Journal of Molecular Structure 842 (2007) 1–5

www.elsevier.com/locate/molstruc

Synthesis and spectroscopic structural investigations

of the charge-transfer complexes formed in the reaction
of 2,6-diaminopyridine with -acceptors TCNE, chloranil, and DDQ
Hassan S. Bazzi a,¤, Adel Mostafa a, Siham Y. AlQaradawi b, El-Metwally Nour b
a
Department of Chemistry, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
b
Department of Chemistry, College of Arts and Sciences, Qatar University, P.O. Box 2713, Doha, Qatar

Received 30 October 2006; received in revised form 4 December 2006; accepted 4 December 2006
Available online 24 January 2007

Abstract

Molecular charge-transfer complexes of the donor 2,6-diaminopyridine (2,6-DAPY) with -acceptors tetracyanoethylene (TCNE),
2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetrachloro-p-benzoquinone(chloranil) were studied spectrophotometrically in
chloroform at room temperature. All formed complexes exhibit well resolved charge-transfer bands in the regions where neither donor
nor acceptors have any absorption. The stoichiometries of the reactions were determined from photometric titration methods. The results
obtained show the formed CT complexes have the structures [(2,6-DAPY)(TCNE)3], [(2,6-DAPY)(DDQ)2], and [(2,6-DAPY)(chloranil)].
These three complexes were isolated as solids and further characterized by elemental analysis and infrared measurements.
 2006 Elsevier B.V. All rights reserved.

Keywords: 2,6-Diaminopyridine; TCNE; Chloranil; DDQ; CT-complexes; Spectra

1. Introduction chloro-p-benzoquinone(chloranil) to form CT-complexes

The study of CT-interactions between aromatic electron
acceptors and various electron donors containing nitrogen,
oxygen, or sulfur atoms have attracted increased interest
over the last years. This is because of the important roles
these interactions play in biological systems; beside that
CT-complexes act as intermediates in a wide variety of
reactions involving nucleophiles and electron deWcient mol-
ecules. Some of the CT-complexes show interesting physical
properties such as electrical conductivities [1–9]. It has been
shown that both aza-aromatics and polyazacyclic com-
pounds react with - and -acceptors to form stable CT-
complexes. The stoichiometries, structure, spectral, thermal,
and electric properties of the complexes depend strongly on
the type and nature of the donor base as well as the electron
acceptors. For example, 2,3-diaminopyridine (DAPY)
reacts with the -acceptor iodine and the -acceptor tetra-
[(DAPY)(I2)2] and [(DAPY)(chloranil)] with diVerent stoi-
chiometries of 1:2 and 1:1, respectively [10–14].
In the paper herein, we report the formation of the
three new CT-complexes obtained from the reaction of
the donor 2,6-diamionpyridine (2,6-DAPY) with the -
acceptors tetracyanoelthylene (TCNE), tetrachloro-p-benzo-
quionone(chloranil) and 2,3-dichloro-5,6-dicyano-p-benzo-
quinone (DDQ) in chloroform as the solvent. The purpose of
this work is to make an assessment of the correct nature
and stoichiometry of each of the resulting new complexes
formed with each acceptor and also to investigate the eVect
of both the n (lone pair on the nitrogen) and  electrons of
the donor 2,6-DAPY on the nature of CT-interactions.
2. Experimental
2.1. Materials and spectral measurements

*
Corresponding author. Tel.: +974 5576010; fax: +974 492 7398. All Chemicals used were purchased from Sigma–
E-mail address: bazzi@tamu.edu (H.S. Bazzi). Aldrich, USA, and used as received. The electronic

0022-2860/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2006.12.005
2 H.S. Bazzi et al. / Journal of Molecular Structure 842 (2007) 1–5

