Synthesis, characterization and dielectric properties of phosphazenes containing chalcones

Article abstract of DOI:10.1016/j.poly.2014.04.070

The new hexasubstitue-cyclophosphazene compounds containing chalcone derivatives (2-11) were obtained from the reactions of hexachlorocyclotriphosphazene (1) with several hydroxy chalcones in K ₂CO₃/acetone system. All products were generally obtained in high yields. The structures of the compounds were defined by elemental analysis, FT-IR, ¹H, ¹³C and ³¹P NMR spectroscopy. Dielectric measurements for phosphazenes containing chalcone compounds (5-8) were carried out by means of an impedance analyzer as a function of temperature and frequency. Dielectric properties of samples prepared in a plate form were measured at room temperature over the frequency range 50 Hz to 2 kHz and given as compared with each other.

Full text of DOI:10.1016/j.poly.2014.04.070

Accepted Manuscript
Synthesis, Characterization and Dielectric Properties of Phosphazenes Contain-
ing Chalcones
Kenan Koran, Furkan Özen, Gülben Torğut, Güzin Pıhtılı, Erol Çil, A. Orhan
Görgülü, Mustafa Arslan
PII:
S0277-5387(14)00316-7
DOI:
http://dx.doi.org/10.1016/j.poly.2014.04.070
POLY 10732
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
10 February 2014
24 April 2014
Please cite this article as: K. Koran, F. Özen, G. Torğut, G. Pıhtılı, E. Çil, A. Orhan Görgülü, M. Arslan, Synthesis,
Characterization and Dielectric Properties of Phosphazenes Containing Chalcones, Polyhedron (2014), doi: http://
dx.doi.org/10.1016/j.poly.2014.04.070
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Synthesis, Characterization and Dielectric Properties of Phosphazenes Containing
Chalcones
Kenan Korana,*, Furkan Özena, Gülben Torꢀuta, Güzin Pıhtılıa, Erol Çilb, A. Orhan Görgülüa,
Mustafa Arslanc
aChemistry Department, Science Faculty, Firat University, 23169, Elazig, Turkey
bScience Education Department, Education Faculty, Firat University, 23169, Elazig, Turkey
cScience Education Department, Education Faculty, Yildiz Technical University, Istanbul,
Turkey
*Correspondence; Department of Chemistry, Firat University, 23119, Elazig, Turkey,
E-mail:kenan.koran@gmail.com,
Fax: (+90) 424 2330062
ABSTRACT
The new hexasubstitue-cyclophosphazene compounds containing chalcone derivatives (2-11)
were obtained from the reactions of hexachlorocyclotriphosphazene (1) with several hydroxy
chalcones in K2CO3/acetone system. All products were generally obtained in high yields. The
structures of the compounds were defined by elemental analysis, FT-IR, 1H, 13C and 31P NMR
spectroscopy. Dielectric measurements for phosphazenes containing chalcone compounds (5-
8) were carried out by means of an impedance analyzer as a function of temperature and
fruquence. Dielectric properties of samples prepared in a plate form were measured at room
temperature over the frequency range 50 Hz–2 kHz and given as compared with each other.
Keywords: Hexachlorocyclotriphosphazene, Chalcone-Phosphazenes, Dielectric Properties
1

1. Introduction
Phosphazenes are compounds containing a phosphorus-nitrogen double bond in their
skeleton. They are also known as iminophosphoranes and phosphine imides. Phosphazenes
fall into three categories: the cyclo-, poly-, and monophosphazenes. The cyclo- and
polyphosphazenes probably are the best known and most intensively studied phosphorus-
nitrogen compounds because they are more stable than monophosphazenes[1]. The properties
of phosphazene materials can be varied over a broad range by attaching different substituents
to the main backbone[2]. The synthesis of phosphazene compounds has become significant,
because phosphazene compounds have many potential applications, including biomaterials[3],
drug delivery systems[4,5], fuel cell membranes[6,7], ionic conductors[8], flame retardants[9]
and optical materials[10,11]. The study of gas permeability and seperations of phosphazene
derivatives membrane such as (NPR2)n or (NPR1R2)n has received special attention in
industrial and academic research[11]. For example, polyphosphazenes containing suitable side
groups can be used as membrane seperators in the field of gas permeation[12], organic liquid
seperation and evaporation[13-16], ion seperation[17], ultra filtration[18] and micro
filtration[19]. Cyclophosphazenes such as N3P3Az6, N4P4Az8 and N4P4pyro8 were reported to
have the function of anticancer agents[20-24]. It has been demonstrated that some
phosphazenes were suitable for development of implantable antitumor devices[11,25].
Chalcones are an important class of natural compounds. They are precursors in flavonoid
biosynthesis and they also play an ecological role in relation to plant colour [26,27]. Synthetic
chalcones and their heterocyclic analogues are most commonly prepared by means of various
modifications of the Claisen–Schmidt condensation[28,29]. Another general route involves
the Friedel–Crafts acylation of a substituted aromatic compound with a substituted cinnamoyl
chloride derivative[30]. Due to the presence of the reactive ketovinylenic group in their
molecules chalcones and their analogues exhibit various biological activities, such as
antibacterial[31-33],
antiviral[34],
antiprotozoal[35],
antifungal[36,37],
anti-
inflammatory[30,38], and antineoplastic[39]. The mode of antibacterial action has been
suggested to be by the reaction of chalcones with important thiol groups on essential
enzymes[31,40].
Dielectric constant measurements are one of the most popular methods of evaluating solid
materials such as electric insulators and polymers, because dielectric constant measurements
can be performed easier than chemical analysis techniques. Impedance spectroscopy is a
relatively new and powerful method of characterizing many of the electrical properties of
2

