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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 1012–1019

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Spectrophotometric and thermal studies on the charge – Transfer

complexes of 4-(aminomethyl) piperidine as donor
with r- and p-electron acceptors
Adel Mostafa a, Nada El-Ghossein a, Siham Y. AlQaradawi b,⇑
a
Science Program, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
b
Department of Chemistry and Earth Sciences, College of Arts and Sciences, Qatar University, P.O. Box 2713, Doha, Qatar

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Three CT-complexes of 4-
(aminomethyl) piperidine with the
acceptors DDQ, TBCHD and iodine are
obtained.
 The adduct 7,7,8-tricyano-8-amino-
methylpiperidinylquinodimethane
[TCAMPQDM] is yielded with TCNQ.
 These CT-complexes are
characterized through FTIR, UV–vis,
elemental and thermal analysis.
0
 The values of KC, eCT, ECT and DG are
calculated.

a r t i c l e i n f o a b s t r a c t

Article history: The spectroscopic characteristics of the solid charge-transfer molecular complexes (CT) formed in the
Received 21 June 2013 reaction of the electron donor 4-(aminomethyl) piperidine (4AMP) with the r-acceptor iodine and the
Received in revised form 6 September 2013 p-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,4,4,6-tetrabromo-2,5-cyclohexadie-
Accepted 26 September 2013
none (TBCHD) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been studied in chloroform at
Available online 9 October 2013
25 °C. These were investigated through electronic, infrared spectra and thermal analysis as well as
elemental analysis.
Keywords:
The results show that the formed solid CT-complexes have the formulas ½ð4AMPÞ Iþ I
3 , [(4AMP)(DDQ)2]
4-(Aminomethyl) piperidine
DDQ
and [(4AMP)(TBCHD)] while in the case of 4AMP-TCNQ reaction, a short-lived CT complex is formed
TBCHD followed by rapid N-substitution by TCNQ forming the final reaction product 7,7,8-tricyano-8-amin-
TCNQ omethylpiperidinylquinodimethane [TCAMPQDM] in full agreement with the known reaction stoichiom-
Spectra etries in solution as well as the elemental measurements and the thermal analysis confirmed the
structure of the obtained compounds. The formation constant kCT, molar extinction coefficient eCT, free
energy change DG0 and CT energy ECT have been calculated for the CT-complexes ½ð4AMPÞ Iþ I 3,
[(4AMP)(DDQ)2] and [(4AMP)(TBCHD)].
Ó 2013 Elsevier B.V. All rights reserved.

Introduction charge-transfer (CT) complexes which absorb radiation in the

The molecular interactions between electron donors and accep-
tors are generally associated in the formation of intensity colored
⇑ Corresponding author. Tel.: +974 55507904; fax: +974 44835750.
E-mail address: siham@qu.edu.qa (S.Y. AlQaradawi).
visible region [1–9]. The photometric methods based on these
interactions are usually simple and convenient because of the
rapid formation of the complexes. The chemical and physical prop-
erties of charge-transfer (CT) complexes formed in the reactions of
p- and r-electron acceptors with different donors like amines,
crown ethers, polysulfur bases and oxygen–nitrogen mixed bases

