Journal of Molecular Structure 1011 (2012) 172180

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Synthesis, spectroscopic and thermal studies of charge-transfer molecular

complexes formed in the reaction of 1,4-bis (3-aminopropyl) piperazine
with r- and p acceptors
Siham Y. AlQaradawi a,, Adel Mostafa b, Hassan S. Bazzi b
a
b

Department of Chemistry and Earth Sciences, College of Arts and Sciences, Qatar University, P.O. Box 2713, Doha, Qatar
Department of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar

a r t i c l e

i n f o

Article history:
Received 26 November 2011
Received in revised form 1 January 2012
Accepted 2 January 2012
Available online 9 January 2012
Keywords:
1,4-Bis (3-aminopropyl) piperazine
Iodine
TBCHD
Charge-transfer
Spectra
Thermal analysis

a b s t r a c t
In the present study, solid charge-transfer (CT) molecular complexes formed in the reaction of the electron donor 1,4-bis (3-aminopropyl) piperazine (APPIP) with the r-electron acceptor iodine and p-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano1,4-benzoquinone (DDQ), and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) have been investigated
spectrophotometrically in chloroform at 25 C. These were characterized through electronic and infrared
spectra as well as elemental and thermal analysis. The obtained results showed that the formed solid CTcomplexes have the formulas [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)2(TCNE)3], [(APPIP)(DDQ)] and
[(APPIP)(TBCHD)] in full agreement with the known reaction stoichiometries in solution as well as the
elemental measurements. The formation constant KCT, molar extinction coefcient eCT, free energy
change DG0, CT energy ECT and the ionization potential Ip have been calculated for the CT complexes
[(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)(DDQ)] and [(APPIP)(TBCHD)].
2012 Elsevier B.V. All rights reserved.

1. Introduction
The piperazines are a broad class of chemical compounds, many
with important pharmacological properties which contain a core
piperazine functional group. Piperazines are also used in the manufacture of plastics, resins, pesticides and brake uid. The chargetransfer (CT) complexes formed in the reactions of r- and p-electron acceptors with organic electron donors have a great attention
for non-linear optical materials and electrical conductivities and
owing to their signicant physical and chemical properties [14].
The chemical and physical properties of charge-transfer (CT) complexes formed in the reactions of p- and r-electron acceptors with
different donors like amines, polysulfur, crown ethers bases and
oxygennitrogen mixed bases have been the subjects of many
studies both in solution and in solid state [514]. The formation
of a particular polyiodide species depends strongly on the nature
of the donor base and in some cases on the method of preparation
[1518]. The p-electron acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)
and tetracyanoethylene (TCNE) are known to form stable colored
CT-complexes with many donor bases. The increased interest in
the study of charge-transfer interactions stems from the various
applications that CT-complexes can have. These include solar cells,
Corresponding author. Tel.: +974 55507904; fax: +974 44838650.
E-mail address: siham@qu.edu.qa (S.Y. AlQaradawi).
0022-2860/$ - see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2012.01.002

electronics, optical devices and others [19]. These interactions play

in biological systems very important roles [20]; beside that CTcomplexes act as intermediate in a wide variety of reactions
involving nucleophiles and electron decient molecules. In the paper herein, we report the formation of ve new CT-complexes produced from the reaction of 1,4-bis (3-aminopropyl) piperazine
with the p-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ),
tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone
(TBCHD) and r-acceptor iodine in CHCl3 as the solvent. The aim
of this work is to make an assessment of the correct nature and
stoichiometry of each of the resulting new CT-complexes formed
with each acceptor.
2. Experimental
Reagent grade chemicals were used in this study and purchased
from SigmaAldrich, USA, and used as received. The electronic
absorption spectra of the CHCl3 solutions of the solid CT-complexes
formed in the reactions of the donor 1,4-bis (3-aminopropyl) piperazine (APPIP) and the acceptors iodine, 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3-dichloro-5,
6-dicyano-1,4-benzoquinone (DDQ), and 2,4,4,6-tetrabromo-2,
5-cyclohexadienone (TBCHD) as well as the reaction products were
checked in the region 1200250 nm using a lambda 950 Perkin Elmer UVVisNIR spectrometer with quartz cell of 1.0 cm path