electrolyte materials and their interfaces with electronically conducting electrodes.
Permittivity of a material describes its ability to absorb, transmit and reflect electromagnetic
energy. Permittivity is a complex quantity, consisting of the dielectric constant (ꢁ) and the
dielectric loss factor (εꢂ), where ꢁ is the real component and is related to the capacitance of
the substance and its ability to store electrical energy and εꢂ is the imaginary component and
is related to various absorption mechanisms of energy dissipation[41-43].
The literature contains reports on the synthesis of different linear, cyclic or poly
phosphazenes[44-57]. There are limited reports (only three reports) in literature on the
synthesis of phosphazenes containing chalcone derivatives[58-60].
In view of the important properties of the chalcone derivatives and phosphazene
compounds, it was planned to the synthesis of some new phosphazene derivatives bearing
different chalcones, such derivatives could possess interesting and useful properties. In this
study, 4'-hydroxy chalcones were prepared by reaction of 4-hydroxyacetophenone with
different benzaldehydes according to a method reported in the literature[28,29]. New
cyclophosphazenes containing chalcones were hereby isolated for the first time from the
reactions of (1) with 4'-hydroxy chalcones in acetone in the presence of K2CO3. Dielectric
properties of the compounds 5-8 were also investigated in this study. The dielectric constant
and dielectric loss behaviour of the investigated samples were studied as a function of
frequency. The conductance (Gp) parameter, was measured as a function of frequency in the
range from 50 Hz to 2 kHz, in the room temperature (25oC).
2. Experimental
2.1. Materials
Solvents
and
other
liquids
were
dried
by
conventional
methods.
Hexachlorocyclotriphosphazene was recrystallized from hexane. Other chemicals were used
as purchased. 4'-hydroxy chalcones were prepared by reaction of 4-hydroxyacetophenone
with different benzaldehydes according to a method reported in the literature[28,29]. The
reactions of (1) with hydroxy chalcones were carried out under dry nitrogen. The deuterated
solvents (Chloroform-d and DMSO-d6) for NMR spectroscopy and the following chemicals
were obtained from Merck; acetone, ethanol, K2CO3, anhydrous MgSO4, NaOH, KOH,
CH2Cl2 and silica gel 60.
3

