New Polymer Syntheses Part 57: Thermally Stable New...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 198652 9 pageshttpdxdoiorg1011552013198652

Research ArticleNew Polymer Syntheses Part 57Thermally Stable New Ferrocene-PolyazomethinesSynthetic Methodology and Characterization

Mona Ahmed Abdel-Rahman1 Mahmoud Ali Hussein1 2

Kamal Ibrahim Aly1 and Abdelwareth Abdel-Haleam Sarhan1

1 Polymer Laboratory 122 Chemistry Department Faculty of Science Assiut University Assiut 71516 Egypt2 Chemistry Department Faculty of Science King Abdulaziz University PO Box 80203 Jeddah 21589 Saudi Arabia

Correspondence should be addressed to Mona Ahmed Abdel-Rahman manoush00yahoocom

Received 1 July 2012 Accepted 10 October 2012

Academic Editor Franck Le Derf

Copyright copy 2013 Mona Ahmed Abdel-Rahman et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited

A new interesting category of higher thermally stable polyazomethines containing ferrocene in the polymers main chain 6andashe wassynthesized by solution-polycondensation reaction of 1-(m-formylphenyl)-110158401015840-(5-formyl-2-methoxyphenyl)-ferrocene monomer 4with different aliphatic and aromatic diamines A model compound 5 was synthesized from dialdehyde monomer 4 with anilineand was characterized by elemental and spectral analyses The desirable resulting polymers were characterized by elemental andspectral analyses in addition to solubility measurement using different solvents The thermal properties of these polymers wereevaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)measurementsThe redox behaviourswere studied for the ferrocene polymers in comparison with both the parent ferrocene monomer and the model compound byusing cyclic voltammetry (CV)

1 Introduction

Metal-containing polymers have emerged as an importantcategory of polymeric materials The impetus for the devel-opment of these materials is based on the premise thatpolymers-containing metals are expected to possess proper-ties significantly different from those of conventional organicpolymers Ferrocene remains after about 55 years since itsdiscovery a molecule of intrigue and continued interest Thesustained interest in ferrocene is in part due to the rich chem-istry of iron (II) center and the variety of synthetic methodsavailable for functionalizing the cyclopentadienyl ligands [1ndash9] Ferrocene derivatives with good donor abilities (ie nitro-gen sulfur oxygen phosphorus etc) have attracted muchinterest as the coordination of a metal to these heteroatomsgenerates multicenter molecules which have potential inmany different areas Amongst these N-substituted ligandsferrocenyl Schiff bases play pivotal role in the field of catalysis[10ndash17]

A class of the particularly attractive polymers is the aro-matic polyazomethines or Schiff base polymers because theyshow good mechanical strength attractive thermal stabilityand fiber-forming properties [18] They are synthesized bycondensation polymerization of dialdehydes or diketoneswith diamines to give high-molecular weight polymersHowever poor solubility in organic solvents limited theirpractical applications in various fields [19] A few groupsof researchers have synthesized soluble polyazomethines byintroducing alkyl or alkoxy groups into the polymer chainsand investigated their structure and physical properties suchas electric conductivity and mechanical properties [20] Inlast years there has been increasing interest in the synthesis ofnew polymers with unusual thermal optical andmechanicalproperties Among these ones polyazomethines were inves-tigated with respect to their properties including thermalstability [21] optical and electrical response [22ndash25] conduc-tivity [26 27] syn-anti isomerization [28] opto(electronic)and liquid crystal properties [29ndash31] and film or fiber

2 Journal of Chemistry

forming ability [32 33] The inclusion of ferrocene unitsinto polymeric arrays has attracted much attention due tothe electronic donating ability reversible redox chemistrysteric properties and ready functionalization of this stablefragment

The approach chosen in this study deals with the synthesisand characterization of new polyazomethines containingferrocene moiety in the polymers main chain The electro-chemical behaviours of these polymers were investigated bycyclic voltammetry Moreover solubility thermal stabilityand morphology of the synthesized polymers had beenexamined and the data were discussed

2 Experimental Part

21 Materials All polymers are new details of the syn-thesis and characterization of these compounds are givenin the experimental part All ferrocene monomers wereprepared following the previously reported methods [34]Dichloromethane (DCM) and chloroform from El-NasrChemical Company (Egypt) were freshly distilled before usepropane-13-diamine (gt99) Merck decane-110-diamine(gt96) Merck dodecane-112-diamine (gt98) Merck p-phenylenediamine (gt98)Merck and 4410158401015840-diaminodiphenylether (gt98) Merck Reagents and solvents were purchasedand used as received unless otherwise stated All reactionswere performed under nitrogen atmosphere Silica gel 60M(Macherey-Nagel 004ndash0063mm230ndash400mesh) was usedas a stationary phase for column chromatography Wheneverpossible reactions were monitored by thin-layer chromatog-raphy (TLC) using TLC silica gel coated aluminum plates60F254 (Merck)

22 Instrumentation Fourier transform Infrared spectro-photometer (FT-IR) spectra were recorded onNicolet 6700mdashThermo Fisher Scientific by using the KBr pellet tech-nique 1H-NMR spectra were recorded on a Bruker AM200 (1H 200MHz) spectrometer and chemical shifts arereported as 120575120575 values (ppm) relative to internal Me4Si High-resolution MALDI-TOF mass spectrometry (MS) analysiswas performed by the MS-service of the Laboratorium furOrganische Chemie at ETH Zurich Elemental analyses wereperformed by theMikrolabor of the Laboratorium furOrgan-ische Chemie ETH Zurich The samples were dried rigor-ously under vacuum prior to analysis to remove strongly-adhering solvent molecules High-resolution thermogravi-metric analysis (TGA) was performed on a Q500 thermo-gravimetric analyzer (TA Instruments NewCastle DEUSA)and differential thermal gravimetric (DTG) were carried outin air with Shimadzu DTG-60 at heating rate of 10∘Cminin air All measurements were carried out in an air-streamunder the same conditionsThemass loss was plotted againstincreasing temperature as well as its first derivative (DTG)that represents the change in decomposition rate Differentialscanning calorimetry (DSC) measurements were performedusing the DSC Q1000 differential scanning calorimeter fromTA Instruments in a temperature range of minus80ndash+200∘C witha heating rate of 10∘Cminminus1 Samples of a total weight ranging

between 3 and 10mg were closed into aluminum pans of40 120583120583L covered by a holed cap and analyzed under a nitrogenatmosphere The glass transition temperature (119879119879119892119892) was takenin the second heating run CV was measured on a cyclicvoltammetric analyzer using glassy carbon electrode (GCE)Bioanalytical System USA starting potential 00V and finalpotential +15 V at Analytical Chemistry Unit ACAL AssiutUniversity Egypt

