits are monoexponential andshow the goodness of fitting parameters

5 Conclusions

Thephotos-cross-linkable liquid crystalline polymers P1 andP2 were synthesized by free radical polymerization in THFusing AIBN as initiator The synthesized polymers have beencharacterized by H1-NMR C13-NMR and UV-Vis spectralstudies The TGA analysis clearly indicates that the polymersshow 50 weight loss near to 400∘C which exhibit goodcharacteristics of thermal and thermo-oxidative stabilityThepolydispersity index (PDI) values 150 and 151 obtained fromGPC indicate that polymerization was terminated by freeradical combination The photo-cross-linking and fluores-cence lifetime study of polymers show their indispensableimportance in photoresist applicationsThe liquid crystallineproperty of the polymers was identified from DSC andconfirmed by HOPM images at 147∘C and 126∘C From theaverage lifetime values 532 ns and 477 ns at infinite UV-irradiation on both P1 and P2 reveal that the photo physicalbehavior of polymers using the time-correlated single photoncounting (TCSPC) method Thus the synthesized polymersexhibit both photoresponsive as well as liquid crystallineproperty and they might be useful in optical data recordingand nonlinear optical (NLO) applications

Acknowledgments

The authors are thankful to Professor (Dr) S GanesanDirector of Students Affair Anna University Chennai Indiafor providing fluorescence lifetime facility to carry out thisresearch and sincerely thankful to Dr T NarasimhaswamyScientist CLRI Adyar Chennai for carrying out POMstudies

References

[1] D Creed A C Griffin J R D Gross C E Hoyle and KVenkataram ldquoMolecular crystals and liquid crystals incorpo-rating nonlinear opticsrdquoMolecular Crystals and Liquid Crystalsvol 155 no 1 pp 57ndash71 1988

[2] T Ikeda H Itakura C Lee F M Winnik and S TazukeldquoTopochemical photodimerization in polymer liquid crystalsrdquoMacromolecules vol 21 no 12 pp 3536ndash3537 1988

[3] P Keller ldquoPhoto-crosslinkable liquid-crystalline side-chainpolysiloxanesrdquo Chemistry of Materials vol 2 no 1 pp 3ndash41990

[4] M JWhitecombe AGilbert AHiraj andG RMitchell ldquoCin-namate ester containing liquid crystalline side chain polymersrdquoJournal of Polymer Science Part A vol 29 no 2 pp 251ndash2591991

[5] M J Whitecombe A Gilbert and G R Mitchell ldquoThe photo-Fries rearrangement in a side-chain liquid-crystalline polymerrdquoPolymer vol 34 no 7 pp 1347ndash1353 1993

[6] A C Griffin C E Hoyle J R D Gross K VenkataramD Creed and C B McArdle ldquoLaser-induced photo-opticalrecording on free-standing films of a main-chain nematicpolyesterrdquo Die Makromolekulare Chemie vol 9 no 7 pp 463ndash477 1988

[7] C H Legge M J Whitcombe A Gilbert and G R MitchellldquoPhotoinduced phase transitions in novel liquid-crystallinecopolymersrdquo Journal of Materials Chemistry vol 1 no 2 pp303ndash304 1991

[8] S Marturukakul I J Chen L Li R J Jeng J Kumar andS K Tripathy ldquoAn interpenetrating polymer network as astable second-order nonlinear optical materialrdquo Chemistry ofMaterials vol 5 no 5 pp 592ndash594 1993

[9] W Becker Advanced Time-Correlated Single Photon CountingTechniques Springer Berlin Germany 2005

[10] W Becker The TCSPC Handbook Becker amp Hickl GmbhBerlin Germany 3rd edition 2008

[11] A V Rami Reddy K Subramanian V Krishnasamy and JRavichandran ldquoSynthesis characterization and properties ofnovel polymers containing pendant photocrosslinkable chal-cone moietyrdquo European Polymer Journal vol 32 no 8 pp 919ndash926 1996

[12] A V Rami Reddy K Subramanian and J SeshasainathldquoPhotosensitive polymers synthesis characterization and pho-tocrosslinking properties of polymers with pendant 120572120573-unsaturated ketone moietyrdquo Journal of Applied Polymer Sciencevol 70 no 11 pp 2111ndash2120 1998

[13] K Subramanian V Krishnasamy S Nanjundan andA V RamiReddy ldquoPhotosensitive polymer synthesis characterizationand properties of a polymer having pendant photocrosslinkablegrouprdquo European Polymer Journal vol 36 no 11 pp 2343ndash23502000


[14] R Mohan Kumar C Saravanan S Senthil and P KannanldquoSynthesis characterization and photolysis studies on liq-uid crystalline poly[4-(41015840-x-biphenyl)yl-4