2.2. Equipment
FT-IR spectra were recorded on an Perkin Elmer FT-IR spectrometer. Microanalysis was
1
carried out by a LECO 932 CHNS-O apparatus. H, 13C, and 31P NMR spectra were recorded
1
using a Bruker DPX-400 spectrometer. The H, 13C and 31P NMR chemical shifts were
measured using tetramethylsilane as an internal standard, whereas those for 31P were
measured using 85% H3PO4 as an external standard. For the NMR studies, the DMSO-d6 was
used as solvent for the compounds 3, 6, 7 and 11. The chloroform-d was used as solvent for
the compounds 2, 4, 5, 8, 9 and 10. Chemical shifts down field from the standard were
assigned positive δ values. In the results of NMR spectra, s, d, t and m indicate singlet,
doublet, triplet and multiplet respectively. Dielectric properties were carried out at room
temperature with a QuadTech 7600 precision LRC Meter impedance analyzer over the
frequency range 50 Hz–2 kHz.
2.3. Synthesis
2.3.1.General Synthetic Procedures for 4'-hydroxy chalcones
4'-hydroxy chalcones were prepared according to a method reported in the
literature[28,29]. The general method for the synthesis of 4’-hydroxy chalcones is stated as
below:
To a solution of 4’-hydroxyacetophenone in ethanol (10 mL/mmol) was added the
appropriate substituted aldehyde ( 1.5 equiv). The mixture was stirred for 15 min, followed by
0
addition of an aqueous solution KOH (3 equiv) at 0 C. The mixture was refluxed overnight.
After the reaction reached completion, it was quenched with water (20 mL). The resulting
mixture was concentrated in vacuo, diluted with water (50 mL), acidified with 1 M HCl to pH
3, and extracted with ethyl acetate. The organic layer was dried over MgSO4 and concentrated
in vacuo. The residual solid was purified by column chromatography to yield the desired
product.
2.3.2.Synthesis of Compound ( 2 )
A mixture of hexachlorotriphosphazene (1) (1.0 g, 2.88 mmol), 4'-hydroxychalcone (a)
(5.16 g, 23.01 mmol) and K2CO3 (3.18 g, 23.01 mmol) was stirred in acetone (100 mL) at 0
oC and then was reacted at ambient temperature for 24 h. The solvent was removed under
vacuum. The residue was extracted with CH2Cl2 (4x25 mL). The solvent was concentrated on
a rotary evaporator under reduced pressure. The residue was dissolved in chloroform and
4

washed with 10% NaOH solution for three times and then with water, dried over anhydrous
magnesium sulfate. The solvent was concentrated on a rotary evaporator under reduced
pressure. After the solvent was removed, a white solid (2) formed 3.48 g (82%). Anal. Calc.
for [C90H66N3O12P3] (MW= 1474.42): found: C, 73.01; H, 4.59; N, 2.88%; requires; C, 73.31;
H, 4.51; N, 2.85%. FT-IR (KBr,cm-1): 3059 and 3001 νAr-CH, 2923 νAliphatic-CH, 1657 νC=O
1598, 1574 and 1500 νC=C, 1183 and 1207 νP=N, 1287 νP-N-P, 949 νP-O-C
31P NMR (CDCl3)
,
.
δ/ppm: 8.27 (s). 1H NMR (CDCl3) δ/ppm: 7.93 ( 12H, d, H3 ), 7.73 ( 6H, d, H7 ), 7.60 ( 12H, t,
H10 ), 7.51 ( 6H, d, H6 ),7.41-7.43 ( 18H, m, H9 and H11), 7.12 ( 12H, d, H2 ), 13C NMR
(CDCl3) δ/ppm: 188.59 C5, 153.27 C1, 145.24 C7, 135.41 C8, 134.46 C4, 130.52 C3, 130.18
C10, 128.72 C9, 128.56 C11, 120.89 C6, 120.81 C2.
The same general procedure gave coumpounds (3-11), with scale (gram, mmol [b-m]),
reaction times, yield, and spectroscopy data given below.
2.3.3.Synthesis of Compound ( 3 )
4'-hydroxy-4-methoxychalcone (b) (5.85 g, 23.01 mmol), 24 h. Yield: 3.81 g, 80%. Anal.
Calc. for [C96H78N3O18P3] (MW= 1654.57): found: C, 69.72; H, 4.71; N, 2.49%; requires; C,
69.69; H, 4.75; N, 2.54%. FT-IR (KBr, cm-1): 3065 and 3000 νAr-CH, 2932 νAliphatic-CH, 1660
νC=O, 1597, 1571 and 1511 νC=C, 1178 and 1202 νP=N, 1293 νP-N-P, 947 νP-O-C.
31P NMR
(DMSO-d6) δ/ppm: 8.39 (s). 1H NMR (DMSO-d6) δ/ppm: 7.88 ( 12H, d, H3 ), 7.67 ( 6H, d, H7
), 7.52 ( 6H, d, H6 ), 7.35 ( 12H, d, H9), 7.07 ( 12H, d, H2 ), 6.90 ( 12H, d, H10 ), 3.84 (18H, s,
13
H14 ), C NMR (DMSO-d6) δ/ppm: 188.61 C5, 161.58 C11, 152.84 C1, 145.07 C7, 135.64 C4,
130.41 C3, 130.09 C8, 127.24 C9, 120.86 C2, 118.45 C6, 114.13 C10, 055.26 C14 .
2.3.4.Synthesis of Compound ( 4 )
4'-hydroxy-2-methoxychalcone (c) (5.85 g, 23.01 mmol), 24 h. Yield: 3.33 g, 70%. Anal.
Calc. for [C96H78N3O18P3] (MW= 1654.57): found: C, 69.67; H, 4.77; N, 2.51%; requires; C,
69.69; H, 4.75; N, 2.54%. FT-IR (KBr,cm-1): 3071 and 3000 νAr-CH, 2936 νAliphatic-CH, 1660
νC=O, 1598, 1572 and 1501 νC=C, 1181 and 1203 νP=N, 1287 νP-N-P, 947νP-O-C.
31P
1
NMR(CDCl3) δ/ppm: 7.94 (s). H NMR (CDCl3) δ/ppm: 8.08 ( 6H, d, H7 ), 7.96 ( 12H, d, H3
), 7.67 ( 6H, d, H13 ), 7.60 ( 6H, d, H6), 7.37 ( 6H, t, H11), 7.14 ( 12H, d, H2 ), 6.99 ( 6H, t, H12
), 6.91 ( 6H, d, H10 ), 3.87 (18H, s, H14 ), 13C NMR (CDCl3) δ/ppm: 188.66 C5, 169.39 C9,
5