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.09.091
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A. Mostafa et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 1012–1019
have been the subjects of many studies both in solution and in
solid state [10–14]. The donor 4-(aminomethyl) piperidine
(4AMP) is evaluated as small molecule inhibitor of CD4 – gp 120
binding and involved in solvothermal preparation of germanium
oxide hydroxide 3D net zeotype, zeolite synthesis and coupling agent
for adhesive systems. It was found that the reaction stoichiometries
as well as the structure of these CT-complexes depend strongly on
the number of nitrogen donor atoms as well as on their terminal
attached groups, hydrogen or donating groups like alkyl or withdraw-
ing atoms like halogens. Electrons donating like alkyl groups were
found to enhance the acceptor:donor stoichiometry [15].
Interestingly, most of the CT-complexes have many applications
in chemical analysis like quantitative drug estimation and some
complexes have interesting physical properties like electrical con-
ductivities [16–19]. In this paper, we report the formation of three
new CT-complexes formed on the reaction of 4-(aminomethyl)
piperidine (4AMP) with r-acceptor iodine and different types of
p-acceptors like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) but
with the acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) an
adduct 7,7,8-tricyano-8-aminomethylpiperidinylquinodimethane
[TCAMPQDM] has been formed.
Experimental
Materials and instrumentation
The chemicals used in this study were of high grade and
obtained from Sigma–Aldrich, USA, and used without further
purification.
The UV–vis electronic absorption spectra of the CHCl3 solutions
of the solid CT-complexes formed in the reactions of the donor
4-(aminomethyl) piperidine (4AMP) and the acceptors iodine,
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tet-
rabromo-2,5-cyclohexadienone (TBCHD) as well as the reaction
products were checked in the region 1100–250 nm using a lambda
950 Perkin Elmer UV–vis spectrometer with quartz cell of 1.0 cm
path length.
The adduct 7,7,8-tricyano-8-benzylpiperidinylquinodimethane
[TCAMPQDM] formed in the reaction of the donor 4-(amino-
methyl) piperidine (4AMP) and 7,7,8,8-tetracyanoquinodimethane
(TCNQ) has been checked using Agilent GC/MS model 7890A with
the thermal separation probe (TSP). Elemental analysis was done
using a Perkin Elmer CHNSO elemental analyzer model 2400 series
1013
II. The infrared spectra of the reactants, (4AMP), DDQ, TBCHD and
TCNQ and the obtained CT-complexes (KBr pellets) were recorded
on a spectrum one Perkin Elmer FTIR spectrometer.
Photometric titration
The measurements of Photometric titration were obtained for
the reactions between the donor (4AMP) and each of the acceptors
DDQ, TBCHD and iodine in CHCl3 at 25 °C in order to determine the
reaction stoichiometries according to a literature method [5,20].
The measurements were conducted under the conditions of fixed
donor (4AMP) concentration while those of the acceptors DDQ,
TBCHD and iodine 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 absorbancies 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 com-
plexes (KBr pellets) were recorded on a spectrum one Perkin–El-
mer FTIR spectrophotometer.
The three solid CT-complexes formed in the reaction of (4AMP)
with each of DDQ, TBCHD and iodine were prepared in CHCl3 by the
drop wise addition of a saturated solution (75 ml) of each of the do-
nors to a saturated solution (90 ml) of each of the acceptors. In each
case the mixing of reactants was associated with a strong change in
color. The resulting precipitate in each case was filtered off, washed
with minimum amounts of CHCl3 and dried in vacuum over P2O5.
The complexes were characterized using spectroscopic techniques
(FTIR and UV–vis) and by elemental analysis: (theoretical values
are shown in brackets): [TCAMPQDM] light yellow complex (M/
W: 291.38 g); C, 70.11% (70.01%) H, 5.79% (5.83%); N, 24.08%
(24.02%); ½ð4AMPÞ Iþ I3 brown complex (M/W: 621.81C, 11.53%
(11.58%); H, 2.23% (2.25%); N, 4.48% (4.50%); [(4AMP)(DDQ)2] dark
brown complex (M/W: 568.19 g); C, 46.39% (46.46%); H, 2.43%
(2.46%); N, 14.71% (14.78%) and [(4AMP)(TBCHD)] dark brown
complex (M/W: 523.89 g); C, 27.44% (27.49%); H, 3.06% (3.05%);
N, 12.44% (5.34%).
Results and discussion
Electronic absorptions spectra
The UV–vis spectra of the CHCl3 solution of the formed solid
complexes, ½ð4AMPÞ Iþ I 3 , [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)]
are given in Table 1. The elemental analysis of these solid products
strongly supports the proposed complex structures and in good
agreement with stoichiometrics reaction based on photometric
titration method as indicated below.
Reaction of 4AMP with TCNQ
When adding the donor 4-aminomethylpiperidine (1  103 M)
to a solution of TCNQ (3  103 M) in CHCl3, a brown color is
formed which changes very fast forming a stable yellow yield.
Fig. 1 shows the electronic spectrum recorded at region
430–1100 nm of the reactants 4AMP and 7,7,8,8-tetracyanoquino-
dimethane (TCNQ) along that of the final yellow product.
Interestingly, both reactants do not show any absorption in the
region of study while the reaction product has a number of three
absorptions at 852, 754 and 654 nm. The formation of the short
– lived brown product which gives the stable yellow reaction
product is understood on the basis that 4AMP acts as an electron
donor reacts with p-acceptor TCNQ forming 4AMP-TCNQ
CT-complex. This short-lived product (brown in color) undergoes
elimination reaction forming the yellow final product which
is identified by elemental analysis to be 7,7,8-tricyano-8-amin-
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Table 1
Spectroscopic data for the CHCl3 solutions of solid CT-complexes of 4AMP with the acceptors iodine, DDQ, TCNQ and TBCHD.