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

173

of each of the donors to a saturated solution (85 ml) of each of

the acceptors. The mixture in each case was stirred for about
1015 min. The mixing of reactants was associated with a strong
change in color. The resulting precipitate in each case was ltered
immediately and washed several times with minimum amounts of
CHCl3 and dried under vacuum. The complexes were characterized
using spectroscopic techniques (FTIR and UVVis) and by elemental analysis (theoretical values are shown in brackets):
[(APPIP) I]+ I
3 dark brown complex (M/W: 707.94 g); C, 16.89%
(16.95%) H, 3.36% (3.39%); N, 7.89% (7.91%); [(APPIP)(TCNQ)] dark
green complex (M/W: 404.51 g); C, 65.31% (65.26%); H, 6.96%
(6.92%); N, 27.65% (27.69%); [(APPIP)(TCNE)] yellow complex (M/
W: 784.91 g); C, 58.15% (58.1%); H, 6.18% (6.11%); N, 35.63%
(35.67%). [(APPIP)(DDQ)] reddish pink complex (M/W: 427.33 g);
C, 50.51% (50.55%); H, 5.66% (5.62%); N, 19.69% (19.66%) and [(APPIP)(TBCHD)] apricot complex (M/W: 610.02 g); C, 31.51%
(31.47%); H, 4.29% (4.26%); N, 9.21% (9.18%).

3. Results and discussion

3.1. UVVis absorption spectra

C N
N C

CN

NC

C N

N C

Cl

NC

TCNE

Br

Br

Cl
O

NC

O
NC

Br

Br

CN

TCNQ

DDQ

TBCHID

length. Elemental analysis was done using a Perkin Elmer CHNSO

elemental analyzer model 2400 series II. The infrared spectra of
the reactants, APPIP, TCNQ, TCNE, DDQ and TBCHD (iodine has no
infrared activity) and the obtained CT-complexes (KBr pellets) were
recorded on a spectrum one Perkin Elmer FTIR spectrometer while
thermogravimetric analysis (TG & DTG) were performed using Perkin Elmer computerized thermal analyzer model Pyris 6 TGA under
ow of nitrogen gas (20 ml min1) with heating rate of 10 C min1.
Photometric titration measurements were performed for the
reactions between the donor APPIP and each of the acceptors iodine, TCNQ, TCNE, DDQ and TBCHD in CHCl3 at 25 C in order to
determine the reaction stoichiometries according to a literature
method [5,21]. The measurements were conducted under the conditions of xed donor APPIP concentrations while those of the
acceptors I2, TCNQ, TCNE, DDQ, and TBCHD were changed over a
wide range, to produce in each case reaction solutions where the
molar ratio of donor:acceptor varies from 1:0.25 to 1:4. The peak
absorbencies of the formed CT complexes were measured for all
solutions in each case and plotted as a function of the acceptor
to donor molar ratio. The infrared spectra of the reactants and
the formed CT complexes (KBr pellets) were recorded on a spectrum one PerkinElmer FTIR spectrophotometer.
The ve solid CT-complexes formed in the reaction of APPIP
with each of I2, TCNQ, TCNE, DDQ and TBCHD were isolated in
CHCl3 by the drop wise addition of a saturated solution (70 ml)

The UV/vis absorption spectra of 1  103 M solution of the donor 1,4-bis (3-aminopropyl) piperazine (APPIP) with acceptors iodine (1  103 M), 7,7,8,8-tetracyanoquinodimethane (TCNQ)
(3  103 M), tetracyanoethylene (TCNE) (5  103 M), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) (3  103 M), and
2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) (5  103 M)
solutions along with those of the formed CT-complexes in CHCl3
are shown in Figs. 15, respectively. Once the donor and acceptor
solutions were mixed, strong change in color was observed and
was associated with the appearance of new absorption bands in regions where neither donor nor acceptors have any absorption. This
is a clear indication of the formation of CT-complexes. These CT
absorptions appeared at 367 and 296 nm for (APPIP)iodine mixture, 860, 758 and 633 nm for (APPIP)(TCNQ) mixture, 426 and
404 nm for (APPIP)(TCNE) mixture, 742, 488 nm for (APPIP)
(DDQ) mixture and at 513 nm for (APPIP)(TBCHD) mixture. Table
1 shows the spectroscopic data of the resulting CT-complexes.
Photometric titration measurements were performed to determine the course of the reaction in CHCl3 between the donor and
each of the acceptors. These measurements were based on the
absorption bands of the formed CT-complexes.
Strong change in color is observed upon mixing of CHCl3 solution of iodine with the donor 1,4-bis (2-aminopropyl) piperazine

Fig. 1. Electronic absorption spectra of 1,4-bis (3-aminopropyl) piperazine (APPIP)

I2 reaction in CHCl3. (A) [APPIP] = 1  103 M; (B) [I2] = 1  103 M; (C) 1:2 APPIPI2
mixture, [APPIP] = [I2] = 1  103 M.