151.33 C1, 145.44 C7, 135.66 C4, 129.38 C3, 129.35 C12, 129.14 C6, 128.01 C11, 126.14 C13,
119.99 C2, 118.23 C6, 116.39 C10, 050.46 C14 .
2.3.5.Synthesis of Compound ( 5 )
4'-hydroxy-2-fluorochalcone (d) (5.57 g, 23.01 mmol), 24 h. Yield: 3.41 g, 75%. Anal.
Calc. for [C90H60F6N3O12P3] (MW= 1582.36): found: C, 68.23; H, 3.85; N, 2.69%; requires;
C, 68.31; H, 3.82; N, 2.66%. FT-IR (KBr,cm-1): 3063 and 3001 νAr-CH, 2956 νAliphatic-CH, 1665
νC=O, 1605, 1576 and 1502 νC=C, 1184 and 1207 νP=N, 1282 νP-N-P, 952 νP-O-C.
31P
NMR(CDCl3) δ/ppm: 7.97 (s). 1H NMR (CDCl3) δ/ppm: 7.98 ( 12H, d, H3 ), 7.74 ( 6H, d, H7
), 7.68 ( 6H, t, H11 ), 7.58 ( 6H, d, H13 ),7.48 ( 6H, d, H6), 7.14-7.19 ( 18H, m, H2 and H12 ),
7.107 (6H, d, H10), 13C NMR (CDCl3) δ/ppm: 188.65 C5, 163.03 C9, 153.62 C1, 137.83 C7,
135.36 C4, 132.05 C3, 130.44 C8, 129.70 C11, 124.52 C13, 122.87 C6, 121.03 C2, 116.31 C12,
116.09 C10.
2.3.6.Synthesis of Compound ( 6 )
4'-hydroxy-3-fluorochalcone (e) (5.57 g, 23.01 mmol), 24 h. Yield: 3.18 g, 70%. Anal.
Calc. for [C90H60F6N3O12P3] (MW= 1582.36): found: C, 68.36; H, 3.85; N, 2.70%; requires;
C, 68.31; H, 3.82; N, 2.66%. FT-IR (KBr,cm-1): 3061 νAr-CH, 2956 and 2920 νAliphatic-CH, 1665
νC=O, 1607, 1581 and 1503 νC=C, 1190 and 1206 νP=N, 1271 νP-N-P, 953 νP-O-C.
31P NMR
1
(DMSO-d6) δ/ppm: 7.99 (s). H NMR (DMSO-d6) δ/ppm: 8.09 ( 12H, d, H3 ), 7.91( 6H, d,
H11 ), 7.75 ( 6H, d, H7), 7.56-7.65 ( 12H, m, H6 and H12), 7.45 ( 6H, d, H13), 7.26 ( 6H, s, H9),
7.19 (12H, d, H2), 13C NMR (DMSO-d6) δ/ppm: 187.95 C5, 161.66 C10, 153.44 C1, 143.25
C7, 137.52-137.44 C4 and C8, 135.18 C12, 131.25 C3, 126.06 C9, 123.23 C13, 121.18 C6,
117.91 C11, 115.18 C2.
2.3.7.Synthesis of Compound ( 7 )
4'-hydroxy-4-fluorochalcone (f) (5.57 g, 23.01 mmol), 24 h. Yield: 3.86 g, 85%. Anal.
Calc. for [C90H60F6N3O12P3] (MW= 1582.36): found: C, 68.36; H, 3.85; N, 2.70%; requires;
C, 68.31; H, 3.82; N, 2.66%. FT-IR (KBr,cm-1): 3062 νAr-CH, 2956 and 2917 νAliphatic-CH, 1666
νC=O, 1606, 1577 and 1503 νC=C, 1182 and 1207 νP=N, 1282 νP-N-P, 953 νP-O-C.
31P
NMR(DMSO-d6) δ/ppm: 7.97 (s). 1H NMR (DMSO-d6) δ/ppm: 7.99 ( 12H, d, H3 ), 7.68 ( 6H,
13
d, H7 ), 7.59 ( 6H, d, H6 ), 7.38 ( 12H, d, H9), 7.23 ( 12H, d, H2 ), 7.12 ( 12 H, d, H10 ), C
6