3. Results and discussion

3.1. Electronic spectra

H2N N NH2
The electronic absorption spectra of 1 £ 10¡4 M solu-
2,6-Diaminopyridine tions of the donor 2,6-diaminopyridine (2,6-DAPY) with
acceptors tetracyanoethylene (TCNE) (3 £ 10¡4 M), 2,3-
dichloro-5,6-dicyano-p-benzoquinone (DDQ) (2 £ 10¡4 M)
absorption spectra of the reactants, 2,6-DAPY, TCNE, and for 1 £ 10¡3 M solutions of each of 2,6-DAPY and tet-
chloranil, and DDQ as well as of the reaction products rachloro-p-benzoquinone(chloranil), along with those of
were recorded in the region 1200–250 nm using a lambda the formed CT-complexes in CHCl3 are shown in Figs. 1–3,
950 Perkin Elmer UV–vis spectrophotometer with a quartz respectively. Once the donor and acceptor solutions were
cell of 1.0 cm path length. The infrared spectra of the reac- mixed, strong change in color was observed and was associ-
tants and the formed CT complexes (KBr pellets) were ated with the appearance of new absorption bands in
recorded on a Spectrum One Perkin Elmer FTIR spectro- regions where neither donor nor acceptors have any
photometer. Elemental analysis was done at the Galbraith absorption. This is a clear indication of the formation of
Laboratories, Knoxville, TN, USA. CT-complexes. These CT-absorptions appeared at 574 nm
Photometric titration measurements were performed for (2,6-DAPY)–(TCNE) mixture, 815 and 465 nm for (2,6-
for the reactions between the donor 2,6-DAPY and each DAPY)-(DDQ) mixture, and at 533 nm for (2,6-DAPY)-
of the acceptors in CHCl3 at 25 °C in order to determine chloranil mixture. Table 1 shows the spectroscopic data of
the reaction stoichiometries according to a literature the resulting CT-complexes.
method [15]. The concentration of 2,6-DAPY in the reac-
tion mixture was kept Wxed at 1 £ 10¡4 M for the reac-
tions with TCNE and DDQ and at 1 £ 10 ¡3 M for the
reaction with chloranil while the concentration of the
acceptor in each case was changed over a wide range of
concentrations, to produce reaction solutions where the
molar ratio of 2,6-DAPY:acceptor varies from 1:0.25 to
1:8. The peak absorbencies of the formed CT complexes
were measured and plotted as a function of the acceptor
to 2,6-DAPY molar ratio. This shows the reaction stoi-
chiometries (2,6-DAPY vs acceptor) are 1:3, 1:2, and 1:1
for the acceptors TCNE, DDQ, and chloranil, respec-
tively. These stoichiometries were used to prepare the
solid CT-complexes.

2.2. Preparation of the solid complexes Fig. 1. Electronic absorption spectra of 2,6-DAPY–TCNE reaction in CHCI3.
(A) [TCNE] D 1 £ 10¡4 M; (B) [2,6-DAPY] D 1 £ 10¡4 M; (C) 1:3 (2,6-DAPY-
TCNE) mixture, [2,6-DAPY] D 1 £ 10¡4 M, and [TCNE] D 3 £ 10¡4 M.
All three solid CT-complexes [(2,6-DAPY)(TCNE)3],
[(2,6-DAPY)(chloranil)], and [(2,6-DAPY)(DDQ)2] were
prepared following the same method: to a solution of
2,6-DAPY (1.09 g, 9.99 mmol) in CHCl3 (40 mL), a solu-
tion of the acceptor (3.00 mmol TCNE, 10.01 mmol
chloranil and 2.00 mmol DDQ) in CHCl3 (70 ml) was
added dropwise and stirred for 10 min with heating at
40 °C. The resulting precipitate was Wltered oV, washed
with minimum amounts of CHCl3 and dried in vacuum
over P2O 5. The complexes were characterized spectro-
scopically and by elemental analysis: (theoretical values
are shown in brackets): [(2,6-DAPY) (TCNE)3] blue
complex (M/w: 493.4 g): C, 55.86 (55.98%); H, 1.37%
(1.42%), and N, 42.51% (42.6%); [(2,6-DAPY)(chlora-
nil)] brown complex (M/w: 355.01 g): C, 37.07%
(37.18%); H, 1.82% (1.97%), and N, 11.74% (11.83%);
[(2,6-DAPY) (DDQ)2] grey complex, (M/w: 563.13 g): C, Fig. 2. Electronic absorption spectra of 2,6-DAPY–DDQ reaction in CHCl3:
44.67% (44.75%); H, 1.31% (1.24%), and N, 17.46% (A) [DDQ] D 3 £ 10¡4 M; (B) [2,6-DAPY] D 1 £ 10¡4 M; (C) 1:2 (2,6-DAPY-
(17.40%). DDQ) mixture, [2,6-DAPY] D 1 £ 10¡4 M, and [DDQ] D 3 £ 10¡4 M.
 H.S. Bazzi et al. / Journal of Molecular Structure 842 (2007) 1–5 3