10158401015840

-(m-methacryloyl-oxyalkyloxy) cinnamate]rsquosrdquo European Polymer Journal vol 43no 6 pp 2648ndash2659 2007

[15] S C Mathur and B Kumar ldquoCharge transport calculations inanthraquinonerdquoMolecular Crystals and Liquid Crystals vol 23no 1-2 pp 85ndash98 1973

[16] A Bobrovsky andV Shibaev ldquoA study of photooptical processesin photosensitive cholesteric azobenzene-containing polymermixture under an action of the polarized and nonpolarizedlightrdquo Polymer vol 47 no 12 pp 4310ndash4317 2006

[17] Gangadhara and K Kishore ldquoA new class of photo-cross-linkable side chain liquid crystalline polymers containingbis(benzylidene)cyclohexanone unitsrdquoMacromolecules vol 28no 4 pp 806ndash815 1995

[18] J R Lakowicz Principles of Fluorescence Spectroscopy KluwerAcademicPlenum Publishers New York NY USA 2nd edi-tion 1999

[19] N O McHedlov-Petrossyan N A Vodolazkaya Y N Surovand D V Samoylov ldquo2457-tetranitrofluorescein in solutionsnovel type of tautomerism in hydroxyxanthene series asdetected by various spectral methodsrdquo Spectrochimica Acta PartA vol 61 no 11-12 pp 2747ndash2760 2005

[20] A J Merer and R S Mulliken ldquoUltraviolet spectra and excitedstates of ethylene and its alkyl derivativesrdquo Chemical Reviewsvol 69 no 5 pp 639ndash656 1969

[21] V Knyukshto E Zenkevich E Sagun A Shulga and SBachilo ldquoPathways for photoinduced electron transfer inmeso-nitro-phenyl-octaethylporphyrins and their chemical dimersrdquoChemical Physics Letters vol 304 no 3-4 pp 155ndash166 1999

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


O

F

O

OH

OH

+

F

C

O

H3C10ndash15∘C

EthanolNaOH

Scheme 1 Synthesis of HPFSK

This research work may kindle significant scientific workand practical contribution with respect to the developmentof unique photo-cross-linkable liquid crystalline polymericmaterials

2 Experimental

21 Materials 4-Fluorobenzaldehyde and 4-hydroxyaceto-phe none were purchased from Spectrochem Chemicals4-bromobutanols 6-bromoheaxnol methacryloyl chlor-ide were purchased from Aldrich Chemicals Ethanoltetrahydrofuran ethylacetate chloroform and diethyletherwere purchased from Merck and all the solvents weredistilled as per standard methods Thin Layer Chroma-tography (TLC) technique was carried out on Merckaluminium plates with 02mm silica gel Anhydrous sodiumsulphate was used to dry all organic extracts AIBN wasrecrystallised using 1 1 methanol and chloroform

22 Measurements The FT-IR spectra of the polymers wererecorded on Perkin Elmer FT-IR Spectrometer RXI Thespecimen was prepared in the pellet form using KBr 1H-NMR spectroscopic measurement was recorded with BrukerMSC 300 spectrometer Thermal stability of polymers wasinvestigated by TGA using NETZSCH STA 409CCD Thenumber average and weight average molecular weight ofthe polymer were determined by PL-GPC 650 Glass tran-sition temperature of polymer was measured from Dif-ferential Scanning Calorimeter (DSC) NETZSCHDSC204The photo-cross-linking studies have been done by PerkinElmer Lambda 35 UV-Visible SpectrometerThe fluorescencespectrum of the polymer has been recorded in FluroMax 20The texture of the prepared sample was studied by Euromaxpolarizingmicroscope equippedwith a LinkenHFS91 heatingstage The sample was prepared by a small quantity of thematerial beingmelted between two thin glass cover slips to getuniformfilm and anisotropic behavior observed by heating aswell as cooling with Toshiba digital camera

221 Fluorescence Lifetime Measurements Lifetime mea-surements were made using time-correlated single photoncounting system (TCSPC HORIBA JOBIN YUVON IBHUK) by exciting the sample using 280 nm Nano-LED (pulsewidth lt1 ns) and 460 nm Nano-LED (pulse width gt1 ns)a fast response red sensitive PMT (Hamamatsu PhotonicsJapan) detectorThefluorescence emissionwas collected to 90degree from the path of the light source The electrical signalwas amplified by a TB-02 pulse amplifier (Horiba) fed to the

constant fraction discriminator (CFD Phillips The Nether-lands) The first detected photon was used as a start signalby a time-to-amplitude converter (TAC) and the excitationpulse triggered the stop signal The multichannel analyzer(MCA) recorded repetitive start-stop signals from the TACand generated a histogram of photons as a function of time-calibrated channels (557 pschannel) until the peak signalreached 1000 counts The instrument response function wasobtained using a Rayleigh scatter of Ludox-40 (40wtsuspension in water Sigma-Aldrich) in a quartz cuvette at280 nm excitation and 460 nm excitation Decay analysissoftware (DAS6 v60 Horiba) was used to extract the lifetimecomponents The goodness of fit was judged by the chi-square values Durbin-Watson parameters as well as visualobservations of fitted line residuals and autocorrelationfunctions