NMR (DMSO-d6) δ/ppm: 188.66 C5, 160.49 C11, 153.59 C1, 137.85 C7 ,135.35 C4, 132.08
C9,13, 130.46 C3, 129.84 C8, 122.85 C2, 121.05 C6, 116.32 C10,12
.
2.3.8.Synthesis of Compound ( 8 )
4'-hydroxy-2-chlorochalcone (g) (5.95 g, 23.01 mmol), 18 h. Yield: 4.01 g, 83%. Anal.
Calc. for [C90H60Cl6N3O12P3] (MW= 1681.09): found: C, 64.36; H, 3.57; N, 2.53%; requires;
C, 64.30; H, 3.60; N, 2.50%. FT-IR (KBr,cm-1): 3064νAr-CH, 2958 νAliphatic-CH, 1663 νC=O
1599, 1562 and 1500 νC=C, 1182 and 1206 νP=N, 1271 νP-N-P, 946 νP-O-C
31P NMR (CDCl3)
,
.
δ/ppm: 8.10 (s). 1H NMR (CDCl3) δ/ppm: 8.19 ( 6H, d, H7 ), 7.94 ( 12H, d, H3 ), 7.88 ( 6H, t,
H13 ), 7.50 ( 6H, d, H6 ),7.42 ( 6H, t, H11), 7.33-7.36 ( 12H, m, H10 and H12 ), 7.12 (12 H, d,
H2), 13C NMR (CDCl3) δ/ppm: 188.66 C5, 153.57 C1,141.12 C7, 135.61 C8, 135.32 C4, 132.90
C9, 131.40 C12, 130.49 C3, 130.20 C10, 127.99 C13, 127.18 C11, 123.66 C6, 121.09 C2.
2.3.9.Synthesis of Compound ( 9 )
4'-hydroxy-2-methylchalcone (h) (5.48 g, 23.01 mmol), 15 h. Yield: 3.40 g, 76%. Anal.
Calc. for [C96H78N3O12P3] (MW= 1558.58): found: C, 73.95; H, 5.10; N, 2.74%; requires; C,
73.98; H, 5.04; N, 2.70%. FT-IR (KBr,cm-1): 3059 and 3016 νAr-CH, 2950 and 2923 νAliphatic-
CH, 1662 νC=O, 1596, 1570 and 1500 νC=C, 1181 and 1204 νP=N, 1295 νP-N-P, 947 νP-O-C.
31P
NMR (CDCl3) δ/ppm: 7.97 (s). 1H NMR (CDCl3) δ/ppm: 8.11 ( 6H, d, H7), 7.97 ( 12H, d, H3
), 7.80 ( 6H, d, H13 ), 7.46 ( 6H, d, H6 ),7.20-7.33 ( 18H, m, H10, H11 and H12), 7.15 ( 12H, d,
H2 ), 2.38 ( 18H, s, H14 ), 13C NMR (CDCl3) δ/ppm: 188.65 C5, 153.53 C1,142.87 C7, 138.56
C8, 135.60 C4, 133.64 C9, 130.88 C12, 130.44 C10, 130.39 C3, 126.61 C13, 126.38 C11, 122.03
C6, 120.98 C2, 019.77 C14.
2.3.10. Synthesis of Compound ( 10 )
4'-hydroxy-3-methylchalcone (k) (5.48 g, 23.01 mmol), 15 h. Yield: 3.09 g, 69%. Anal.
Calc. for [C96H78N3O12P3] (MW= 1558.58): found: C, 73.81; H, 5.01; N, 2.74%; requires; C,
73.98; H, 5.04; N, 2.70%. FT-IR (KBr,cm-1): 3059 and 3016 νAr-CH, 2949 and 2921 νAliphatic-
CH, 1659 νC=O, 1602, 1574 and 1502 νC=C, 1183 and 1205 νP=N, 1269 νP-N-P, 950 νP-O-C.
31P
NMR (CDCl3) δ/ppm: 7.97 (s). 1H NMR (CDCl3) δ/ppm: 7.93 ( 12H, d, H3 ), 7.69 ( 6H, d, H7
), 7.49 ( 6H, d, H6 ), 7.41 ( 6H, d, H13 ), 7.29-7.34 ( 12H, m, H9 and H12), 7.26 (6H, d, H11 ),
7.12 (12H, d, H2 ), 2.41 (18H, s, H14 ), 13C NMR (CDCl3) δ/ppm: 188.81 C5, 153.40 C1,
7