Complex/adduct Color Absorptiona (nm) Stoichiometry (donor:acceptor)

½ð4AMPÞ Iþ I
3
Brown 382 s, 294 s 1:2
[(4AMP)(DDQ)2] Dark brown 830 s, 483 s 1:2
[(4AMP)(TBCHD)] Dark brown 555 m 1:1
a
The reactants 4AMP, I2, DDQ and TBCHD have no measurable absorptions in the region of study with used concentrations; m, medium; s, strong; sh,
shoulder.

NH2

N CN

Fig. 1. Electronic absorption spectra of 4-(aminomethyl) piperidine (4AMP) – TCNQ

reaction in CHCl3. (A) [4AMP] = 1  103 M; (B) [TCNQ] = 3  103 M; (C) 4AMP-
TCNQ mixture, [4AMP] = 1  103 M and [TCNQ] = 3  103 M.

NC CN

Formula 1. 7,7,8-Tricyano-8-aminomethylpiperidinylquinodimethane (TCAMQDM).

omethylpiperidinylquino-dimethane (TCAMPQDM), Formula 1. A
general mechanism for the reaction is proposed as follows:

(i) Formation of CT-complex:

TCNQ þ 4AMP!½ð4AMPÞðTCNQ Þðbrown short  livedÞ

(ii) N-substitution by TCNQ:

½ð4AMPÞðTCNQ Þ!7; 7; 8  tricyano  8

 aminomethylpiperidinylquino
 dimethaneðTCAMPQDMÞ þ HCNðyellow; stableÞ

Our results agree quite well with that reported by Frey et al.
[21] on their reaction between the p-acceptor tetracyanoethylene
and electron donor like aniline where the later undergoes rapid
N-substitution by TCNE:

C6 H5 NH2 þ C2 ðCNÞ4 ! C6 H5 NHðC2 ðCNÞ3 Þ þ HCN

and with the work on the reaction of TCNE and o-phenylenediamine

[21,22]
C6 H8 N2 þ C2 ðCNÞ4 ! C6 H6 N2 ðC2 ðCNÞ2 Þ þ 2HCN
Mass spectral measurements were performed only for 4AMP –
TCNQ adduct TCAMPQDM. Fig. 2 shows the mass spectrum in the
region m/z = 30–300. The molecular ion M+ is observed as a short
peak at m/z = 292 in good agreement with the calculated value
for the molecular weight of the reaction product (TCAMPQDM) of
291.38 g. The found difference of about 0.62 between the observed
and calculated molecular weight value is acceptable within the al-
lowed experimental errors. The mass spectrum (Fig. 2) also shows
a number of other peaks. The peaks at m/z 179, 97 and 83 are re-
lated to the formation of fragments shown in (A), (B) and (C)
respectively.
Reaction of 4AMP with I2, DDQ and TBCHD
Fig. 3 shows the electronic absorption spectra of the reaction of
the r-acceptor iodine with the donor 4-(aminomethyl) piperidine
(4AMP). While none of the spectra of the reactants display any
measurable absorption in the region 250–650 nm, the resulting
CT-complex shows strong absorptions centered on 382 and
294 nm. These absorptions are associated with the strong change
in color to dark brown observed upon mixing of reactants and
reflect the electronic transitions in the formed CT-complexes.
Photometric titration measurements for the reaction in CHCl3 were
performed. The molar ratio was found to be 1:2, as shown in Fig. 4.
This reaction stoichiometry was supported by the obtained
elemental analysis of the formed solid product. However, the two
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Fig. 2. Mass spectrum for 7,7,8-tricyano-8-aminomethylpiperidinylquinodime-
thane (TCAMPQDM).
Fig. 3. Electronic absorption spectra of 4-(aminomethyl) piperidine (4AMP) –
iodine reaction in CHCl3. (A) [4AMP] = 5  103 M; (B) [I2] = 1  103 M; (C) 1:2
4AMP-I2 mixture, [4AMP] = 5  103 M and [I2] = 1  103 M. The band at 294 nm
of diluted solution of 4AMP/I2 CT-complex (inset).
Fig. 4. Photometric titration curves for 4AMP–iodine reaction in CHCl3 measured at
382 nm absorptions.
absorption bands of the formed iodine complex around 382 and
294 nm in Fig. 3, are known to be characteristics of the formation
of the polyiodide ion of the type I
3 [23]. Based on this, the structure
of the formed CT-complex should be ½ð4AMPÞ Iþ I 3 and the forma-
tion of iodide intermediate [(4AMP) I]+. I is characterized by its
known absorption [24] at 245 nm and the formation of
1015
Fig. 5. Electronic absorption spectra of 4-(aminomethyl) piperidine (4AMP) – DDQ
reaction in CHCl3. (A) [4AMP] = 1  103 M; (B) [DDQ] = 1  103 M; (C) 1:2 4AMP-
DDQ mixture, [4AMP] = [DDQ] = 1  103 M.
Fig. 6. Photometric titration curve for 4AMP–DDQ reaction in CHCl3 measured at
483 nm absorptions.
½ð4AMPÞ Iþ I
3 could be understood considering the three reaction
steps, the first involves the formation of the outer complex:
(i) ð4AMPÞ þ I2 !½ð4AMPÞ  I2
 Formation of the inner complex,
(ii) ½ð4AMPÞ:I2 !½ð4AMPÞ Iþ  I
 Formation of the triiodide CT-complex
(iii) ½ð4AMPÞ Iþ I þ I2 ½ð4AMPÞ Iþ I
3
Fig. 5 shows the electronic spectrum recorded in the region
400–1100 nm of the reaction of 2,3-dichloro-5,6-dicyano-1,
4-benzoquinone (DDQ) with 4AMP. Similar to the reaction with the
previous acceptor, strong change in color is observed upon mixing.
Reddish brown color indicates the formation of the
4AMP – DDQ charge-transfer complex and is associated with the
electronic transitions at 787 and 483 nm. Photometric titration
measurements were performed for 4AMP – DDQ reaction in CHCl3
as shown in Fig. 6. The results showed that the donor – DDQ molar
ratio was found to be 1:2. This is in good agreement with the
obtained elemental analysis of the solid CT-complex which
accordingly can be formulated as [(4AMP)(DDQ)2].
Fig. 7 shows the electronic spectrum obtained in the region
350–750 nm of the reaction of 2,4,4,6-tetrabromo-2,5-cyclohexa-
dienone (TBCHD) with 4AMP. Strong change in color is observed
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Fig. 7. Electronic absorption spectra of 4-(aminomethyl) piperidine (4AMP) –

TBCHD reaction in CHCl3. (A) [4AMP] = 5  103 M; (B) [TBCHD] = 1  103 M; (C)
1:1 4AMP-TBCHD mixture, [4AMP] = 5  103 M and [TBCHD] = 1  103 M.

Fig. 9. Spectral determination of formation constant and molar extinction Coeffi-

cients of CT-complexes: ½ð4AMPÞ Iþ I
3 at 360 nm and (4AMP)(DDQ)2] at 830 nm.

Fig. 8. Photometric titration curve for 4AMP–TBCHD reaction in CHCl3 measured at

555 nm absorptions.