23 Monomers Syntheses

231 1-(m-Formylphenyl)-110158401015840-(5-formyl-2-methoxphenyl)ferro-cene (4) Monomer 4 was synthesized in our previous work[34] as follows A mixture of ferrocene-dialcohols 3 (300 g670mmol) and MnO2 (3000 g) in CHCl3 was stirred atroom temperature for 15 h The reaction mixture was filteredoff through glass wool and the filtrate was evaporated underreduced pressure at 30∘C The product was purified bycolumn chromatography on silica gel (CHCl3 hexane 3 1ratio) as orange red crystals 71 mp 87-88∘C

C25H20FeO3 Calcd C 7077 H 475 Found C 7101H 451 FT-IR (KBr) 120584120584 C=O 1702 cmminus1 1H-NMR (CDCl3)120575120575 = 381 (s 3H OCH3) 432 (s 2H ferrocene-H) 436 (s2H ferrocene-H) 461 (s 2H ferrocene-H) 482 (s 2Hferrocene-CH) 667 (m 1H ArndashH) 718ndash762 (m 6H ArndashH) 97 (s 1H CHO) 98 (s 1H CHO) FABMSme () [M+424]

24 Model Compound Synthesis

241 1-(m-anilinemethinephenyl)-110158401015840-(2-methoxy-5-aniline-methinephenyl)ferrocene (5) Amixture of 1-(m-formylphen-yl)-110158401015840-(5-formyl-2-methoxphenyl)ferrocene (4) (0424 g1000mmol) and aniline (0245 g 2200mmol) was dissolvedin 30mL absolute EtOH in presence of few drops piperidineThe reaction mixture was stirred in oil bath at 80∘C undernitrogen for 6 h A solid product separated out duringreflux which was filtered off and dried Purification byrecrystallization from ethanol as orange red crystals yield75 mp 114minus116∘C

C37H30FeN2O Calcd C 7735 H 526 N 488 Found C7704 H 594 N 500 FT-IR (KBr) 120584120584 CH=N 1622 cmminus1 1H-NMR (CDCl3) 120575120575 = 389 (s 3H OCH3) 431 (t 2H ferrocene-CH) 435 (t 2H ferrocene-CH) 464 (t 2H ferrocene-CH)485 (t 2H ferrocene-CH) 671 (d 4H ArndashH) 674 (d 4HArndashH) 716ndash745 (m 3H ArndashH) 763 (d 4H ArndashH) 767 (d4H ArndashH) 782 (d 2H ArndashH) 826 (s 1H CH=N) 831 (s1H CH=N) MS (MALDI-TOF)119898119898119898119898119898 = 57517 [M]+

25 Polymer Syntheses

251 General Procedure In a three-necked flask equippedwith a condenser dry nitrogen inlet outlet and drop-ping funnel a mixture of 1-(m-formylphenyl)-110158401015840-(5-formyl-2-methox-phenyl)ferrocene (4) (10mmol) and diamine(11mmol) was dissolved in 30mL absolute EtOH in presenceof few drops piperidine The reaction mixture was stirred inan oil bath at 80∘C under nitrogen for 6ndash10 h A solid product

Journal of Chemistry 3

separated out during reflux which was filtered off washedwell with hot ethanol was dried under high vacuum

Fc-Polyazomethine 6a The title compound was synthesizedaccording to general procedure of polymerization from com-pound4 (0424 g 1000mmol) propane-13-diamine (0081 g1100mmol) and piperidine (few drops) in absolute EtOH(30mL) (6 h at 80∘C) as an orange precipitate (68)

C28H26FeN2O Calcd C 7273 H 567 N 606 found C7372 H 556 N 596 FT-IR (KBr) 120584120584 CH=N 1642 cmminus1 1H-NMR (CDCl3) 120575120575 = 150 (q 2H CH2) 373 (t 4H CH2) 378(s 3H OCH3) 417ndash470 (m 8H ferrocene-H) 660ndash813 (m9H ArndashH amp CH=N)

Fc-Polyazomethine 6b The title compound was synthesizedaccording to general procedure of polymerization from com-pound 4 (0424 g 1000mmol) decane-110-diamine (0189 g1100mmol) and piperidine (few drops) in absolute EtOH(30mL) (6 h at 80∘C) as an orange film (74)

C35H40FeN2O Calcd C 7499 H 719 N 500 found C7219 H 696 N 481 FT-IR (KBr) 120584120584 CH=N 1644 cmminus1 1H-NMR (CDCl3) 120575120575 = 130 (t 16H CH2) 357 (q 4H CH2) 379(s 3HOCH3) 427ndash477 (m 8H ferrocene-H) 668ndash816 (m9H ArndashH amp CH=N)

Fc-Polyazomethine 6c The title compound was synthesizedaccording to general procedure of polymerization fromcompound 4 (0424 g 1000mmol) dodecane-112-diamine(0220 g 1100mmol) and piperidine (few drops) in absoluteEtOH (30mL) (6 h at 80∘C) as a reddish brown precipitate(73)

C37H44FeN2O Calcd C 7550 H 753 N 476 found C7198 H 784 N 505 FT-IR (KBr) 120584120584 CH=N 1646 cmminus1

Fc-Polyazomethine 6d The title compound was synthesizedaccording to general procedure of polymerization from com-pound 4 (0424 g 1000mmol) p-phenylenediamine (0118 g1100mmol) and piperidine (few drops) in absolute EtOH(30mL) (10 h at 80∘C) as an orange precipitate (65)


Fc-Polyazomethine 6e The title compound was synthesizedaccording to general procedure of polymerization from com-pound 4 (0424 g 1000mmol) 4410158401015840-diaminodiphenyl ether(0118 g 1100mmol) and piperidine (few drops) in absoluteEtOH (30mL) (10 h at 80∘C) as an orange precipitate (69)

C37H28FeN2O2 Calcd C 7552 H 480 N 476 foundC 7425 H 533 N 509 FT-IR (KBr) 120584120584 CH=N 1621 cmminus11H-NMR (CDCl3) 120575120575= 375 (s 3HOCH3) 434ndash497 (m 8Hferrocene-H) 643ndash779 (m 15H ArndashH) 809 (s 2H CH=N)