174

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

Fig. 2. Electronic absorption spectra of 1,4-bis (3-aminopropyl) piperazine (APPIP)

TCNQ reaction in CHCl3. (A) [APPIP] = 1  103 M; (B) [TCNQ] = 3  103 M; (C) 1:1
APPIPTCNQ mixture, [APPIP] = 1  103 M and [TCNQ] = 3  103 M.

Fig. 5. Electronic absorption spectra of 1,4-bis (3-aminopropyl) piperazine (APPIP)

TBCHD reaction in CHCl3. (A) [APPIP] = 1  103 M; (B) [TBCHD] = 5  103 M; (C)
1: APPIPTBCHD mixture, [APPIP] = 1  103 M and [TBCHD] = 5  103 M.

Table 1
Spectroscopic data for the CHCl3 solutions of solid CT-complexes of APPIP with the
acceptors I2, TCNQ, TCNE, DDQ and TBCHD.
Complex

Color

Absorptiona
(nm)

Stoichiometry
(donor:acceptor)

[(APPIP) I]+ I
3

Dark
brown
Dark
green
Yellow
Reddish
pink
Apricot

367s, 296s

1:2

860m, 758w,
633sh
426s, 404m
742h, 488s

1:1

513h

1:1

[(APPIP)(TCNQ)]
[(APPIP)2(TCNE)3]
[(APPIP)(DDQ)]
[(APPIP)(TBCHD)]

1:1
1:1

The reactants APPIP, Iodine, TCNQ, TCNE, DDQ and TBCHD have no measurable
absorptions in the region of study with used concentrations; m, medium; s, strong;
sh, shoulder; h, hump.

Fig. 3. Electronic absorption spectra of 1,4-bis (3-aminopropyl) piperazine (APPIP)

TCNE reaction in CHCl3. (A) [APPIP] = 1  103 M; (B) [TCNE] = 5  103 M; (C) 1:1
APPIPTCNE mixture, [APPIP] = 1  103 M and [TCNE] = 5  103 M.

Fig. 6. Photometric titration curves for 1,4-bis (3-aminopropyl) piperazine (APPIP)

I2 reaction in CHCl3 measured at 367 and 296 nm.

Fig. 4. Electronic absorption spectra of 1,4-bis (3-aminopropyl) piperazine (APPIP)

DDQ reaction in CHCl3. (A) [APPIP] = 1  103 M; (B) [DDQ] = 3  103 M; (C) 1:1
APPIPDDQ mixture, [APPIP] = 1  103 M and [DDQ] = 3  103 M.

(APPIP), as the solution turned into an intense dark brown color.

This color, that is not associated with either of the reactants, indicates the existence of charge-transfer interactions between iodine
and the donor. The electronic absorption spectra of the reactants
along with the CT-complex formed with iodine/APPIP are shown
in Fig. 1.

Strong absorption bands, due to the formed product, appeared

at 365 and 290 nm for APPIPI2. Photometric titration measurements for the reaction in CHCl3 were performed. The molar ratio
was found to be 1:2, as shown in Fig. 6. This reaction stoichiometry
was supported by the obtained elemental analysis of the formed
solid products. However, the two absorption bands of the formed
iodine complex around 367 and 296 nm in Fig. 1, are known to
be characteristics of the formation of the polyiodide ion of the type
I
3 [22]. The reactions should be as in the following steps.

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

175

(i) APPIP I2 ! APPIP  I2

 Formation of the inner complex,
(ii) APPIP  I2 ! APPIPI  I
 Formation of the triiodide CT-complex,
(iii) APPIPI I I2 ! APPIPI I
3
The structure of the formed CT-complex should be [(APPIP) I]+
I
and
the formation of iodide intermediate [(APPIP) I]+I is char3
acterized by its known absorption [23] at 245 nm and the formation of [(APPIP) I]+ I
3 could be understood considering the
previous three reaction steps.
Interestingly, the donoracceptor molar ratio was found to be
the same for TCNQ, DDQ and TBCHD and different for TCNE. The
APPIP:acceptor ratios were found to be 1:1 for the TCNQ, DDQ
and TBCHD complexes and 1:1 for TCNE complex as shown in
Figs. 610. These obtained reaction stoichiometries are in very
good agreement with the obtained elemental analysis for the solid
CT-complexes.
Accordingly, the formed CT-complexes are formulated as [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)2(TCNE)3], [(APPIP)(DDQ)]
and [(APPIP)(TBCHD)] with colors dark brown, dark green, yellow,
reddish pink and apricot, respectively.
This variation in reaction stoichiometries (donor:acceptor)
could be associated with the molecular steric hindrance of the
acceptor which is expected to be higher in the case of TCNQ,
DDQ and TBCHD lowering the donor:acceptor ratio compared with
that of TCNE where the ratio is 1:1. This nding agrees quite well
with the fact that TCNE always form CT-complexes with higher ra-

Fig. 9. Photometric titration curve for 1,4-bis (3-aminopropyl) piperazine (APPIP)

DDQ reaction in CHCl3 measured at 488 nm.