23 Synthesis of Pendant Chalcone (Scheme 1) The pendantchalcone compound HPFSK was synthesized according tothe reported literatures [11 12] The obtained products werepurified by recrystallisation in ethanol and then identifiedusing 1H 13C-NMR and FT-IR spectra

24 Hydroxyphenyl-41015840-flurostyryl Ketone (HPFSK) In athree-necked flask equipped with a mechanical stirrer anddropping funnel a solution of NaOH (8 g) in distilledwater (40mL) was added to 4-hydroxyacetophenone(680 g 005mol) in 50mL of ethyl alcohol The reactionwas cooled using an ice bath (10ndash15∘C) A solution of 4-fluorobenzaldehyde in 50mL of ethyl alcohol was then addeddropwise with constant stirring and the temperature was notallowed to exceed 25∘C After 12 h the reaction mixture wasneutralized with 2M HCl to isolate the product The yellowcoloured solid product was filtered and washed several timeswith ice-cold water The crude product was recrystallizedfrom methanol into a yellow crystalline product HPFSK(Scheme 1)

FT-IR (KBr pellet cmminus1) 1497 (aromatic C=C) 1590(olefinicCH=CH) 1650 (ketoC=O) 3550 (Ar-OH)1H-NMR(CDCl

3 120597 in ppm) (Figure 1) 68ndash8 (2d 8H Ar-H) 75 78

(2d 2H olefinic ndashCH=CHndash) and 64 (S 1H ndashOH)

25 4-[41015840-Flurobenzoylstyryloxy]butyl Methacrylate(FBSOBMA) (M1) (Scheme 2) In a two-necked roundbottom flask chalcone (HPFSK) (3 g 00123mol) wasdissolved in 100mL of DMF and stirred well and K

2CO3

(339 g 00246mol) and a pinch of KI were added intothe above solution and allowed stiring for 30 minutes in


F

C

+

F

C

O

O

O+

O

F

C

O

O OC

O

F

C

O

O OC

O

Chalcone

DMFKIK2CO3


119899

119899

119899

119899

119899

Ethylmethylketone

OH

OH

Cl

OHBr

minus5 to 0∘CTEA

Monomers (M1-M2)


Polymers (P1-P2)

119899 = 4 6

119899 = 4 6









10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

2 099

204

106

198

2 084

084


1011 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity







10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity






(119860119900minus 119860infin)

times 100 (1)

where 119860119900 119860119905 and 119860








F H O

O H

O

CO

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

10

10

9

9

8

8

7

7

6

6

5

5

4

4

119899

3

3

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity




119899)



119899and 119872


C

CF O O O

O

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

21

21

20

20

10

10

9

9

8

8

7

7

6

6

5

5

4

3

3

4

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

119899


100 200 300 400 500 600 700 8000

20

40

60

80

100W

eigh

t los

s (

)

Temperature (∘C)








119898(∘C) 119879

119894(∘C) Δ119879 = 119879






(119860119900)

times 100 (2)

where119860119900and119860






260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)


240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds





CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


F

C

+

F

C

O

O

O+

O

F

C

O

O OC

O

F

C

O

O OC

O

Chalcone

DMFKIK2CO3


119899

119899

119899

119899

119899

Ethylmethylketone

OH

OH

Cl

OHBr

minus5 to 0∘CTEA

Monomers (M1-M2)


Polymers (P1-P2)

119899 = 4 6

119899 = 4 6









10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

2 099

204

106

198

2 084

084


1011 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity







10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity






(119860119900minus 119860infin)

times 100 (1)

where 119860119900 119860119905 and 119860








F H O

O H

O

CO

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

10

10

9

9

8

8

7

7

6

6

5

5

4

4

119899

3

3

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity




119899)



119899and 119872


C

CF O O O

O

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

21

21

20

20

10

10

9

9

8

8

7

7

6

6

5

5

4

3

3

4

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

119899


100 200 300 400 500 600 700 8000

20

40

60

80

100W

eigh

t los

s (

)

Temperature (∘C)








119898(∘C) 119879

119894(∘C) Δ119879 = 119879






(119860119900)

times 100 (2)

where119860119900and119860






260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)


240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds





CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity

2 099

204

106

198

2 084

084


1011 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity







10 9 8 7 6 5 4 3 2 1 0(ppm)