Fig. 3. Electronic absorption spectra of 2,6-DAPY–chloranil reaction in

CHCl3: (A) [chloranil] D 1 £ 10¡3 M; (B) [2,6-DAPY] D 1 £ 10¡3 M; (C)
1:1(2,6-DAPY-chloranil) mixture, and [2,6-DAPY] D [chloranil] D 1 £ 10¡3 M.

Table 1
Fig. 5. Photometric titration curves for 2.6-DAPY–DDQ reaction in
Spectroscopic data for the formed (2,6-DAPY)-acceptor complexes
CHCl3.
Complex Color CT-absorption Stoichiometry
(nm) (2,6-DAPY:acceptor)
[(2,6-DAPY)(TCNE)3] Blue 574 1:3
[(2,6-DAPY)(DDQ)2] Grey 815, 465 1:2
[(2,6-DAPY)(chloranil)] Brown 533 1:1

Photometric titration measurements were performed to

determine the course of the reaction in CHCl3 between the
donor and each of the acceptors. Theses measurements
were based on the absorption bands of the formed CT-
complexes. Interestingly, the donor–acceptor molar ratio
was found to vary from one acceptor to another. The 2,6-
DAPY:acceptor ratios were found to be 1:3, 1:2, and 1:1
for the TCNE, DDQ, and chloranil complexes, respec-
tively, as shown in Figs. 4–6. 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
[(2,6-DAPY) (TCNE)3], [(2,6-DAPY)(DDQ)2], and [(2,6-
Fig. 4. Photometric titration curve for 2.6-DAPY–TCNE reaction in
CHCl3.
Fig. 6. Photometric titration curve for 2.6-DAPY–chloranil reaction in
CHCl3.
DAPY)(chloranil)]. This variation in reaction stoichiome-
tries (donor:acceptor) could be associated with the molec-
ular steric hindrance of the acceptor which is expected to
be higher in the case of chloranil and DDQ lowering the
donor:acceptor ratio compared with that of TCNE where
the ratio is 1:3. This Wnding agrees quite well with the fact
that TCNE always form CT-complexes with higher ratios
compared with the aromatic acceptors [11,12]. It is of
interest to note that the CT-electronic transition in the
three complexes has diVerent band structure and occurs at
diVerent wavelength values. In the case of [(2,6-DAPY)
(TCNE)3)] the CT band is centered at 573 nm with two
broad shoulders at 630 and 540 nm. This triplet structure
agrees with the stoichiometry of the reaction of 3:1,
TCNE: 2,6-DAPY, and the coordination of each the 3
TCNE units to the donor is not equivalent to the other
two. This phenomenon is much more pronounced in the
case of [(2,6-DAPY)(DDQ)2] where the absorption spec-
trum (Fig. 3) shows two well deWned CT-absorptions
4 H.S. Bazzi et al. / Journal of Molecular Structure 842 (2007) 1–5

