Synthesis of fluorescence organocyclotriphosphazene derivatives having functional groups such as formyl, Schiff base and both formyl and Schiff base without using Ar or N2 atmosphere

Article abstract of DOI:10.1016/j.molstruc.2017.01.047

In the present study, hexa(4-formyl-phenoxy)cyclotriphosphazene(2) and hexa(4-formyl-2-methoxy-phenoxy)cyclotriphosphazene(3), which were previously synthesized in boiling solvent under N₂ atmosphere, were produced again at room conditions with

Full text of DOI:10.1016/j.molstruc.2017.01.047

Accepted Manuscript
Synthesis of fluorescence organocyclotriphosphazene derivatives having
functional groups such as formyl, Schiff base and both formyl and Schiff base
without using Ar or N atmosphere
2
Fatih Aslan, Ali İhsan Öztürk, Bayram Söylemez
PII:
S0022-2860(17)30066-2
10.1016/j.molstruc.2017.01.047
MOLSTR 23352
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Revised Date:
Accepted Date:
09 June 2016
01 January 2017
16 January 2017
Please cite this article as: Fatih Aslan, Ali İhsan Öztürk, Bayram Söylemez, Synthesis of
fluorescence organocyclotriphosphazene derivatives having functional groups such as formyl,
Schiff base and both formyl and Schiff base without using Ar or N atmosphere, Journal of
2
Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.01.047
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ACCEPTED MANUSCRIPT
O
O
O
O
O
O
X
X
X
X
O
O
O
O
N
N
O
O
P
P
O
X
O
P
P
O
X
THF
H2N
6
+
N
N
N
N
room. temp.
X
X
X
X
OH
P
P
O
O
O
O
O
X
X
O
N
O
N
OH
X
X
Comp. 2 : -H
Comp. 3 : -OCH3
O
N
Comp. 2o : -H
HO
O
Comp. 3o : -OCH3
O
HO

ACCEPTED MANUSCRIPT
Organocyclotriphosphazenes bearing six formyl from hexachlorocyclotriphosphazene are
generated in high yield without Ar or N2 atmosphere. Organocyclotriphosphazenes involving
six Schiff base groups do not occur from each of the aniline derivatives. The
organocyclotriphosphazenes carrying both formyl and Schiff base units derivate from some
aniline derivatives