3 Results and Discussion

31 Monomers Syntheses The synthetic sequences tomonomers 2ndash4 are delineated in Scheme 1 as done inour previous work [34] Appling Gombergrsquos arylation of

ferrocene with diazonium salt of the methyl 3-amino-4-methoxybenzoate to give the corresponding 1-(3-methoxycarbonyl-2-methoxyphenyl)ferrocene which wassubjected to diazotization with diazonium salt derived frommethyl 3-aminobenzoate to give the corresponding diester2 then reduction with Lithium aluminium hydride (LAH)to give monomer 3 which was oxidized with activatedMnO2 in dry CHCl3 to get the target monomer 1-(m-formylphenyl)-110158401015840-(5-formyl-2-methoxyphenyl)ferrocene(4) in 71 yield

32 Synthesis of Model Compound Before attempting poly-merization model compound 5 was synthesized by theinteraction of 1 mole of monomer 4 with 2 moles of anilinein EtOH piperidine as described in Scheme 2 The struc-ture of this model compound was confirmed by elementaland spectral analysis The FT-IR spectrum showed a newcharacteristic absorption band at 1622 cmminus1 due to CH=Nstretching in addition to other characteristic absorptionbands of the FendashCp stretching vibrations at 1074 975 and823 cmminus1 The 1H-NMR spectrum of model compound 5(in CDCl3) was in accordance with the proposed structure(Figure 1) It showed the molecular ion peak in the matrix-assisted laser desorptionionization time-of-flight (MALDI-TOF) mass spectrum

33 Polymerization and Polymer Characterization Usingsolution polycondensation technique [35] by the interactionof one mole of monomer 4 with one mole of diaminecompounds in presence of few drops piperidine give new Fc-polyazometines 6andashe as described in Scheme 3

The structures of the resulting polymers were alsoestablished from elemental analyses and spectral data Theelemental analyses of all the polymers coincided with thecharacteristic repeating units of each polymer the data areincluded in the experimental part The FT-IR spectral data ofall polyazomethine derivatives showed characteristic absorp-tion band at 3078ndash3085 cmminus1 for CndashH aromatic at 2833ndash2926 cmminus1 for CndashH aliphatic 1619ndash1646 cmminus1 due to C=Nbands of the FendashCp stretching vibrations at 1079 970 and815 cmminus1 In addition other characteristic absorption bandsdue to specific groups present in the various polymers Alsothe 1H-NMR spectra of Fc-polyazomethine 6a 6band 6e(in CDCl3) were in accordance with the proposed structures(Figure 2 1H-NMR of Fc-polyazomethine 6b)

34 Solubility The solubility of the Fc-polyazomethines 6andashd was tested using solvents including dimethyl sulfoxide(DMSO) dimethyl formamide (DMF) chloroform benzenehexane and formic acid 50mg of the polymer were addedto 1mL of the chosen solvent and the solution analyzed byvisual inspection The results are shown in Table 1 All Fc-polyazometines 6andashe are clearly less soluble in polar aproticsolvents DMSO and DMF except Fc-polyazomethines whichcontain aliphatic moieties 6andashc are virtually insoluble inDMSO All Fc-polyazomethines 6andashe are soluble in hexaneand formic acid


Fe

Fe Fe

FeCOOMe

a

b

OMe OMe

OMe

MeOOC

HOOH

HO

OH

c

1 2

34

Scheme 1 Synthesis procedure of ferrocene monomer 4 Reagents and conditions a (i) diazonium salt of methyl 3-amino-4-methoxybenzoate AcOH (ii) diazonium salt of methyl 3-aminobenzoate b LAH EtOH rt cMnO2 CHCl3 rt

HO

OH

4

2

a

HN

NH

5

Fe

OMe

Fe

OMe

NH2+

Scheme 2 Synthesis procedure ofmodel compound 5 Reagents andconditions (a) EtOH piperidine reflux

Table 1 Room-temperature solubility characteristics of Fc-polya-zomethines 6a 6b 6c 6d and 6e

Polymernumber DMF DMSO CHCl3 Benzene Hexane HCOOH

6a + minus ++ ++ ++ ++6b + minus ++ ++ ++ ++6c + minus + ++ ++ ++6d + + + + ++ ++6e + + ++ + ++ ++++ soluble according to visual inspection + partially soluble minus insoluble

All Fc-polyazomethines which contain aliphatic moi-eties 6andashc are freely soluble in chloroform and benzeneexcept 6c which is partially soluble in chloroform All Fc-polyazomethines which contain aromatic moieties 6dndashe arepartially soluble in chloroform and benzene except 6e whichis freely soluble in chloroform The study succeeded ininserting the ferrocene moieties in the polymer main chainAs expected the presence of such moieties in the polymer

Table 2 Thermal properties of Fc-polyazomethines 6a 6b 6c 6dand 6e

Polymernumber

Temperature (∘C) for various decomposition levelslowast

10 20 30 40 50 PDTmax

6a 140 170 385 430 440 4396b 430 430 431 432 433 4336c 435 450 455 480 510 5166d 340 340 345 350 370 3736e 395 396 397 398 400 402lowastThe values were determined by TGA at heating rate of 10∘Cminminus1

backbone will lead to increasing chain packing distances anddecreasing interchain interactions such as hydrogen bond-ing thereby increasing the solubility compared with otherpolyazomethines [36] It can be clarified that the solubilityof Fc-polyazomethines 6andashe is based on the aliphatic oraromatic spacers in the polymer backbone It was found thatthe presence of aliphatic spacers in the polymer backboneincrease the flexibility of the polymer chains and allow thesolvent molecules to go through them which increase theprobability of solubility

35 TGA and DSC Studies The thermal behaviour of theFc-polyazomethines 6andashd was evaluated by TGA in air withheating rate of 10∘Cmin TGA curves show a small weight-loss in the range 05ndash45 starting at 50∘C until 235∘C exceptFc-polyazomethine 6a Table 2 shows the temperatures forthe various weight loss The initial decomposition ofthese polymers (10 loss) is considered to be polymer-decomposition temperature (PDT) [35] which occurred inrange 140∘C to 435∘C The maximum polymer degradationtemperature (PDTmax) corresponds to the temperature atwhich themaximum rate of weight loss occurred PDTmax forFc-polyazomethines 6andashd were 439∘C 432∘C 516∘C 373∘Cand 402∘C respectively The degradation steps involve thescission of azomethine groups scission of many bonds withthe liberation of free shorter chains depending upon the