at 815 and 465 nm in agreement with the reaction stoichi-
ometry of 2:1, DDQ:2,6-DAPY. In the case of the third
complex [(2,6-DAPY)(chloranil)], where the reaction stoi-
chiometry is 1:1, only one CT transition occurs as a rela-
tively weak absorption at 533 nm. The two CT-
absorptions of the DDQ complex with relatively large
diVerence in wavelength (815 and 465 nm) are shown to
belong to one species, both have the same photometric
titration behavior (Fig. 5).
3.2. Infrared spectra
The infrared spectra of the 2,6-DAPY along with those
of the formed CT-complexes [(2,6-DAPY)(TCNE)3], [(2,6
DAPY)(DDQ)2] and [(2,6-DAPY)(chloranil)] are shown
in Fig. 7, and their band assignments are given in Table 2.
The observation of the main infrared bands of the donor
2,6-DAPY and acceptors TCNE, DDQ, and chloranil in
the respective complex spectra strongly support the for-
mation of CT-complexes. However, the bands of the
donor and acceptors in these complexes reveal small shifts
in both band intensities and wavenumber values from
those of the free molecules. This is normal due to the
expected symmetry and electronic structure changes upon
complexation. For example, the (CCN) vibrations are
observed as a doublet at 2196 and 2182 cm¡1 in the spec-
trum of free TCNE and at 2203 cm¡1 in the spectrum of
free DDQ. These vibrations occur at 2206 and 2219 cm¡1
in the spectra of the corresponding [(2,6-DAPY)(TCNE)3]
and [(2,6-DAPY)(DDQ)2] complexes, respectively. Inter-
estingly, a smaller number of absorptions along with large
wavenumber shifts in the (NAH) vibrations of 2,6-
DAPY are observed upon complexation with diVerent
acceptors (Table 2). The (NAH) of free 2,6-DAPY
occurs at 4 well deWned absorptions at 3392, 3376, 3309,
and 3208 cm¡1 and as 3 bands at 3369, 3304, and
3211 cm¡1 in the spectrum of [(2,6-DAPY)(TCNE)3], 2
bands at 3341 and 3203 cm¡1 in the spectrum of [(2,6-
DAPY)(DDQ)2], and 2 bands at 3364 and 3322 cm¡1 in
the spectrum of [(2,6-DAPY)(chloranil)]. This clearly
demonstrates that the two amine groups are mainly
involved in the complexation process between 2,6-DAPY
and the acceptors rather than the nitrogen of the pyridine
ring. This is supported by the fact that the main vibration