ACCEPTED MANUSCRIPT
Synthesis of fluorescence organocyclotriphosphazene derivatives having functional
groups such as formyl, Schiff base and both formyl and Schiff base without using
Ar or N2 atmosphere
Fatih Aslan*, Ali İhsan Öztürk*, Bayram Söylemez*,
* Harran University, Art&Science Faculty, Department of Chemistry, Sanliurfa, Turkey.
Abstract
In the present study, hexa(4-formyl-phenoxy)cyclotriphosphazene(2) and hexa(4-
formyl-2-methoxy-phenoxy)cyclotriphosphazene(3), which were previously synthesized
in boiling solvent under N2 atmosphere, were produced again at room conditions
without using Ar or N2 atmosphere by the same method. We detected that both 2 and 3
formed with very high yields even under this mild conditions. After that, 1 equiv of the
compounds (2 and 3) were reacted with 12 equiv of some anilines derivatives with
different substituted groups such as hydroxyl, cyano, mercapto, heterocyclic, carboxyl,
chloro for the synthesis of new organocyclotriphosphazene derivatives incorporating six
non-conjugated Schiff base groups. However, such compounds did not form from all of
the selected anilines derivatives. The reactions of the compounds (2 and 3) with 4-
carboxy-aniline
and
4-cyano-aniline
led
to
the
formation
of
the
organocyclotriphosphazenes bearing both formyl and Schiff base units. The structures
1
of the synthesized molecules were determined using FT-IR, H NMR and 31P NMR.
Then, the synthesized compounds were photophysically investigated by UV absorption
and fluorescence emission spectroscopy in solution state. Photophysical studies indicate
that the compound 1 and all of the obtained compounds have luminescence properties
and large Stoke’s shifts. Some compounds showed blue-red emission peak having rather
large Stoke’s shifts in the range of 390 to 800 nm.
Keywords: Cyclotriphosphazene, organophosphazene, phosphazene, Schiff base,
fluorescence.
Corresponding author: Fatih Aslan; Harran University, Art & Science Faculty, Department of
Chemistry, Sanliurfa, TURKEY, Tel: +904143183590, e-mail: fa33@outlook.com.tr
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1. Introduction
The
production
of
organocyclotriphosphazenes
from
hexachlorocyclotriphosphazene has still continued to attracted great attention for several
reasons since 1960. First, large number of organocyclotriphosphazene is possible to
prepare from the reactions of hexachlorocyclotriphosphazene with various organic
compounds such as alcohol, phenol, amine, thiol, Grignard or organolithium reagents
[1-7]. But, the majority of the reported organocyclotriphosphazenes were synthesized
from alcohol, phenol and amine derivatives. Second, these compounds have large
potential applications in wide area such as chemistry, biochemistry and industry [8].
Third, these compounds are stable to air and water [9].
Among reported organocyclotriphosphazenes, there are relatively few studies
related to the synthesis of organocyclotriphsopahazenes bearing functional groups like
formyl, Schiff base, carboxyl acid, thiol, nitro, amino, hydroxyl, cyano, diazo or
halogen in the literature. They are very important compounds for new
organocyclotriphosphazenes derived from them. For example, different
organocyclotriphosphazene derivatives carrying Schiff base, hydroxyl, carboxylic acid,
ester or ether are generated from condensation, oxidation, reduction or substitution
reaction of organocyclotriphosphazenes involving formyl groups. Until today, this type
of compounds has been obtained from some formyl substituted phenol derivatives, such
as
4-hydroxybenzaldehyde,
2-hydroxybenzaldehyde,
4-hydroxy-3-
methoxybenzaldehyde,
4-hydroxy-2-methoxybenzaldehyde,
5-chloro-2-
hydroxybenzaldehyde and 5-bromo-2-hydroxybenzaldehyde in the literature [10-14].
Researchers prepare such organocyclotriphosphazenes by two different methods [15].
Both methods are performed under Ar or N2 atmosphere. The preparation of
organocyclotriphosphazenes from hexachlorocyclotriphosphazene is generally
performed under Ar or N2 atmosphere.
There have been relatively few reports on the synthesis of
organocyclotriphosphazenes containing non-conjugated six Schiff base moieties from
organocyclotriphosphazene bearing formyl groups [11, 14, 16-18]. Especially, the
organocyclotriphosphazenes containing both formyl and Schiff base groups are not
available in the literature. The Schiff bases with one or two imine groups without
phosphazene generally reported in the literature. There are relatively few works about
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the synthesis of conjugated Schiff base macrocyclic containing six or more than six