HO

OH

4

+ a

HN

H

RR

N

O

eFeF

OMe

NH2

OMe

(CH2)3(CH2)10(CH2)12

H2N

6a6b6c

6d

6e

6andasheR =

R =

R =

R =R =

Scheme 3 Synthesis procedure of Fc-polyazomethines 6andashe Reagents and conditions (a) EtOH piperidine reflux

N

N

NH

H

H

HFe

OCH3

OCH3Fc

01234(ppm)

56789101112

Ar

HC

minus1

(5)mdash

mdashmdash

Figure 1 1H-NMR spectrum of model compound 5 in CDCl3

95 9 85 8 75 7 65 6 55 5 45 4 35 3 25 2 15 1

(ppm)

CH N

g

a

d

FeH

H

d

d

N N

e

e

e

c

ccc

ccb

b

cb

a

a

OMe

f

f

g 6b

H

H

Fc

Armdash

mdash

Figure 2 1H-NMR spectrum of Fc-polyazomethine 6b in CDCl3


Wei

ght (

)

Der

iv w

eigh

t (

minus15

minus10

minus5

0

0

20

40

60

80

10050

4518(008349 mg)

23535872 4651

(008595 mg)

395

8666(1601 mg)

7799(1441 mg)

590 900

43293

100 200 300 400 500 600 700 800 900Temperature ( ∘C)

∘ C)

∘C∘C

∘C

∘C

∘C∘C

∘C

Figure 3 TGA curve of Fc-polyazomethine 6b

100 200 300 400 500 600 700 800 900Temperature (

Der

iv w

eigh

t (

Wei

ght (

)

0

20

40

60

80

100

minus3

minus8

minus13

minus18

50300

1593(002743 mg)

485

40214

871(15 mg)

900

8564(1475 mg)

∘C)

∘ C)

∘C

∘C ∘C

∘C∘C

Figure 4 TGA curve of Fc-polyazomethine 6e


Table 3 Cyclic voltammetric parameters of monomer 4 model compound 5 Fc-polyazomethines 6a 6b 6c 6d and 6e at 20mVsminus1

Compound number 119864119864pc (mv) 119864119864pa (mv) ∘119864119864 (mv) Δ119864119864119901119901 (mv) 119868119868pc (120583120583A) 119868119868pa (120583120583A)1198751198751 1198751198752 1198751198751 1198751198752 1198751198751 1198751198752 1198751198751 1198751198752 1198751198751 1198751198752 1198751198751 1198751198752

4 249 mdash 437 637 343 mdash 188 mdash +198 mdash minus079 minus2145 346 mdash 480 565 413 mdash 134 mdash +740 mdash minus1127 minus44186a 303 mdash 467 540 385 mdash 164 mdash +164 mdash minus758 minus5536b 303 mdash 467 mdash 385 mdash 164 mdash +289 mdash minus1328 mdash6c 346 mdash 510 mdash 428 mdash 164 mdash +162 mdash minus440 mdash6d 358 mdash 528 619 443 mdash 170 mdash +363 mdash minus924 minus10726e 382 mdash 419 643 401 mdash 37 mdash +867 mdash minus240 minus4354

nature of these polymers This observation is in agreementwith that observed in the literature [26] TGA curve forFc-polyazomethine 6a shows mass loss between 12762 and25094∘C (minus1703) in first region between 25342 and36782∘C (minus590) in the second region and between 36787and 50551∘C (minus5811) in third region Fc-Polyazomethine6b shows mass loss between 35872 and 39500∘C (minus465)in first region between 39500 and 43293∘C (minus7799) in thesecond region (Figure 3) Fc-Polyazomethine 6c shows massloss between 21940 and 40331∘C (minus556) in first regionbetween 40477 and47325∘C (minus2867) in the second regionand between 47423 and 56960∘C (minus5021) in third regionFc-Polyazomethine 6d shows mass loss between 22761 and34074∘C (minus3777) in first region between 33976 and44743∘C (minus4638) in the second region Fc-Polyazomethine6e shows mass loss between 30000 and 48500∘C (minus8564)in one region (Figure 4) From the TGA data it is noticed thatthe fast degradation step in all Fc-polyazomethines 6andashe didnot start before 27761∘C Thus it is quite acceptable to claimthat these polymers are thermally stable till high temperature

The thermal behaviour of two selected polymers Fc-polyazomethine 6b and 6e as containing different aliphaticand aromatic spacers in the main chain was studied by differ-ential scanning calorimetry (DSC) which revealed that thesecompounds have 119879119879119892119892 values at 55∘C and 150∘C respectivelyindicating that Fc-polyazomethine containing aromatic spac-ers has higher 119879119879119892119892 values than that which contains aliphaticspacers and this may be due to the more flexibility effect ofthe aliphatic spacers on the polymer chains

36 Electrochemical Study The electrochemical behavioursof some ferrocene derivatives were investigated by cyclicvoltammetry showing interesting behaviour [34 37 38] thisencouraged us to study the electrochemical behaviour ofsome new polyazomethines with ferrocene moiety in themain chain The electrochemical redox properties of thenewly synthesized polyazomethines 6andashe based ferrocenemoiety were studied by cyclic voltammetry at room tem-perature in (dry CH2Cl2 absolute ethanol 1 1) solutionsusing glassy carbon electrode as working electrode Pt gauzeas a counter electrode and AgAgCl as a reference elec-trode and tetra-n-butylammonium perchlorate (TBAP) asthe supporting electrolyte The electrochemical data of the