Rela

tive i

nten

sity






(119860119900minus 119860infin)

times 100 (1)

where 119860119900 119860119905 and 119860








F H O

O H

O

CO

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

10

10

9

9

8

8

7

7

6

6

5

5

4

4

119899

3

3

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity




119899)



119899and 119872


C

CF O O O

O

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

21

21

20

20

10

10

9

9

8

8

7

7

6

6

5

5

4

3

3

4

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

119899


100 200 300 400 500 600 700 8000

20

40

60

80

100W

eigh

t los

s (

)

Temperature (∘C)








119898(∘C) 119879

119894(∘C) Δ119879 = 119879






(119860119900)

times 100 (2)

where119860119900and119860






260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)


240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds





CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


F H O

O H

O

CO

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

10

10

9

9

8

8

7

7

6

6

5

5

4

4

119899

3

3

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity




119899)



119899and 119872


C

CF O O O

O

19

19

18

18

17

17

16

16

15

15

14

14

13

13

12

12

11

11

21

21

20

20

10

10

9

9

8

8

7

7

6

6

5

5

4

3

3

4

2

2

1

1

200 180 160 140 120 100 80 60 40 20 0(ppm)

Rela

tive i

nten

sity

119899


100 200 300 400 500 600 700 8000

20

40

60

80

100W

eigh

t los

s (

)

Temperature (∘C)








119898(∘C) 119879

119894(∘C) Δ119879 = 119879






(119860119900)

times 100 (2)

where119860119900and119860






260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)


240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds





CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




119898(∘C) 119879

119894(∘C) Δ119879 = 119879






(119860119900)

times 100 (2)

where119860119900and119860






260 280 300 320 340 3600

02

04

06

08

1

12

14

16

Seco

nds

0510153045607590120150200250300350450550650750

Wavelength (nm)Ab

sorb

ance

inte

nsity

(au

)


240 260 280 300 320 340 360 380 4000

05

1

15

2 0510153045607590120150200250300350450550650

Wavelength (nm)

Abso

rban

ce in

tens

ity (a

u)

Seco

nds





CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


CO

F

OO

OO

OO

OO

O

O

FF

OO

OO

119899

119899

119899

119899

119899

119899


119899 = 4 6


0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Phot

ocon

vers

ion

()


P1P2




350 375 400 425 450 475 500 5250

10000

20000

30000

40000

50000

6000005101530456090120150200250350450550650750900

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)

Seco

nds





350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


350 400 450 500 5500

100

200

300

400

500

6000510153045607590120150200250350450550650750

Seco

nds

Wavelength (nm)

Fluo

resc

ence

inte

nsity

(cou

nts

s)






(a)

(b)






(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b)


50 100 150 200minus05

minus04

minus03

minus02

minus01

0

Hea

t flow

(Wg

)

Temperature (

Polymer P1

Polymer P2



119898and 119879





120591av =12057211205911

2+ 12057221205912

2+ 12057231205913

2

12057211205911+ 12057221205912+ 12057231205913

(4)



where 1205911 1205912 and 120591


states and 1205721 1205722 and 120572




100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


100

1000

10000

600 800 1000 1200 1400

0123

Channels

Cou

nts (

log)

minus3minus2minus1

PromptDecayFit

Resid

uals CHISQ = 115

(a)

=CHISQ 112

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2minus1

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

100

1000

10000

600 800 1000 1200 1400

0123

Channels

minus3minus2minus1

CHISQ = 113

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)






=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


=CHISQ 118

100

1000

10000

600 800 1000 1200 1400

012

Channels

minus2

minus1

Cou

nts (

log)

Resid

uals

PromptDecayFit

(a)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus3

minus2minus1

Channels

=CHISQ 11

PromptDecayFit

Cou

nts (

log)

Resid

uals

(b)

600 700 800 900 1000 1100 1200 1300 1400

100

1000

10000

0123

minus2minus1

Channels

=CHISQ 109

minus3

Cou

nts (

log)

Resid

uals

PromptDecayFit

(c)



Polymers 120582119860(nm) 120582


1(ns) 120572

11205912(ns) 120572

21205913(ns) 120572

3lt120591gt 120594

2

0 307 04601 04287 03657 905 01742 594 115P1 313 430 150 272 04417 04761 02899 763 02683 560 112

infin 240 04349 04469 02790 712 02862 532 1060 319 04946 08282 03312 960 01742 605 118

P2 313 430 150 265 05065 06778 02663 723 02271 491 110infin 261 04848 06154 02926 701 02226 477 109





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





5 Conclusions


Acknowledgments


References
















10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



10158401015840


















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Synthesis and Characterisation of Photo-Cross-Linkable Liquid ...

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