upon mixing giving a dark brown color indicating the formation of

the 4AMP-TBCHD charge-transfer complex and is associated with
the electronic transitions at 555 nm. Photometric titration mea-
surements were performed for 4AMP-TBCHD reaction in CHCl3 as
shown in Fig. 8. The results showed that the donor-TBCHD molar
ratio was found to be 1:1. This is in good agreement with the ob-
tained elemental analysis of the solid CT-complex which accord-
ingly can be formulated as [(4AMP)(TBCHD)].
These obtained UV–vis spectra of the CT-complexes Fig. 10. Benesi–Hildebrand plots for the CT-complexes: (A) [(4AMP)(TBCHD)] at
½ð4AMPÞ Iþ I3 , [(4AMP)(DDQ)2], and [(4AMP)(TBCHD)] have clari- 555 nm.
fied that the variation of the CT-absorption of iodine, DDQ and
TBCHD should be related to the electron affinity of each acceptor
with the donor 4AMP. well as the sterric hinderance between reactants. All of these fac-
These pronounced variations of CT-interaction stoichiometries tors are expected to play an important role on the electron dona-
are relatively complicated issue to be sorted out. It is definitely tion process from the nitrogen electron pairs of the donor 4AMP
connected to many factors such as the donor molecular symmetry, and the aromatic ring of DDQ, TCNQ and TBCHD acceptors. The
the type of electron withdrawing groups or atoms Cl, Br or C„N as aromatic ring in TBCHD has lower electron accepting ability com-

Table 2
Spectrophotometric and free energy results of CT-complexes ½ð4AMPÞ Iþ I
3 , [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] in CHCl3.

Complex KCT (l mol1) DG0 (cal mol1) ECT (eV) kmax (nm) eCT (l mol1 cm1)
5 3
½ð4AMPÞ Iþ I
3
13.801  10 8.38  10 3.26 382 0.980  103
[(4AMP)(DDQ)2] 0.670  105 6.58  103 1.50 830 1.192  103
[(4AMP)(TBCHD)] 0.017  105 4.41  103 2.24 555 0.097  103
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A. Mostafa et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 1012–1019
(A)
(B)
(C)
%T
(D)
(E)
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
Wavenumber (cm-1)
Fig. 11. IR spectra of: (A) 4-(aminomethyl) piperidine (4AMP); (B) [TCAMPQDM];
(C) [(4AMP)(DDQ)2]; (D) ½ð4AMPÞ Iþ I
3 and (E) [4AMP)(TBCHD)].
pared with that in DDQ, related to the lower electron withdrawing
process of the substituent Br in TBCHD compared with C„N in
DDQ. This certainly, allows stronger electron donation from
4AMP base to DDQ compared with that with TBCHD. In case of
4AMP-TBCHD the steric hindrance is high and the stoichiometric
ratio is lower (1:1) than that of the other two acceptors (1:2).
The formation constant (KCT) and molar extinction coefficient
(eCT) values for the formed CT-complexes of the donor 4-amino-
methylpiperidine (4AMP) with iodine, DDQ and TBCHD in CHCl3
at 25 °C were calculated. The 1:1 modified Benesi–Hildebrand Eq.
(1) [25,26] was used to calculate the values of the formation
Table 3
Infrared wavenumbers ðcm1 Þ and tentative band assignments for 4-(aminomethyl) piperidine (4AMP), ½ð4AMPÞ Iþ I
m, medium; s, strong; w, weak; br, broad; m, stretching; d, bending.
1017
constant, KCT (L mol1) and the molar extinction coefficient eCT
(L mol1 cm1), for the complex [(4AMP)(TBCHD)].
A0 D 0 ‘ 1 A0 þ D 0
¼ þ ð1Þ
A ke e
The formation constant, KCT (l mol1), and the molar extinction
coefficient eCT (l mol1 cm1) have been calculated for the com-
plexes ½ð4AMPÞ Iþ I
3 and [(4AMP)(DDQ)2], using the known [27]
Eq. (1) of 1:2 complexes:
ðA0 Þ2 D0 ‘ 1 A0 ðA0 þ 4D0 Þ
¼ þ ð2Þ
A ke e
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 light path length (1 cm).
The data obtained throughout this calculation are given in
Table 2. Plotting the values (A0)2D0 ‘/A versus A0(A0 + 4D0) values
of Eq. (1), straight lines were obtained with a slop of 1/eCT and
intercept of 1/KCT eCT as shown in Figs. 9 and 10.
These complexes show high values of both the formation
constant (KC) and the molar extinction coefficient (eCT). These high
values of KCT confirm the expected high stabilities of the formed
CT-complexes as a result of the expected high donation of 4-(ami-
nomethyl) piperidine. The formation constants are strongly depen-
dent on the nature of the used acceptors including the type of
electron withdrawing substituent on it such as cyanide group in
DDQ.
The free energy change DG0 (cal mol1) values of the complexes
½ð4AMPÞ Iþ I
3 [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] were calcu-
lated from Gibbs free energy of formation according to the follow-
ing equation [28,29]:
DG0 ¼ RT ln K CT ð3Þ
where DG0 is the free energy of the charge transfer complexes; R
the gas constant (1.987 cal mol1 K); T the temperature in Kelvin
degrees; KCT the formation constant of donor–acceptor 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 spontaneous. The results of DG0 are generally
more negative as the formation constants of the CT-complexes
3 , [(4AMP) (DDQ)2], [(4AMP)(TBCHD)] and [TCAMPQDM].
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1018 A. Mostafa et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 1012–1019