investigated compounds were compared with those of Fc-monomer 4 and Fc-model compound 5 the results aresummarized in Table 3 The Cyclic voltammetric behaviourof these compounds showed one cathodic peak and thecorresponding oxidation peak in the potential range of 250ndash650mV at the glassy carbon electrode The separation ofthe anodic and the cathodic peak potentials Δ119864119864p were188 134 170 37 164 164 and 164mV at 20mVsminus1 for Fc-monomer 4 Fc-model 5 and Fc-polyazomethines 6andasherespectively These values are larger than that expected fora reversible two-electron transfer reaction which is givenby 57zmV where z is the number of electrons transferredin the process [39] indicating that the irreversibility ofthe electron-transfer process was maintained under thiscondition The formal potential 1198641198640 taken as the average of119864119864pc and 119864119864pa were 343 413 443 401 385 385 and 428mVfor Fc-monomer 4 Fc-model 5 and Fc-polyazomethines6andashe respectively 1198641198640 shifted to more positive potentialsby ca 100mV for Fc-polyazomethine 6d in comparing toFc-monomer 4 This revealed that the reduction of Fc-polyazomethine 6d becomes more easily at the glassy carbonelectrode One couple of redox waves is observed clearlyin the cyclic voltammograms for all compounds in thepotential range ca 000ndash150VThe couple redox waves in thepotential range ca 240ndash530mV is due to the redox process offerroceneferrocenium+ system Also there is another anodicwave for all compounds in potential range 540ndash650mV thisis due to the conjugation through the conjugated aromaticsystem The second anodic wave did not appear in thecase of Fc-polyazomethines 6b and c due to the increasingof methyl spacer which cut the conjugation through theconjugated aromatic system on the other hand in case ofFc-polyazomethine 6e this anodic wave increased becauseof the presence of ether aromatic linkage and the lone pairsof electron relay the conjugation through the conjugatedaromatic system

4 Conclusion

In this research a new interesting series of thermally stable Fc-polyazomethines 6andashewas synthesized via polycondensationreactions of ferrocene-dialdehyde derivative with differentdiamines The ferrocene-dialdehyde was prepared through


three- step reactions Ferrocene was converted to ferrocene-diester derivative through Gombergrsquos arylation reactionReduction of ferrocene-diester derivative using LAH con-verted it to ferrocene-dialcohol derivativeThe latter was oxi-dizedwith activatedMnO2 in dryCHCl3 to get the ferrocene-dialdehyde derivativeThe thermal behaviour of these newFe-polyazomethines showed that the polymer decompositiontemperature (PDT) of them did not start before 340∘C exceptfor Fe-polyazomethine 6a at 140∘C which indicated thatthese new Fe-polyazomethines are thermally-stable till hightemperature Also the electrochemical properties of thesenew Fe-polyazomethines were studied in comparison withboth Fc-monomer 4 and Fc-model 5 by CV SEM study ofFe-polyazomethines 6b indicated that its surface possesses aglobular structure and for Fe-polyazomethines 6d the surfacepossesses a globular structure with some coalescence presentThe research team is interested in modifying the chemicalstructure of these polymers aiming to improve their chemicaland physical properties This work is presently in progress

Acknowledgment

The authors cordially thank Professor A D Schluter forhelping in making some analyses through his group in ETHZurich

References

[1] B M Culbertson and C U Pittman New Monomers andPolymers Plenum Press New York NY USA 1984

[2] C E Carraher J E Sheats and C U Pittman Advances inOrganometallic and Inorganic Polymer Science Marcel DekkerNew York NY USA 1982

[3] Z Zoric V Rapic S Lisac and M Jukic ldquoFerrocene com-pounds XXV synthesis and characterization of ferrocene-containing oligoamides their precursors and analoguesrdquo Jour-nal of Polymer Science A vol 37 no 1 pp 25ndash36 1999

[4] P Kannan S Senthil R Vijayakumar and R MarimuthuldquoSynthesis and characterization of liquid crystalline polymerscontaining aromatic ester mesogen and a nonmesogenic fer-rocene unit in the spacerrdquo Journal of Applied Polymer Sciencevol 86 no 14 pp 3494ndash3501 2002

[5] A S Abd-El-Aziz P O Shipman B N Boden and WS McNeil ldquoSynthetic methodologies and properties oforganometallic and coordination macromoleculesrdquo Progress inPolymer Science vol 35 no 6 pp 714ndash836 2010

[6] A S Abd-El-Aziz E K Todd R M Okasha and T EWood ldquoNovel approach to oligomers and polymers containingneutral and cationic iron moieties within and pendent to theirbackbonesrdquo Macromolecular Rapid Communications vol 23no 13 pp 743ndash748 2002

[7] S Mehdipour-Ataei and S Babanzadeh ldquoNew types of heat-resistant flame-retardant ferrocene-based polyamides withimproved solubilityrdquoReactiveampFunctional Polymers vol 67 no10 pp 883ndash892 2007

[8] G Sathyaraj D Muthamilselvan M Kiruthika T Wey-hermuller and B U Nair ldquoFerrocene conjugated imidazole-phenols as multichannel ditopic chemosensor for biologicallyactive cations and anionsrdquo Journal of Organometallic Chemistryvol 716 pp 150ndash158 2012

[9] J A Lee B NWilliams K R Ogilby K LMiller and P L Dia-conescu ldquoSynthesis of symmetrically and unsymmetrically 35-dimethylbenzyl-substituted 1110158401015840-ferrocene diaminesrdquo Journal ofOrganometallic Chemistry vol 696 pp 4090ndash4094 2011

[10] Z Akhter A Nigar M Y Razzaq and HM Siddiqi ldquoSynthesisand physico-analytical studies of some novel ferrocenyl Schiffbase derivativesrdquo Journal of Organometallic Chemistry vol 692no 16 pp 3542ndash3546 2007

[11] D Pou A E Platero-Prats S Perez et al ldquoSchiff basescontaining ferrocenyl and thienyl units and their utility inthe palladium catalyzed allylic alkylation of cinnamyl acetaterdquoJournal of Organometallic Chemistry vol 692 no 22 pp 5017ndash5025 2007

[12] T R Younkin E F Connor J I Henderson S K FriedrichR H Grubbs and D A Bansleben ldquoNeutral single-componentnickel (II) polyolefin catalysts that tolerate heteroatomsrdquo Sci-ence vol 287 no 5452 pp 460ndash462 2000

[13] S Yadav and R V Singh ldquoFerrocenyl-substituted schiff basecomplexes of boron synthesis structural physico-chemical andbiochemical aspectsrdquo Spectrochimica Acta A vol 78 no 1 pp298ndash306 2011

[14] D J Jones V C Gibson S M Green and P J MaddoxldquoDiscovery of a new family of chromium ethylene polymerisa-tion catalysts using high throughput screening methodologyrdquoChemical Communications vol 38 no 10 pp 1038ndash1039 2002