Fig. 10. Photometric titration curve for 1,4-bis (3-aminopropyl) piperazine

(APPIP)TBCHD reaction in CHCl3 measured at 513 nm.

Fig. 7. Photometric titration curves for 1,4-bis (3-aminopropyl) piperazine (APPIP)

TCNQ reaction in CHCl3 measured at 860, 758 and 633 nm.

tios compared with the aromatic acceptors. [24,25]. It is of interest

to note that the CT-electronic transition in the ve complexes has
different band structure and occurs at different wavelength values
as claried above. The formation constant (KCT) and molar extinction coefcient (eCT) values for the formed CT-complexes of the donor 1,4-bis (3-aminopropyl) piperazine (APPIP) with iodine, TCNQ,
DDQ and TBCHD in CHCl3 at 25 C were calculated.
The 1:1 modied BenesiHildebrand Eq. (1) [26] was used to
calculate the values of the formation constant, KCT (L mol1), and
the molar extinction coefcient eCT (L mol1 cm1), for the complexes [(APPIP)(TCNQ)], [(APPIP)(DDQ)] and [(APPIP)(TBCHD)].

A0 D 0
1 A0 D 0

A
ke
e

The corresponding spectral parameters for the complex [(APPIP)

I]+ I
3 , was calculated using the known [27] Eq. (2) of 1:2
complexes:

A0 2 D0
1 A0 A0 4D0

A
ke
e

Fig. 8. Photometric titration curves for 1,4-bis (3-aminopropyl) piperazine (APPIP)

TCNE reaction in CHCl3 measured at 426 and 404 nm.

where A0 and D0 are the initial concentrations of the acceptors and

donors, respectively, while A is the absorbance at the mentioned CT
bands and is the cell path length (1 cm).
The data obtained throughout this calculation are given in
Table 2.
Plotting the values of A0D0/A against (A0 + D0) values of Eq. (1)
and plotting values of (A0)2D0/A versus A0 (A0 + 4D0) values of Eq.

176

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

Table 2
Spectrophotometric and free energy change results of CT-complexes of [(APPIP) I]+ I
3,
[(APPIP)(TCNQ)], [(APPIP)(DDQ)] and [(APPIP)(TBCHD)] in CHCl3.
Complex

KCT
(L mol1)
+ 

kmax
(nm)
3

[(APPIP) I] I3
33.0  10
[(APPIP)(TCNQ)] 13.28  103
[(APPIP)(DDQ)]
1.49  103
[(APPIP)(TBCHD)] 0.16  103

296
860
488
513

D G 0
(cal mol1)
3

6.160  10
5.622  103
4.327  103
3.001  103

ECT
(eV)

eCT

4.20
1.45
2.55
2.42

0.434  103
0.438  103
0.700  103
0.237  103

(L mol1 cm1)

Fig. 11. The plots of A0 (A0 + 4D0) values against [(A0)2D0/A] values of the chargetransfer complex [(APPIP) I]+ I
3 at 296 and 367 nm.

Fig. 13. BenesiHildebrand plots for the CT-complexes: (A) [(APPIP)(DDQ)] at

488 nm and (B) [(APPIP)(TBCHD)] at 513 nm.

Fig. 12. BenesiHildebrand plots for the CT-complex [(APPIP)(TCNQ)] at 860, 756
and 633 nm.

(2), straight lines were obtained with a slop of 1/eCT and intercept
of (1/KCT eCT) as shown in Figs. 1113.
In general these complexes show high values of both the formation constant (KCT) and the molar extinction coefcient (eCT). These
high values of KCT conrm the expected high stabilities of the
formed CT-complexes as a result of the expected high donation
of 1, 4-bis (3-aminopropyl) piperazine (APPIP) which contains four
donor nitrogen atoms.
The formation constants are strongly dependent on the nature
of the used acceptors including the type of electron withdrawing
substituent to it such as cyano and halogen groups. The obtained
data show that the CT-complex [(APPIP)(TBCHD)] has much lower
value of KCT compared with that of [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)]
and [(APPIP)(DDQ)]. The value of formation constant of [(APPIP)(TCNQ)] is higher than that of [(APPIP)(DDQ)] and this can be
understood on the basis of the differences in the electronic structure of the acceptors TCNQ, DDQ and TBCHD, while TCNQ acceptor