145.64 C7, 138.52 C8, 135.66 C4, 134.61 C10, 131.54 C9, 130.36 C3, 129.44 C11, 128.78 C12,
125.93 C13, 121.08 C6, 120.75 C2, 021.35 C14 .
2.3.11. Synthesis of Compound ( 11 )
4'-hydroxy-4-nitrochalcone (m) (6.20 g, 23.01 mmol), 10 h. Yield: 3.01 g, 60%. Anal.
Calc. for [C90H60N9O24P3] (MW= 1744.41): found: C, 62.01; H, 3.41; N, 7.30%; requires; C,
61.97; H, 3.47; N, 7.23%. FT-IR (KBr,cm-1): 3062 and 3032 νAr-CH, 2947 and 2923 νAliphatic-
CH, 1668 νC=O, 1612, 1598, and 1515νC=C, 1193 and 1209 νP=N, 1287 νP-N-P, 955 νP-O-C.
31P
1
NMR (DMSO-d6) δ/ppm: 7.95 (s). H NMR (DMSO-d6) δ/ppm: 8.15 ( 12H, d, H3 ), 8.09 (
12H, d, H10), 7.95-8.01 ( 18H, m, H7 and H9), 7.68 (6H, d, H6 ), 7.22 ( 12H, d, H2 ), 13C NMR
(DMSO-d6) δ/ppm: 187.75 C5, 153.56 C1, 148.35 C11, 141.77 C8, 141.30 C7, 134.93 C4,
131.33 C10, 130.25 C3, 125.67 C6, 124.19 C9, 121.20 C2.
2.4. Dielectric Properties
Dielectric studies on organic–inorganic hybrid material, which posses the excellent
properties of both organic and inorganic compounds, are recently extensively investigated.
Dielectric constant and dielectric loss measurements were performed on pellet sample of
compounds 5-8. The pellet was prepared from the pure powder sample through high-pressure
of 5.0 MPa. The pressed-powder pellets deposited with carbon conducting glue were used for
dielectric investigation. The capacitance of electrodes which was made by imitating the
parallel-plate capacitor was measured with different frequencies. The dielectric constant and
dielectric loss have been calculated using Eqs. (1) and (2):
where ꢃ′ is the dielectric constant, ε0 is the dielectric constant of vacuum (8,854ꢄ10-12 ), d is
the thickness (m) and A is the area (m2) of the sample and C is the capacitance (F) of test
device. The frequency dependent dielectric was measured with frequency of 50 Hz to 2 kHz
at room temperature.
2.4.1. Electrical properties
The ac electrical conductivity of the samples has been studied. Conductance (Gp) is a
measure of how easily electricity flows along a certain path through an electrical element. The
8

SI derived unit of conductance is the Siemens[61]. The frequency utilized in the study was
from 50 Hz to 2 kHz. The measured conductance, Gp from 50 Hz up to 2 kHz was used to
calculate ac conductivity, ꢅ(ꢆ) using the following expression:
where d is the thickness of the sample and A is the cross-sectional area of the electrode. Fig. 5
shows the ac electrical conductivity of composite films.
3. Results and discussion
The reactions of (1) with 6.1 equiv. of hydroxy chalcones in the presence of K2CO3 in
acetone gave hexasubstituted products (2-11). The structures of the compounds were
13
31
elucidated by FT-IR, 1H, C and P NMR spectroscopy as well as by elemental analysis. All
products were generally obtained in high yields. General presentation of the all reactions is
shown in Scheme 1 and structures of the compounds 2–11 are shown in Scheme 2.
The characteristic stretching peaks in the FT-IR spectra of the phosphazenes have been
assigned as in experimental section. The P=N stretching vibrations, which are observed
between 1186 and 1193 cm–1, are characteristic of cyclophosphazenes. These peaks are
shifted to longer wavelengths for 2–11 than in (1), which appeared at 1218 cm–1. The absence
of the OH stretching vibration in the FT-IR spectra of 2–11 indicates that all hydrogen atoms
of the OH groups have been replaced. In similarly, in the FT-IR spectra of 2–11, the P-O-C
stretching vibrations which were observed between 945 and 955 cm-1 and the C=O stretching
vibrations which were observed between 1657 and 1666 cm-1 also indicate the hexasubstitue
phosphazene compounds.
The NMR data of compounds 2-11 were given in experimental section. Example spectra
(1H and 13C NMR spectra of 2) was presented in Fig.1,2. As expected, there is one peak in
the 31P NMR spectra of 2-11. These single peaks which were observed between 7.94 and 8.39
ppm in the 31P NMR spectra of 2-11 confirm the structures of 2–11.
The 1H and 13C NMR data also confirm the structures of 2–11 (Scheme 2). In the 1H NMR
spectra of 2-11, the absence of the OH protons indicates the hexasubstitue phosphazene
products. The aliphatic CH protons which were numbered as 6 and 7 in all compounds were
observed between 7.46 and 7.68 ppm and 7.67 and 8.11 ppm respectively. The methyl protons
9