[15] N Nomura R Ishii M Akakura and K Aoi ldquoStereose-lective ring-opening polymerization of racemic lactide usingaluminum-achiral ligand complexes exploration of a chain-endcontrol mechanismrdquo Journal of the American Chemical Societyvol 124 no 21 pp 5938ndash5939 2002

[16] Y Yoshida J I Mohri S I Ishii et al ldquoLiving copolymerizationof ethylene with norbornene catalyzed by bis(pyrrolide-imine)titanium complexes withMAOrdquo Journal of the American Chem-ical Society vol 126 no 38 pp 12023ndash12032 2004

[17] Z Tang X Chen Y Yang et al ldquoStereoselective polymerizationof rac-lactide with a bulky aluminumschiff base complexrdquoJournal of Polymer Science A vol 42 no 23 pp 5974ndash59822004

[18] P W Morgan S L Kwolek and T C Pletcher ldquoAromaticazomethine polymers and fibersrdquo Macromolecules vol 20 no4 pp 729ndash739 1987

[19] T Olinga O Inganas and M R Andersson ldquoSynthesis andproperties of a soluble conjugated poly(azomethine) with highmolecular weightrdquo Macromolecules vol 31 no 8 pp 2676ndash2678 1998

[20] C J Yang and S A Jenekhe ldquoConjugated aromatic polyimines2 synthesis structure and properties of new aromatic polya-zomethinesrdquoMacromolecules vol 28 no 4 pp 1180ndash1196 1995

[21] U Min and J H Chang ldquoThermotropic liquid crystallinepolyazomethine nanocomposites via in situ interlayer polymer-izationrdquo Materials Chemistry and Physics vol 129 no 1-2 pp517ndash522 2011

[22] D Sek B Jarzabek E Grabiec et al ldquoA study of thermal opticaland electrical properties of new branched triphenylamine-based polyazomethinesrdquo SyntheticMetals vol 160 no 19-20 pp2065ndash2076 2010

[23] D Sek A Iwan B Jarzabek et al ldquoHole transporttriphenylamine-azomethine conjugated system synthesis andoptical photoluminescence and electrochemical propertiesrdquoMacromolecules vol 41 no 18 pp 6653ndash6663 2008

[24] I Kaya M Yildirim and A Avci ldquoSynthesis and characteri-zation of fluorescent polyphenol species derived from methyl


substituted aminopyridine based Schiff bases the effect ofsubstituent position on optical electrical electrochemical andfluorescence propertiesrdquo Synthetic Metals vol 160 no 9-10 pp911ndash920 2010

[25] M Yildirim and I Kaya ldquoSynthesis and characterization of anovel kind soluble conjugated and fluorescent chelate polymercontaining fluorene ring in the backbone optical electrical andelectrochemical propertiesrdquo Synthetic Metals vol 161 no 1-2pp 13ndash22 2011

[26] S C Ng H S O Chan P M L Wong K L Tan and B TG Tan ldquoNovel heteroarylene polyazomethines their synthesesand characterizationsrdquo Polymer vol 39 no 20 pp 4963ndash49681998

[27] A Iwan M Palewicz A ChuchmaThla et al ldquoOpto(electrical)properties of new aromatic polyazomethines with fluorenemoieties in the main chain for polymeric photovoltaic devicesrdquoSynthetic Metals vol 162 no 1-2 pp 143ndash153 2012

[28] S Destri I A Khotina and W Porzio ldquo3-Hexyl tetra-substituted sesquithienylene-phenylene polyazomethines withhigh molecular weight Mechanistic considerationsrdquo Macro-molecules vol 31 no 4 pp 1079ndash1086 1998

[29] A Iwan M Palewicz A Sikora et al ldquoAliphatic-aromaticpoly(azomethine)s with ester groups as thermotropic materialsfor opto(electronic) applicationsrdquo Synthetic Metals vol 160 no17-18 pp 1856ndash1867 2010

[30] J C Hindson B Ulgut R H Friend et al ldquoAll-aromaticliquid crystal triphenylamine-based poly(azomethine)s as holetransport materials for opto-electronic applicationsrdquo Journal ofMaterials Chemistry vol 20 no 5 pp 937ndash944 2010

[31] L Marin E Perju and M D Damaceanu ldquoDesigning ther-motropic liquid crystalline polyazomethines based on fluoreneandor oxadiazole chromophoresrdquo European Polymer Journalvol 47 no 6 pp 1284ndash1299 2011

[32] E C Buruiana M Olaru and B C Simionescu ldquoSynthesis andproperties of some new polyazomethine-urethanesrdquo EuropeanPolymer Journal vol 38 no 6 pp 1079ndash1086 2002

[33] B Jarzabek J Weszka B Hajduk J Jurusik M Domanskiand J Cisowski ldquoA study of optical properties and annealingeffect on the absorption edge of pristine- and iodine-dopedpolyazomethine thin filmsrdquo Synthetic Metals vol 161 no 11-12pp 969ndash975 2011

[34] A A O Sarhan and T Izumi ldquoDesign and synthesis of newfunctional compounds related to ferrocene bearing heterocyclicmoieties a new approach towards electron donor organicmaterialsrdquo Journal of Organometallic Chemistry vol 675 no 1-2 pp 1ndash12 2003

[35] S H Hsiao and G S Liou ldquoA new class of aromaticpoly(134-oxadiazole)s and poly(amide-134-oxadiazole)s con-taining (naphthalenedioxy)diphenylene groupsrdquo Polymer Jour-nal vol 34 no 12 pp 917ndash924 2002

[36] N S Al-Muaikel K I Aly andM A Hussein ldquoSynthesis char-acterization and antimicrobial properties of new poly(ether-ketone)s and copoly(ether-ketone)s containing diarylidenecy-cloalkanone moieties in the main chainrdquo Journal of AppliedPolymer Science vol 108 no 5 pp 3138ndash3147 2008

[37] M Senel E Cevik and M F Abasiyanik ldquoAmperometrichydrogen peroxide biosensor based on covalent immobilizationof horseradish peroxidase on ferrocene containing polymericmediatorrdquo Sensors and Actuators B vol 145 no 1 pp 444ndash4502010

[38] A Xiao Z Li S Zhou et al ldquoSynthesis electrochemicalbehaviors and anion recognition of a novel star-[Polystyrene-b-poly(ferrocenyloxy ethyl acrylate)]6 with hexafunctionalcyclotriphosphazene corerdquo Polymer vol 51 no 5 pp 521ndash5252012