has four strong withdrawing cyano groups in conjugation with an

aromatic ring which causes high delocalization leads to a great increase in the Lewis acidity of the acceptor, (TCNQ), and hence the
higher value of KCT for [(APPIP)(TCNQ)] CT-complex compared with
those of the other used acceptors except that of iodine. This certainly, allows stronger electron donation from APPIP base to the
two acceptors DDQ and TCNQ compared with that with TBCHD.
Accordingly the donation from APPIP to acceptors are in the order
of I2 > TCNQ > DDQ > TBCHD. An unsuccessful attempt was made
to calculate the corresponding values of KCT and eCT for the 1:1
complex [(APPIP)2(TCNE)3]. The 1:1 stoichiometric ratio has
many complicated terms to deal with and we might in the future
overcome this problem and publish these results.
The free energy change DG0 (cal mol1) values of the complexes
[(APPIP) I]+ I
[(APPIP)(TCNQ)], [(APPIP)(DDQ)] and [(AP3,
PIP)(TBCHD)] were calculated from Gibbs free energy of formation
according to Eq. (3) [28,29]:

DG0 RT ln K CT

where DG0 is the free energy of the charge transfer complexes; R

the gas constant (1.987 cal mol1 C); T the temperature in Kelvin
degrees; KCT the formation constant of donoracceptor complexes
(L mol1). The DG0 values of the complexes are given in Table 2.
The obtained results of DG0 reveal that the CT-complexes formation
process is exothermic in nature and spontaneous. The results of DG0
are generally more negative as the formation constants of the CTcomplexes increase. As the bond between the components becomes
stronger and thus the components are subjected to more physical
strain or loss of freedom, the values of DG0 become more negative.
The more negative the value for DG0, the farther to the right the
reaction will proceed in order to achieve equilibrium.

177

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

The charge transfer energy ECT of the formed solid CT-complexes is calculated using the following Eq. (4) [30,31]:

ECT

1243:667
kCT

where kCT is the wavelength of the band of the studied CT-complexes [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)] [(APPIP)(DDQ)] and [(AP-

PIP)(TBCHD)]. The ECT values calculated from Eq. (4) are listed in
Table 2. These results (KCT, eCT, DG0 and ECT) are clarifying that
the obtained solid CT-complexes formed in the reaction of the donor APPIP and the acceptors iodine, TCNQ, DDQ and TBCHD have
high CT energy and formation constants KCT.
The ionization potential of the free donor was determined from
the CT energies of the CT band of its complexes. In case of the

Fig. 14. Infrared absorption spectra of: (A) 1,4-bis (3-aminopropyl) piperazine (APPIP), (B) [(APPIP)(TCNQ)], (C) [(APPIP)2(TCNE)3], (D) [(APPIP)(DDQ), (E) [(APPIP)(TBCHD]
and (F) [(APPIP) I]+I
3.

Table 3
Infrared wavenumbers(a) (cm1) and tentative band assignments for 1,4-bis (3-aminopropyl) piperazine (APPIP), and CT-complexes [(APPIP)(TCNQ)], [(APPIP)(DDQ)],
[(APPIP)(TBCHD)] [(APPIP)2(TCNE)3] and [(APPIP)I] I3.
APPIP

[(APPIP)(TCNQ) ]

[(APPIP)(DDQ) ]

[(APPIP)(TBCHD) ]

[(APPIP)2(TCNE)3]

[(APPIP) I] I3

Assignments

3582w
3360m
3284m
2936s, 2874m,
2808s

3431s,br
3357w, 3192m,
3044m
2942m, 2819m

3416s,br
3247w, 3164w, 3016w

3434s,br
3227s, 3082s

3437s,br
3258w, 3000w

3429s,br
3164w, 3104w, 3029s

m(H2O); KBr
m(NAH); APPIP

2951s, 2826s

2941s, 2840s

2945m, 2820m

2928w, 2835s

m(CAH); APPIP

2225m, 2128s,
2174s

2208sm

1658sm

2236w, 2219sm,

m(CN); TCNQ, TCNE and DDQ

1623w
1596s

1596w, 1569w

2193s, 2163s
1579s

m(C@O); DDQ, TBCHD

m(C@C); TCNQ, DDQ,

1478sm, 1451w
389m, 1356m
1274m, 1254w
1161s
1115m

1464sm, 1442m
1335sm, 1314m
1281m, 1256w
1158m
1130m

1598s

TBCHD, TCNE
1462sm, 1372sm,
1349sm
1271sm,
1157s

(a)