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 reac-
tion will proceed in order to achieve equilibrium.
The charge transfer energy ECT of the formed solid CT-com-
plexes is calculated using the following equation [30,31]:
1243:667
ECT ðnmÞ ¼
kCT
where kCT is the wavelength of the band of the studied CT-com-
plexes ½ð4AMPÞ Iþ I 3 [(4AMP)(DDQ)2] and [(4AMP)(TBCHD). The
ECT values calculated from Eq. (4) are listed in Table 2. These results
in Table 2 (KCT, eCT, DG0 and ECT) are clarifying that the obtained so-
lid CT-complexes formed in the reaction of the donor 4AMP with
the p-acceptors DDQ and TBCHD have high CT energy and forma-
tion constants KCT as well as with the r-acceptor iodine. These high
values confirm the expected high stabilities of the formed CT-com-
plexes as a result of the expected high donation of 4AMP.
The degradations steps and their associated temperatures vary
from one complex to another depending on the type of constitu-
ents as well as on the stoichiometry in each case. Obviously, these
two factors have pronounced effects on the type of bonding, rela-
tive complex stabilities and geometries.
It is of interest to see that the triiodide complex ½ð4AMPÞ Iþ I
3
shown in Fig. 12(A) decomposes in five degradation steps; at tem-
peratures 115 and 156 °C correspond to the decomposition of
ð4Þ [4AMP] with a mass loss of 15.54% very close to the calculated va-
lue of 18.36%. This step is followed by another degradation steps at
206, 268 and 353 °C corresponds to the loss of [2 I2] species with a
total mass loss of 79.09% with difference 2.55% from the calculated
value (81.64%). This is an evident that the donor 4AMP represents
18.36% of the complex, Table 4. Accordingly, a proposed mecha-
nism for the thermal decomposition of ½ð4AMPÞ Iþ I 3 as follows:
115;156  C
(i) ½ð4AMPÞ II
3 ! 2½I2  þ 4AMP
206;268;353  C
(ii) 2½I2  ! 2I2

Infrared spectroscopy

The infrared absorption spectra of the donor 4-(aminomethyl) (A)

piperidine (4AMP) and the formed complexes ½ð4AMPÞ Iþ I 3 100 DTG
[(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] in addition to the adduct
[TCAMPQDM] are given in Fig. 11. The infrared band assignments 80
are given in Table 3. These assignments are based on the compar-
Weight %

ison of the spectra of the formed products with the spectra of the 60
free reactants, the donor 4-aminomethylpiperidine, and the accep-
tors iodine, TCNQ, DDQ and TBCHD. Interestingly, the spectra of the 40
reaction products contain the main infrared bands for both the
reactants in each case. 20
This strongly supports the formation of the donor–acceptor CT- TG
complexes. However, the absorptions of 4AMP and acceptors in the 0
formed products show same changes in band intensities and in
Temperature (oC)
some cases small shifts in the frequency wavenumber values.
These changes could be understood on the basis of the expected
symmetry and electronic structure modifications in both donor (B)
100
and acceptor units in the formed products compared with those
DTG
of the free molecules. 80
For example, the m(NAH) vibrations of the free 4-(aminomethyl)
Weight %

piperidine in [(4AMP) (DDQ)2] has two strong absorption at 3327 60

and 3181 cm1 while in the [(4AMP) (TBCHD)], two medium
absorptions are observed at 3288 and 3127 cm1. 40
The outlined changes in m(NAH) upon complexation clearly
support the involvement of the nitrogen atoms of the donor 20
24AMP in the CT-interaction process. It might also to indicate here TG