[39] P Hemmerich C Veeger and H C Wood ldquoProgress in thechemistry and molecular biology of flavins and flavocoen-zymesrdquo Angewandte Chemie-International Edition vol 4 no 8pp 671ndash687 1965

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

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Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

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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


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Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


forming ability [32 33] The inclusion of ferrocene unitsinto polymeric arrays has attracted much attention due tothe electronic donating ability reversible redox chemistrysteric properties and ready functionalization of this stablefragment

The approach chosen in this study deals with the synthesisand characterization of new polyazomethines containingferrocene moiety in the polymers main chain The electro-chemical behaviours of these polymers were investigated bycyclic voltammetry Moreover solubility thermal stabilityand morphology of the synthesized polymers had beenexamined and the data were discussed

2 Experimental Part

21 Materials All polymers are new details of the syn-thesis and characterization of these compounds are givenin the experimental part All ferrocene monomers wereprepared following the previously reported methods [34]Dichloromethane (DCM) and chloroform from El-NasrChemical Company (Egypt) were freshly distilled before usepropane-13-diamine (gt99) Merck decane-110-diamine(gt96) Merck dodecane-112-diamine (gt98) Merck p-phenylenediamine (gt98)Merck and 4410158401015840-diaminodiphenylether (gt98) Merck Reagents and solvents were purchasedand used as received unless otherwise stated All reactionswere performed under nitrogen atmosphere Silica gel 60M(Macherey-Nagel 004ndash0063mm230ndash400mesh) was usedas a stationary phase for column chromatography Wheneverpossible reactions were monitored by thin-layer chromatog-raphy (TLC) using TLC silica gel coated aluminum plates60F254 (Merck)

22 Instrumentation Fourier transform Infrared spectro-photometer (FT-IR) spectra were recorded onNicolet 6700mdashThermo Fisher Scientific by using the KBr pellet tech-nique 1H-NMR spectra were recorded on a Bruker AM200 (1H 200MHz) spectrometer and chemical shifts arereported as 120575120575 values (ppm) relative to internal Me4Si High-resolution MALDI-TOF mass spectrometry (MS) analysiswas performed by the MS-service of the Laboratorium furOrganische Chemie at ETH Zurich Elemental analyses wereperformed by theMikrolabor of the Laboratorium furOrgan-ische Chemie ETH Zurich The samples were dried rigor-ously under vacuum prior to analysis to remove strongly-adhering solvent molecules High-resolution thermogravi-metric analysis (TGA) was performed on a Q500 thermo-gravimetric analyzer (TA Instruments NewCastle DEUSA)and differential thermal gravimetric (DTG) were carried outin air with Shimadzu DTG-60 at heating rate of 10∘Cminin air All measurements were carried out in an air-streamunder the same conditionsThemass loss was plotted againstincreasing temperature as well as its first derivative (DTG)that represents the change in decomposition rate Differentialscanning calorimetry (DSC) measurements were performedusing the DSC Q1000 differential scanning calorimeter fromTA Instruments in a temperature range of minus80ndash+200∘C witha heating rate of 10∘Cminminus1 Samples of a total weight ranging

between 3 and 10mg were closed into aluminum pans of40 120583120583L covered by a holed cap and analyzed under a nitrogenatmosphere The glass transition temperature (119879119879119892119892) was takenin the second heating run CV was measured on a cyclicvoltammetric analyzer using glassy carbon electrode (GCE)Bioanalytical System USA starting potential 00V and finalpotential +15 V at Analytical Chemistry Unit ACAL AssiutUniversity Egypt

23 Monomers Syntheses

231 1-(m-Formylphenyl)-110158401015840-(5-formyl-2-methoxphenyl)ferro-cene (4) Monomer 4 was synthesized in our previous work[34] as follows A mixture of ferrocene-dialcohols 3 (300 g670mmol) and MnO2 (3000 g) in CHCl3 was stirred atroom temperature for 15 h The reaction mixture was filteredoff through glass wool and the filtrate was evaporated underreduced pressure at 30∘C The product was purified bycolumn chromatography on silica gel (CHCl3 hexane 3 1ratio) as orange red crystals 71 mp 87-88∘C

C25H20FeO3 Calcd C 7077 H 475 Found C 7101H 451 FT-IR (KBr) 120584120584 C=O 1702 cmminus1 1H-NMR (CDCl3)120575120575 = 381 (s 3H OCH3) 432 (s 2H ferrocene-H) 436 (s2H ferrocene-H) 461 (s 2H ferrocene-H) 482 (s 2Hferrocene-CH) 667 (m 1H ArndashH) 718ndash762 (m 6H ArndashH) 97 (s 1H CHO) 98 (s 1H CHO) FABMSme () [M+424]

24 Model Compound Synthesis

241 1-(m-anilinemethinephenyl)-110158401015840-(2-methoxy-5-aniline-methinephenyl)ferrocene (5) Amixture of 1-(m-formylphen-yl)-110158401015840-(5-formyl-2-methoxphenyl)ferrocene (4) (0424 g1000mmol) and aniline (0245 g 2200mmol) was dissolvedin 30mL absolute EtOH in presence of few drops piperidineThe reaction mixture was stirred in oil bath at 80∘C undernitrogen for 6 h A solid product separated out duringreflux which was filtered off and dried Purification byrecrystallization from ethanol as orange red crystals yield75 mp 114minus116∘C

C37H30FeN2O Calcd C 7735 H 526 N 488 Found C7704 H 594 N 500 FT-IR (KBr) 120584120584 CH=N 1622 cmminus1 1H-NMR (CDCl3) 120575120575 = 389 (s 3H OCH3) 431 (t 2H ferrocene-CH) 435 (t 2H ferrocene-CH) 464 (t 2H ferrocene-CH)485 (t 2H ferrocene-CH) 671 (d 4H ArndashH) 674 (d 4HArndashH) 716ndash745 (m 3H ArndashH) 763 (d 4H ArndashH) 767 (d4H ArndashH) 782 (d 2H ArndashH) 826 (s 1H CH=N) 831 (s1H CH=N) MS (MALDI-TOF)119898119898119898119898119898 = 57517 [M]+