1464m, 1448w
1380w, 1323s
1273m, 1232m
1193sm
1173m

1466m, 1451w
1347w, 1318s
1284w, 1265m
1169w
1154sm
611sm

m, medium; s, strong; w, weak; br, broad; m, stretching

1466s, 1431s
1347sm, 1325sm
1259m, 1243m
1155s
1098s

m(CH2); APPIP
Free and complexed APPIP

m(CAN); APPIP
m(CAC); APPIP
m(CACl); DDQ

178

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

the spectra of the free reactants, the donor 1,4-bis(3-aminopropyl)

piperazine and the acceptors TCNQ, DDQ, TCNE and TBCHD (iodine
has no infrared activity). Interestingly, the spectra of the reaction
products contain the main infrared bands for both the reactants
in each case. This strongly supports the formation of the donor
acceptor CT-complexes. However, the absorptions of APPIP and
acceptors in the formed products show some changes in band
intensities and in some cases small shifts in the frequency wavenumber values. These changes could be understood on the basis
of the expected symmetry and electronic structure modications
in both donor and acceptor units in the formed products compared
with those of the free molecules. The m(NAH) vibrations of the free
1,4-bis (3-aminopropyl) piperazine are 3360 and 3284 cm1. Three
absorptions for m(NAH) are observed in [(APPIP)(TCNQ)] at 3357,
3192 and 3044 cm1, in [(APPIP)(DDQ) ] at 3247, 3164 and
1
3016 cm1, in the [(APPIP) I]+ I
3 at 3164, 3104, and 3029 cm
while in [(APPIP)(TBCHD)] two absorption are observed at 3227
and 3082 cm1 and in [(APPIP)2(TCNE)3] at 3258 and 3000 cm1.
The outlined changes in m(NAH) upon complexation clearly support the involvement of the nitrogen atom of the amino group in the
donor APPIP through the CT-interaction process. It might also to

acceptors iodine, DDQ, TCNQ and TBCHD the relationship becomes

the following [2729]:

ECT Ip  5:2

1:5
Ip  5:2

where Ip is the ionization potential and ECT is the charge transfer

energy of the formed solid CT-complexes. The obtained values of
Ip are 7.3, 5.9, 7.2 and 6.4 eV for the CT-complexes [APPIP)I]+ I
3,
[(APPIP)(TCNQ)], [(APPIP)(DDQ)] and [(APPIP)(TBCHD)], respectively. It has been reported that the ionization potential of the electron donor may be correlated with the charge transfer transition
energy of the complex [32].
3.2. Infrared spectra
The obtained infrared spectra of the donor 1,4-bis (3-aminopropyl) piperazine (APPIP) along with those of the formed complexes
[(APPIP)I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)(DDQ)], [(APPIP)2(TCNE)3]
and [(APPIP)(TBCHD)] are shown in Fig. 14 and the infrared band
assignments are given in Table 3. These assignments are based
on the comparison of the spectra of the formed products with

90

90

80

80

70

70

60
50

60
50

40

40

30

30

20

20

10

TG

(A)

0
30

200

400

600

DTG

105
100

DTG

Weight (%)

Weight (%)

105
100

800

950

TG

(B)

10

30

100

Temperature ( C)

300

400

500

Temperature ( oC)
105
100

105
100

DTG

90

90

80

80

70

70

Weight (%)

Weight (%)

200

60
50

DTG
60
50

40

40

30

30

20

20
TG

10
0
30

TG

(C)
200

400

600

Temperature (oC)

800

950

10
0
30

(D)
200

400

600

800

900

Temperature (o C)

Fig. 15. (AD) Thermograms of the CT-complexes; (A) [(APPIP) I]I3, (B) [(APPIP)(TCNQ)], (C) [(APPIP)(TBCHD)] and (D) [(APPIP)(DDQ)].

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

Table 4
Thermal data for the CT-complexes [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)(DDQ)],
[(APPIP)(TBCHD)] and [(APPIP)2(TCNE)3].
Complex

Reaction
stoichiometry
donor:acceptor

DTG
max
(C)

TG % mass
loss found/
calculated

Lost species

[(APPIP) I]+ I
3

1:2

79.9/82.1
16.5/17.9

[(APPIP) I2]I+
[I]

[(APPIP)(TCNQ)]

1:1

47.9/49.5

APPIP

[(APPIP)(DDQ)]

1:1

331
424,
679
163,
269,
313
648,723
195,
337,
419
575,
810
165,
357
421
749

48.7/50.5
49.6/46.9

TCNQ
APPIP

48.7/53.1

DDQ

68.4/72.2

[(APPIP)(Br)3]