for the compounds 3, 4, 9 and 10 were observed at 3.84, 3.87, 2.38 and 2.41 ppm respectively.
The aromatic protons for all the compounds appear between 6.90 and 8.19 ppm.
The detailed 13C NMR spectral data were given in experimental section. The carbonyl
carbon atoms for 2-11 were observed at 1657, 1660, 1660, 1665, 1665, 1666, 1663, 1662,
1659 and 1666 cm-1 respectively. The methyl carbons for the compounds 3, 4, 9 and 10 were
observed at 55.26, 50.46, 19.77 and 21.35 ppm respectively. For the compounds 2-11, the
aliphatic carbons which were numbered as 6 in all compounds were observed at 120.89,
118.45, 118.23, 122.87, 121.18, 121.05, 123.66, 122.03, 121.08 and 125.67 ppm respectively,
while the aliphatic carbons which were numbered as 7 in all compounds were observed at
145.24, 145.07, 145.44, 137.83, 143.25, 137.85, 141.12, 142.87, 145.64 and 141.30 ppm
respectively. Real and imaginary parts of the dielectric constant (ꢃ′, ꢃꢂ), ac conductivity (σac)
of phosphazenes containing chalcones have been calculated in wide frequency a range of 50
Hz–2 kHz at room temperature. The graphical results of dielectric constant, dielectric loss and
conductivity for samples (5,6,7 and 8) are presented in Figs.3, 4 and 5 respectively.
The frequency dependence of dielectric constant measurement shows that as the frequency
increases, the dielectric constant drops sharply and drives to stability is shown Fig.3. This
behavior would be supported by the facts that atoms would be consistent with the direction
change of AEF (alternating electric field) at low frequencies, while in higher frequencies, the
dipole reversal can not keep up with the AEF frequency change, so the ε′ decreases with the
increase of frequency. The dielectric loss (εꢂ/ ꢃ′) remains the similar trend with ꢃ′. As seen
Fig.4 ꢃꢂ decreases with increasing frequency. The decrease in ꢃ′ and ꢃꢂ with increasing
frequency indicated that the interfacial dipoles have less time to orient themselves in the
direction of the alternate field [62]. As a results, the low-frequency region is attributed to the
contribution of charge accumulation at the interface. At high frequencies, due to high periodic
reversal of the field at the interface, the contribution of the charge carriers to the dielectric
constant decreases with increasing frequency [63]. Results of the real part (ꢃ′) is maximum
value showed Table 1.
Fig. 5 shows the variation of the conductivity (ꢅ) with frequency at room temprature for
compound 5-8. The ac conductivity increases with increase of the frequency over a wide
frequency range. The rise of conductivity upon increasing the frequency is a common respond
for polymeric and semiconductor samples[64]. It is due to the tremendous increase of the
mobility of charge carriers in the composite film. As shown in Fig.5, there are two trends
appeared, the first one (from 50 Hz up to 500 Hz) is frequency dependent conductivity and
another (from 500 Hz up to 2 kHz) is frequency independent conductivity. The first trend is
10

contributed by free charges available in the composite system whereas the second, which is
frequency dependent conductivity, is due to trapped charges which is only active at higher
frequency region [65,66]. The maximum conductivity has been found to be respectively
7.3x10-10 S/cm 3.51×10−9 S/cm, 4.97×10−9 S/cm and 2.39×10−9 S/cm at the room temperature
for 5,6, 7 and 8. These Phosphazenes Containing Chalcones have conjugated structure and
where there are many of ꢇ-electrons. Thus we believe that this conjugated structure causing
electrical conductivity. The conjugated double bonds of the compound create a decrease in the
system’s internal energy and apparently allow electron transfer for electronic conduction[67].
All of these parameters were found strong function of frequency and voltage especially in
the inversion and depletion regions at low frequencies due to space charge polarization and
charges at interface states. All of the results are compatible with literature [68,69].
4. Conclusion
In summary, the chalcone substituted cyclotriphosphazene compounds (2–11) were
synthesized for the first time by using of K2CO3/acetone system. All the compounds were
generally obtained in high yields. Comprehensive studies of the AC conductivity, the
dielectric properties of the compound 5-8 have been performed. The conductivity
measurements were sensitivity between 10-9 and 10-10 Siemens. AC conductivity, the
dielectric constant and the dielectric loss of the studied compound seem likely to be frequency
dependent. The dielectric constant and dielectric loss of the sample decrease with increasing
frequency. AC conductivity increase with increasing frequency.
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15