25 Polymer Syntheses

251 General Procedure In a three-necked flask equippedwith a condenser dry nitrogen inlet outlet and drop-ping funnel a mixture of 1-(m-formylphenyl)-110158401015840-(5-formyl-2-methox-phenyl)ferrocene (4) (10mmol) and diamine(11mmol) was dissolved in 30mL absolute EtOH in presenceof few drops piperidine The reaction mixture was stirred inan oil bath at 80∘C under nitrogen for 6ndash10 h A solid product





















Fe

Fe Fe

FeCOOMe

a

b

OMe OMe

OMe

MeOOC

HOOH

HO

OH

c

1 2

34


HO

OH

4

2

a

HN

NH

5

Fe

OMe

Fe

OMe

NH2+







Polymernumber


10 20 30 40 50 PDTmax





HO

OH

4

+ a

HN

H

RR

N

O

eFeF

OMe

NH2

OMe

(CH2)3(CH2)10(CH2)12

H2N

6a6b6c

6d

6e

6andasheR =

R =

R =

R =R =


N

N

NH

H

H

HFe

OCH3

OCH3Fc

01234(ppm)

56789101112

Ar

HC

minus1

(5)mdash

mdashmdash


95 9 85 8 75 7 65 6 55 5 45 4 35 3 25 2 15 1

(ppm)

CH N

g

a

d

FeH

H

d

d

N N

e

e

e

c

ccc

ccb

b

cb

a

a

OMe

f

f

g 6b

H

H

Fc

Armdash

mdash



Wei

ght (

)

Der

iv w

eigh

t (

minus15

minus10

minus5

0

0

20

40

60

80

10050

4518(008349 mg)

23535872 4651

(008595 mg)

395

8666(1601 mg)

7799(1441 mg)

590 900

43293

100 200 300 400 500 600 700 800 900Temperature ( ∘C)

∘ C)

∘C∘C

∘C

∘C

∘C∘C

∘C


100 200 300 400 500 600 700 800 900Temperature (

Der

iv w

eigh

t (

Wei

ght (

)

0

20

40

60

80

100

minus3

minus8

minus13

minus18

50300

1593(002743 mg)

485

40214

871(15 mg)

900

8564(1475 mg)

∘C)

∘ C)

∘C

∘C ∘C

∘C∘C










4 Conclusion




Acknowledgment


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





















Fe

Fe Fe

FeCOOMe

a

b

OMe OMe

OMe

MeOOC

HOOH

HO

OH

c

1 2

34


HO

OH

4

2

a

HN

NH

5

Fe

OMe

Fe

OMe

NH2+







Polymernumber


10 20 30 40 50 PDTmax





HO

OH

4

+ a

HN

H

RR

N

O

eFeF

OMe

NH2

OMe

(CH2)3(CH2)10(CH2)12

H2N

6a6b6c

6d

6e

6andasheR =

R =

R =

R =R =


N

N

NH

H

H

HFe

OCH3

OCH3Fc

01234(ppm)

56789101112

Ar

HC

minus1

(5)mdash

mdashmdash


95 9 85 8 75 7 65 6 55 5 45 4 35 3 25 2 15 1

(ppm)

CH N

g

a

d

FeH

H

d

d

N N

e

e

e

c

ccc

ccb

b

cb

a

a

OMe

f

f

g 6b

H

H

Fc

Armdash

mdash



Wei

ght (

)

Der

iv w

eigh

t (

minus15

minus10

minus5

0

0

20

40

60

80

10050

4518(008349 mg)

23535872 4651

(008595 mg)

395

8666(1601 mg)

7799(1441 mg)

590 900

43293

100 200 300 400 500 600 700 800 900Temperature ( ∘C)

∘ C)

∘C∘C

∘C

∘C

∘C∘C

∘C


100 200 300 400 500 600 700 800 900Temperature (

Der

iv w

eigh

t (

Wei

ght (

)

0

20

40

60

80

100

minus3

minus8

minus13

minus18

50300

1593(002743 mg)

485

40214

871(15 mg)

900

8564(1475 mg)

∘C)

∘ C)

∘C

∘C ∘C

∘C∘C










4 Conclusion




Acknowledgment


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


HO

OH

4

+ a

HN

H

RR

N

O

eFeF

OMe

NH2

OMe

(CH2)3(CH2)10(CH2)12

H2N

6a6b6c

6d

6e

6andasheR =

R =

R =

R =R =


N

N

NH

H

H

HFe

OCH3

OCH3Fc

01234(ppm)

56789101112

Ar

HC

minus1

(5)mdash

mdashmdash


95 9 85 8 75 7 65 6 55 5 45 4 35 3 25 2 15 1

(ppm)

CH N

g

a

d

FeH

H

d

d

N N

e

e

e

c

ccc

ccb

b

cb

a

a

OMe

f

f

g 6b

H

H

Fc

Armdash

mdash



Wei

ght (

)

Der

iv w

eigh

t (

minus15

minus10

minus5

0

0

20

40

60

80

10050

4518(008349 mg)

23535872 4651

(008595 mg)

395

8666(1601 mg)

7799(1441 mg)

590 900

43293

100 200 300 400 500 600 700 800 900Temperature ( ∘C)

∘ C)

∘C∘C

∘C

∘C

∘C∘C

∘C


100 200 300 400 500 600 700 800 900Temperature (

Der

iv w

eigh

t (

Wei

ght (

)

0

20

40

60

80

100

minus3

minus8

minus13

minus18

50300

1593(002743 mg)

485

40214

871(15 mg)

900

8564(1475 mg)

∘C)

∘ C)

∘C

∘C ∘C

∘C∘C










4 Conclusion




Acknowledgment


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Wei

ght (

)

Der

iv w

eigh

t (

minus15

minus10

minus5

0

0

20

40

60

80

10050

4518(008349 mg)

23535872 4651

(008595 mg)

395

8666(1601 mg)

7799(1441 mg)

590 900

43293

100 200 300 400 500 600 700 800 900Temperature ( ∘C)

∘ C)

∘C∘C

∘C

∘C

∘C∘C

∘C


100 200 300 400 500 600 700 800 900Temperature (

Der

iv w

eigh

t (

Wei

ght (

)

0

20

40

60

80

100

minus3

minus8

minus13

minus18

50300

1593(002743 mg)

485

40214

871(15 mg)

900

8564(1475 mg)

∘C)

∘ C)

∘C

∘C ∘C

∘C∘C










4 Conclusion




Acknowledgment


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









4 Conclusion




Acknowledgment


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Acknowledgment


References



















































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

New Polymer Syntheses Part 57: Thermally Stable New...

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