that m(C„N) vibrations of the acceptors TCNQ and DDQ show some 0

changes particularly in terms of band wavenumber values upon

Temperature (oC)
complexation. The m(C„N) vibrations for free TCNQ are observed
as a doublet at 2196 and 2182 cm1 and for free DDQ at
2203 cm1. These vibrations occur at 2217, 2174 and 2127 cm1 (C)
100
in the spectrum of [TCAMPQDM)] and at 2200 cm1 in the spec- DTG
trum of [(4AMP)(DDQ)2] complexes. 80
Weight %

Thermal analysis 60

Thermal analysis (TG and DTG) were carried out for the CT- 40
complexes ½ð4AMPÞ Iþ I3, [(4AMP)(TBCHD)] and the adduct
[TCAMPQDM] under a nitrogen gas flow (20 ml min1) within a 20
temperature range 30–950 °C and heating rate 10 °C ml1 to con- TG
firm the proposed formula and structure for the obtained products 0
as shown in Fig. 12(A)–(C) respectively. The thermogravimetric Temperature (oC)
data for these complexes and adduct are shown in Table 4. The ob-
tained data support the calculated formulas and structures of the Fig. 12. TG–DTG curves of (A) ½ð4AMPÞ Iþ I
3 , (B) [TCAMPQDM] and (C)

formed CT-complexes and the adduct. [4AMP)(TBCHD)].

 Author's personal copy

A. Mostafa et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 118 (2014) 1012–1019 1019

Table 4
Thermal decomposition dataa for the ½ð4AMPÞ Iþ I
3 , [4AMP)(DDQ)2], [(4AMP)(TBCHD)] CT-complexes and the adduct [TCAMPQDM].

a
Thermal measurements were carried out under N2 flow rate at 20 ml min1.

For the adduct [TCAMPQDM] shown in Fig. 12(B); at119 °C cor- duct 7,7,8-tricyano-8-aminomethyl-piperidinylquinodimethane
responds to the loss of C6H13N2 (donor) with total mass loss of [TCAMPQDM]. The resulting CT-complexes were shown to
40.66% (38.78% calculated). The remaining of the adduct has been have the formulas: ½ð4AMPÞ Iþ I 3, [(4AMP)(DDQ)2] and
decomposed at 148 and 165 °C with mass loss of 53.10% (61.09% [(4AMP)(TBCHD)]. Our obtained results indicate that the nitrogen
calculated) and 6.2% remaining residual carbon as clarified below: atom (>NH) of the donor is involved in the complexation with
acceptors for the three CT-complexes. The measurements show
119  C
(i) ½TCAMPQDM ! ½C11 H4 N3  þ 4AMP the donor–acceptor molar ratio is the same for the reactions of
the donor with iodine and DDQ and was found to be 1:2 and 1:1
148;165  C
(ii) ½C11 H4 N3  ! C11 H4 N3 þ 6:2% residual carbon with the acceptor TBCHD.