O
CH
O
3
KOH
HO
EtOH
+
O
HO
R
R
( a-m )
a
b
c
d
e
f
g
h
k
m
-H
p-OCH3 o-OCH3
o-F
m-F
p-F
o-Cl
o-CH3
m-CH3
p-NO2
R
R
R
O
O
R
R
O
Cl
Cl
O
O
P
N
P
N
N
P
N
THF
N
N
+
Cl
6
O
Cl
P
K2CO3
O
O
P
P
HO
Cl
Cl
O
O
O
R
( 1 )
O
O
2
3
4
5
6
7
8
9
10
11
-H p-OCH3 o-OCH3 o-F m-F
p-F
o-Cl o-CH3 m-CH3 p-NO2
R
R
R
( 2-11 )
Scheme 1. General Presentation of the all reactions.

O
4
O
4
5
3
6
9
9
10
10
5
3
6
9
9
10
10
3
1
7
8
11
3
1
7
8
11
O
N3P3
N3P3
2
2
CH3
12
2
2
O
O
( 2 )
( 3 )
O
O
4
5
3
6
13
9
12
5
3
6
13
9
12
10
3
1
4
2
7
8
11
3
1
7
8
11
N3P3
2
10
N3P3
2
O
F
2
CH3
O
14
O
( 4 )
( 5 )
O
4
O
4
5
3
6
9
9
10
10
5
3
6
13
12
10
3
1
7
8
11
F
3
1
7
8
11
N3P3
N3P3
2
2
9
2
2
F
O
O
( 7 )
( 6 )
O
O
4
5
3
6
13
9
12
10
5
3
6
13
9
12
10
3
1
4
2
7
8
11
3
1
7
8
11
N3P3
N3P3
2
2
Cl
H3C
2
14
O
O
( 8 )
( 9 )
O
4
O
4
5
3
6
9
9
10
10
5
3
6
13
9
12
10
3
1
7
8
11
NO2
3
1
7
8
11
N3P3
N3P3
2
2
2
2
CH3
14
O
O
( 11 )
( 10 )
Scheme 2. Structures of the compounds 2-11.

Fig. 1. 1H-NMR Spectrum of Compound 2 (chloroform-d).

Fig. 2. 13C-NMR Spectrum of Compound 2 (chloroform-d).

Fig. 3. 13C-NMR Spectrum of Compound 2 (chloroform-d).

0.5
0.45
0.4
Compound 8
Compound 6
Compound 7
Compound 5
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0
500
1000
Frequency (Hz)
1500
2000
Fig. 4. The variation of the dielectric loss with frequency at room temprature

6E-09
5E-09
4E-09
3E-09
2E-09
1E-09
0
Compound 8
Compound 7
Compound 6
Compound 5
0
500
1000
1500
2000
2500
Frequency (Hz)
Fig. 5. The variation of the conductivity ( σ) with frequency at room temprature

R
R
O
O
R
R
O
O
P
N
N
P
N
P
O
O
O
O
O
O
O
O
R
R
( 2-11
)
2
3
4
5
6
7
8
9
10
11
-H
p-OCH3
o-OCH 3
o-F
m-F
p-F
o-Cl
o-CH3 m-CH3 p-NO2
R

The new cyclophosphazene compounds containing chalcone derivatives (2-11) were obtained
from the reactions of hexachlorocyclotriphosphazene (1) with several hydroxy chalcones in
K2CO3/acetone system. All products were generally obtained in high yields. Dielectric
properties of the synthesized compuonds were also investigated.

Table 1. Results of the ε', εꢂ and ꢅ are maximum value for compound 5-8
Compound
ε'
εꢂ
ꢅ (S/cm)
7.3×10-10
2.95×10−9
5.01×10−9
2.39×10−9
2.61
1.69
2.45
1.62
0.042
0.026
0.046
0.019
(5)
(6)
(7)
(8)
16