[(APPIP)(TBCHD)]

[(APPIP)2(TCNE)3]

1:1

1:1

16.8/15.7
[BrO]
11.9/12.1
[C6H2]
Decomposed with broad
decomposition peak with
one maxima for a complete
loss of the whole compound

indicate here that m(CN) vibrations of the acceptors TCNQ, TCNE

and DDQ show some changes particularly in terms of band wavenumber values upon complexation. The m(CN) vibration for free
TCNQ is observed at 2223 cm1 for free DDQ at 2230 cm1 and
for free TCNE a doublet is observed at 2196 and 2182 cm1.
These vibrations occur at 2225, 2174 and 2128 cm1 in the
spectrum of [(APPIP)(TCNQ)], at 2208 cm1 for [(APPIP)(DDQ)]
and at 2236, 2219, 2193 and 2163 cm1 for [(APPIP)2(TCNE)3].

3.3. Thermal analysis

To conrm the proposed formula and structure for the obtained
CT-complexes, thermogravimetric (TG) and differential TG (DTG)
were carried out under a nitrogen gas ow (20 ml min1) within
a temperature range 30950 C and heating rate 10 C ml1.
Fig. 15AD shows the thermograms of [(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)(TBCHD)] and [(APPIP)(DDQ)], respectively.
The thermogravimetric data for these complexes are shown in Table 4. The obtained data support the calculated formulas and structures of the formed CT-complexes. The degradations steps and
their associated temperatures vary from one complex to another
depending on the type of constituents as well as on the stoichiometry in each case. Obviously, these two factors have pronounced effects on the type of bonding, relative complex stabilities and
geometries.
It is of interest to see that the triiodide complex [(APPIP) I] I3
shown in Fig. 14A decomposes in three degradation steps; at temperature 331 C corresponds to the decomposition of [(APPIP) I2] I+
with a weight loss of 79.9% very close to the calculated value of
82.1%. This step is followed by another two degradations at 424
and 679 C correspond to the loss of [I] species with a total weight
loss of 16.5% with about 1.4% deviation from the calculated value
(17.9%). This is an evident that the donor APPIP represents
28.29% of the complex, Table 4.
Accordingly, a proposed mechanism for the thermal decomposition of [(APPIP) I]+ I
3 as follows:
424, 679 C:
331  C


(i) APPIPI I
3 ! APPIPI2 I I 
424;679

C

(ii) I  ! I 

179

The second CT-complex [(APPIP)(TCNQ)] is shown in Fig. 14 (B)

at 163, 269, 313 C correspond to the loss of the donor APPIP with
total weight loss of 47.9% (49.5% calculated). The acceptor TCNQ
has been decomposed at 648 and 723 C with total weight loss of
48.7% (50.5% calculated).
Fig. 14C shows the third complex [(APPIP)(TBCHD)] decomposes
in four temperatures at 165, 357, 421 and 749 C. The temperatures
165 and 357 C show total weight loss of 65.4% corresponds to the
loss of the donor with three bromine atoms [(APPIP)(Br)3] very
close to the calculated value of 67.3%. The decomposition temperatures at 421 and 749 C are associated with a total weight loss of
33.4% corresponds to the loss of the [C6H2BrO] equivalent to the
acceptor after losing three bromine atoms (in the decomposition
steps at 165 and 357 C) in agreement with the calculated value
of 34.6%. Accordingly, a proposed mechanism for the thermal
decomposition of [(APPIP)(TBCHD)] as follows:
165;357  C