This thermal decomposition mechanism is depending on that a References

molecule of HCN has been removed during the formation of
[1] S.Y. AlQaradawi, Adel Mostafa, H.S. Bazzi, J. Mol. Struct. 1037 (2013) 209.
[TCAMPQDM] (Formula 1).
[2] A.S.N. Murthy, A.P. Bhardwaj, Spectrochim. Acta 39A (1983) 415.
For the CT-complex [(4AMP)(TBCHD)] shown in Fig. 12(C); The [3] J. Casaszar, Acta Phys. Chim. 29 (1998) 34.
decomposition temperature at 125 °C is associated with a mass [4] R. Foster, Organic Charge-Transfer Complexes, Academic Press, New York,
loss of 13.49% corresponds to the loss of one bromine atom [Br] 1969.
[5] E.M. Abd-Alla, A.A.A. Boraei, M.R. Mahmoud, Can. J. Appl. Spectrosc. 39 (1994)
very close to the calculated value 15.25% with difference 1.76%. 123.
At 141 °C the donor 4AMP has been decomposed with mass loss [6] H.S. Bazzi, A. Mostafa, S.Y. AlQaradawi, E.M. Nour, J. Mol. Struct. 842 (2007) 1.
19.1% close to the calculated value 21.8% The remaining part of [7] H.S. Bazzi, S.Y. AlQaradawi, A. Mostafa, E.M. Nour, J. Mol. Struct. 879 (2008) 60.
[8] A. Mostafa, H.S. Bazzi, J. Mol. Struct. 983 (2010) 126.
the acceptor [C6H2Br3O] has been decomposed at five tempera- [9] A. Mostafa, H.S. Bazzi, Spectrochim. Acta Part A 79 (2011) 1613.
tures 166, 349, 362, 379 and 439 °C with total mass loss 65.16% [10] E.M. Nour, Spectrochim. Acta Part A 167 (2000) 56.
very close to the calculated value 62.85%. Accordingly, a proposed [11] S.M. Teleb, M.S. Refat, Spectrochim. Acta Part A 60 (2005) 1579–1586.
[12] L. Shahada, A. Mostafa, E.M. Nour, H.S. Bazzi, J. Mol. Struct. 933 (2009) 1.
mechanism for the thermal decomposition of [(4BP)(TBCHD)] as [13] S.Y. AlQaradawi, E.M. Nour, Spectrosc. Lett. 37 (2004) 337.
follows: [14] A. Mostafa, G. Benjamin Cieslinski, H.S. Bazzi, J. Mol. Struct. 1029 (2012) 45.
[15] A. Fakhro, H.S. Bazzi, A. Mostafa, L. Shahada, J. Mol. Struct. 933 (2009) 1–7.
125  C
(i) ½ð4AMPÞðC6 H2 Br4 OÞ ! ½ð4AMPÞðC6 H2 Br3 OÞ þ Br [16] S.Y. AlQaradawi, E.M. Nour, Spectrochim. Acta Part A 62 (2005) 578.
[17] P.J. Trotter, P.A. White, Appl. Spectrosc. 32 (1978) 323.
141  C
[18] H. Salem, J. Pharm. Biomed. Anal. 29 (2002) 527.
(ii) ½ð4AMPÞðC6 H2 Br3 OÞ ! ½C6 H2 Br3 O þ 4AMP [19] S. Licht, Sol. Energy Mater. Sol. Cells 35 (1995) 305.
[20] D.A. Skoog, F.J. Holler, T.A. Nieman, Principle of Instrumental Analysis, fifth ed.,
166;349;362;379;439  C Saunders College Publishing, New York, 1992 (vol. 347).
(iii) ½C6 H2 Br3 O ! C6 H2 Br3 O [21] J.E. Frey, R.D. Cole, E.C. Kitchen, L.M. Suprenant, M.S. Sylwestzak, J. Am. Chem.
Soc. 748 (1985) 107.
Conclusion [22] A.S. Aljaber, E.M. Nour, Spectrochim. Acta A 70 (2008) 997.
[23] E.M. Nour, Spectrochim. Acta 47A (1991) 743.
[24] M. Mizuno, J. Tanaka, I. Harda, J. Phys. Chem. 85 (1981) 1789.
Charge-transfer interactions between the donor 4-(amino- [25] R. Abu-Eittah, F. Al-Sugeir, Can. J. Chem. 54 (1976) 3705.
methyl) piperidine with the p-acceptors DDQ, TBCHD and TCNQ [26] H.A. Benesi, J.H. Hildebrand, J.Am.Chem. Soc. 71 (1949) 2703–2707.
[27] A. El-Kourashy, Spectrochim. Acta A 37 (1981) 399.
and the r-acceptor iodine were studied in CHCl3 at 25 °C. We were [28] A.A.A. Boraei, Spectrochim. Acta A 58 (9) (2002) 1895.
able to show that the reaction stoichiometry is not the same for the [29] M. Arslan, H. Duymus, Spectrochim. Acta A 67 (2007) 573–577.
acceptors DDQ, TBCHD; the reaction of the donor 4AMP with the [30] G. Briegleb, Z. Angew. Chem. 72 (1960) 401.
[31] G. Briegleb, Z. Angew. Chem. 76 (1964) 326.
acceptor TCNQ has been undergone N-substitution producing ad-