Table 2
Infrared wavenumbers (cm¡1) and band assignments for 2,6-DAPY,[(2,6-DAPY)(TCNE)3], [(2,6-DAPY)(DDQ)2], and [(2,6-DAPY)(chloranil)]
2,6-DAPY [(2,6-DAPY)(TCNE)3] [(2,6-DAPY)(DDQ)2] [(2,6-DAPY)(chloranil)] Assignments
3392s 3369m 3341m 3364shoul (NAH); DAPY
3376s 3304m 3203m 3322ms
3309m 3211m
3208m
3127ms 3182ms (CAH); DAPY
2262w s(CCN); TCNE
2219m (C CN); DDQ
2206vs xs(CCN); TCNE
1691m (CBO); chloranil
1680m
1641ms 1661s 1665m 1652m (CBC):aromatic ring
1594s 1556s 1571wm Stretching vibration;
DAPY, DDQ, and chloranil
1537s (CBC); TCNE
1463m 1508s 1511mw 1505w (CBC); ring stretching vibrations; DAPY, DDQ, and chloranil
1455m 1389w 1453vs 1411w (NH2) and (CAH); deformations; DAPY
1350ms 1332w 1357m DAPY, DDQ
1305m 1302mw 1305m 1300m And chloranil
1270m 1244w 1272mw 1260shoul
1170wm 1174m (CAC); TCNE and DDQ
1155w 1141m
1113s Chloranil; characteristic band
1065 m 1078 m (CAN); DAPY
985w 985w 988w (CH) deformation; DAPY
967 959wm
853m 902ms (CH); out of plane wag; free and complexed DAPY
834m
792ms 783m 780w
744m 769w 751mw 754m (NH2); DAPY
713m (CACl); chloranil
566m 579vw 568w 565m (CH); out of plane ring bending; free and complexed DAPY
546shoul 555w 532m
480m 536w 512w 490w 478w
m, medium; s, strong; shoul, shoulder; w, weak; , stretching; , bending.
 H.S. Bazzi et al. / Journal of Molecular Structure 842 (2007) 1–5
Fig. 7. Infrared absorption spectra of: (A) 2,6-DAPY, (B) [(2,6-
DAPY)(TCNE)3], (C) [(2,6-DAPY)(DDQ)2], and (D) [(2,6-
DAPY)(chloranil)].
of the aromatic ring does not show pronounced changes
upon complexation, it is always observed around
1650 cm¡1. Similar conclusions were reported in the CT-
interactions of the related donor 2,3-diaminopyridine
with the acceptors iodine, TCNE, and chloranil [13,14].
5
4. Conclusion
Charge-transfer interactions between the donor 2,6-diami-
nopyridine and the -acceptors TCNE, DDQ, and chloranil
were studied in CHCl3. We were able to the show that the
reaction stoichiometry is diVerent from one acceptor to
another, and the resulting CT-complexes were shown to have
the formulas: [(2,6-DAPY)(TCNE)3], [(2,6-DAPY)(DDQ)2],
and [(2,6-DAPY)(chloranil)]. Our obtained results indicate
that the two-NH2 groups of 2,6-diaminopyridine are
involved in the complexation with acceptors rather than the
nitrogen of the aromatic ring. Future studies will focus on
using diVerent acceptors and donors to further investigate
the nature of such complexations.
References
[1] L.L. Rodina, V.A. Ryzhakov, Heterocycles 1035 (1995) 40.
[2] H. Skurai, A. Izuoka, T. Sugawara, Mol. Cryst. Liquid Cryst. Sci.
Techol., Sect. A 415 (1997) 306.
[3] S.Y. AlQaradawi, E.M. Nour, J. Mol. Struct. 251 (2006) 794.
[4] A.M. Biasutti, D.J. Anunziata, J.J. Silber, Spectrochim. Acta (A) 169
(1992) 48.
[5] J. Casaszar, Acta Phys. Chem. 29 (1998) 34.
[6] E.M. Nour, Spectrochim. Acta (A) 167 (2000) 56.
[7] P.J. Trotter, P.A. White, Appl. Spectrosc. 323 (1978) 32.
[8] E.M. Nour, L.H. Chen, J. Laane, J. Raman Spectrosc. 467 (1986) 17.
[9] E.M. Nour, A.S. Barakat, A. Amer, A. Ebrahim, Spectrosc. Lett. 115
(1999) 32.
[10] S.Y. AlQaradawi, E.M. Nour, Spectrochim. Acta (A) 578 (2005) 62.
[11] E.M. Nour, S.M. Metwally, M.A.F. ElMosallamy, Y. Gameel, Spec-
trosc. Lett. 115 (1999) 32.
[12] E.M. Nour, L.A. Shahada, A. Sadeek, S.M. Teleb, Spectrochim. Acta
(A) 471 (1995) 51.
[13] S.Y. AlQaradawi, E.M. Nour, Spectrosc. Lett. 337 (2004) 37.
[14] N.A. Al-Hashimi, Spectrochim. Acta (A) 2181 (2004) 60.
[15] D.A. Skoog, F.J. Holler, T.A. Nieman, Principle of Instrumental Analy-
sis, Wfth ed., vol. 347, Saunders College Publishing, New York, 1992.