(i) APPIPC6 H2 Br4 O ! APPIPBr3  C6 H2 BrO

421;749

C

(ii) C6 H2 BrO ! BrO C6 H2 

where the chemical structure of the acceptor TBCHD is C6H2Br4O.
The fourth complex [(APPIP)(DDQ)] is shown in Fig. 14 (D) at
195, 337 and 419 C corresponds to the loss of the donor APPIP
with a weight loss of 49.6% close to the calculated value of 46.9%.
The acceptor has decomposed 575 and 810 C with total weight
loss of 48.7% (53.1% calculated).
The fth CT-complex [(APPIP)2(TCNE)3] decomposes with broad
decomposition peak with one maxima for a complete loss of the
whole compound.
4. Conclusion
Charge-transfer interactions between the donor 1,4-bis (3-aminopropyl) piperazine (APPIP) and the r-acceptor iodine and the pacceptors TCNQ, TCNE, DDQ and TBCHD were studied in CHCl3 at
25 C. We were able to show that the reaction stoichiometry is
the same (1:1) for the acceptors TCNQ, DDQ and TBCHD and is different for TCNE (1:1) and iodine (1:2).
The resulting CT-complexes were shown to have the formulas:
[(APPIP) I]+ I
3 , [(APPIP)(TCNQ)], [(APPIP)2(TCNE)3], [(APPIP)(DDQ)]
and [(APPIP)(TBCHD)]. The obtained data show that the CT-complex [(APPIP)(TBCHD)] has much lower value of KCT compared with
that of [(APPIP)I]+I
3 , [(APPIP)(TCNQ)] and [(APPIP)(DDQ)] and indicate that the nitrogen atom of the amino group in the donor 1,4-bis
(3-aminopropyl) piperazine (APPIP) is involved in the complexation with the acceptors. Further studies will focus on using different acceptors and donors to further investigate the nature of such
complexations.
References
[1] R. Foster, Organic Charge Transfer Complexes, Academic Press, London, 1969.
pp. 51, 387.
[2] R.S. Mulliken, W.B. Person, Molecular Complexes, A Lecture and Reprint
Volume, Wiley, New York, 1969.
[3] K.K. Lahiri, K.K. Mazumdar, Spectrochim. Acta 46A (1990) 1137.
[4] R. Foster, J. Chem. Soc. 1075 (1960).
[5] H.S. Bazzi, A. Mostafa, S.Y. AlQaradawi, E.M. Nour, J. Mol. Struct. 842 (2007) 1.
[6] H.S. Bazzi, S.Y. AlQaradawi, A. Mostafa, E.M. Nour, J. Mol. Struct. 879 (2008) 60.
[7] A. Mostafa, H.S. Bazzi, J. Mol. Struct. 983 (2010) 126.
[8] A. Mostafa, H.S. Bazzi, Spectrochim. Acta Part A 79 (2011) 1613.
[9] S.Y. AlQaradawi, H.S. Bazzi, A. Mostafa, E.M. Nour, Spectrochim. Acta Part A 71
(2008) 1594.
[10] J. Casaszar, Acta Phys. Chim. 29 (1998) 34.
[11] E.M. Nour, Spectrochim. Acta Part A 167 (2000) 56.
[12] A.S.N. Murthy, A.P. Bhardwaj, Spectrochim. Acta 39A (1983) 415.
[13] S.Y. AlQaradawi, E.M. Nour, Spectrosc. Lett. 37 (2004) 337.
[14] E.M. Nour, L.H. Chen, J. Laane, J. Raman Spectrosc. 467 (1986) 17.
[15] P.J. Trotter, P.A. White, Appl. Spectrosc. 32 (1978) 323.

180
[16]
[17]
[18]
[19]
[20]
[21]

S.Y. AlQaradawi et al. / Journal of Molecular Structure 1011 (2012) 172180

E.M. Nour, L.A. Shahada, Spectrochim. Acta 44A (1988) 1277.

W. Kiefer, H.J. Bernstein, Chem. Phys. Lett. 16 (1972) 5.
G.A. Bowmaker, R.J. Knappstein, J. Chem. Soc. Dalton (1977) 1928.
S. Licht, Sol. Energy Mater. Sol. Cells 35 (1995) 305.
H. Salem, J. Pharm. Biomed. Anal. 29 (2002) 527.
D.A. Skoog, F.J. Holler, T.A. Nieman, Principle of Instrumental Analysis, 5th ed.,
vol. 347., Saunders College Publishing, New York, 1992.
[22] E.M. Nour, Spectrochim. Acta 47A (1991) 743.
[23] M. Mizuno, J. Tanaka, I. Harda, J. Phys. Chem. 85 (1981) 1789.
[24] E.M. Nour, S.M. Metwally, M.A.F. ElMosallamy, Y. Gameel, Spectrosc. Lett. 115
(1999) 32.

[25] E.M. Nour, L.A. Shahada, A. Sadeek, S.M. Teleb, Spectrochem. Acta (A) 471
(1995) 51.
[26] R. Abu-Eittah, F. Al-Sugeir, Can. J. Chem. 54 (1976) 3705.
[27] A. El-Kourashy, Spectrochim. Acta A 37 (1981) 399.
[28] M. Arslan, H. Duymus, Spectrochim. Acta A 67 (2007) 573577.
[29] A.A.A. Boraei, Spectrochim. Acta A 58 (9) (2002) 1895.
[30] G. Briegleb, Z. Angew. Chem. 72 (1960) 401.
[31] G. Briegleb, Z. Angew. Chem. 76 (1964) 326.
[32] M. Pandeeswaran, K.P. Elango, Spectrochim. Acta A 65 (2006) 1148.