imines [19, 20].
In recent years, fluorescence properties of the synthesized compounds in
chemistry have been extensively studied [21]. Less research has been reported on the
luminescence of the organophosphazenes, even though many organophosphazenes have
been prepared. The luminescence and the synthesis of Schiff base compounds are much
better known and more studied than organocyclotriphosphazenes. Our group has
previously synthesized new organocyclotriphosphazenes carrying six formyl and six
Schiff base groups In addition, we determined the fluorescence properties of these
compounds [11, 14].
Herein, without using Ar or N2 atmosphere, we firstly synthesized the
organocyclotriphosphazenes
bearing
six
formyl
groups
from
hexachlorocylotriphosphazene in the presence of K2CO3 at room temperature. Some
new organocyclotriphosphazenes bearing six non-conjugated Schiff base moieties were
derived from the reactions of the organocyclotriphosphazenes bearing formyl groups
with aniline and some aniline derivatives. However, we detected surprisingly that the
organocyclotriphosphazenes bearing both formyl and Schiff bases groups derived from
1 equiv of organocyclotriphosphazenes bearing six formyl groups and 12 equiv of 4-
cyano-aniline and 4-carboxyl-aniline. Luminescence has been investigated at room
temperature in THF solution. Some derived organocyclotriphosphazenes are blue-red
luminescent compound.
2. Experimental
2.1. Materials
Hexachlorocyclotriphosphazene (N3P3Cl6), 4-hydroxybenzaldehyde, 4-hydroxy-3-
methoxybenzaldehyde, 4-methoxy-benzylamine, aniline and aniline derivatives were
purchased from Aldrich and used as received. Acetonitrile and THF which used as
solvent in the reactions were purchased from Merck and used without further
purification. All the reactions were carried out at room conditions without N2 or Ar
atmosphere.
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2.2. Instrumentation
NMR spectra were obtained on a Varian Mercury 400 MHz. Infrared spectra
were recorded on a Perkin Elmer Spectrum Two spectrometer with ATR in the region of
4000−400 cm−1. Electronic absorption and fluorescence spectra in solution were
recorded by Shimadzu mini 1240 UV spectrophotometer and Shimadzu RF-1501
spectrofluorometer, respectively. The melting points were measured on a Electrothermal
IA 9200 apparatus in capillary.
2.3. Synthesis
2.3.1. Hexa(4-formyl-phenoxy)cyclotriphosphazene (2). 4-hydroxybenzaldehyde
(17.56 g, 103.55 mmol) was added to a mixture of N3P3Cl6 (1) (3.00 g, 8.63 mmol) and
K2CO3 (14.40 g, 103.55 mmol) in acetonitrile (300 mL) at room conditions. The
reaction was stirred for 24 h at room temperature. After acetonitrile used as solvent was
removed under vacuum, CH2Cl2 (350 mL) was poured into the residual solid. The
mixture was filtered and the solvent was evaporated to about 30 mL. Then solution of
the mixture was slowly added to ethanol (400 mL) and a white solid precipitated out.
The resulting white solid was filtered, washed with hexane and dried at room
temperature. The yield of the compound 2 was 6.02 g (81%): mp:157 ºC. FT-IR (cm-1):
1
1704 (HC=O), 1206, 1180 and 1156 (P=N), 960 (P-O-Aryl). H NMR  (ppm,
(CD3)2CO): 10.0 (H-C=O), 8.0-7.0 (Aryl H). 31P NMR  (ppm): 7.95.
2.3.2. General procedure for synthesis of the compounds 2a-2o from the compound
2. A solution of the compound 2 (0.50 g, 0.580 mmol) and primary amine derivatives
(6.960 mmol) in THF (50 mL) was stirred for 24 h at room temperature. THF was
removed under vacuum. After CH2Cl2 (5 mL) was poured into the residual mixture, the
solution was slowly added to ethanol (80 mL) and a solid precipitated out. The resulting
solid was filtered, washed with hexane and then dried at room temperature. (The name
of the color of the compounds was mentioned in the web site: http://en.wikipedia.org.)
2.3.2.1. Hexa[4-(phenyliminomethyl)phenoxy]cyclotriphosphazene (2a). The
compound 2a was prepared from aniline (0.64 mL, 6.960 mmol) as a beige color solid
according to general procedure. Yield: 0.52 g (68%): mp:175 ºC. FTIR (cm-1): 1626
1
(HC=N), 1199, 1181, 1171, 1156 (P=N), 958 cm-1(P-O-Aryl). H NMR  (ppm,
CDCl3): 8.24 (H-C=N), 7.62-6.93 (Aryl H). 31P NMR  (ppm): 7.93.
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2.3.2.2. Hexa[4-(1-naphthyliminomethyl)phenoxy]cyclotriphosphazene (2b). The
compound 2b was prepared from 1-naphthylamine (0.997 g, 6.960 mmol) as a straw
color solid according to general procedure. Yield: 0.80 g (85%): mp:155 ºC. FTIR (cm-
1
1): 1626 (HC=N), 1201, 1181, 1177, 1156 (P=N), 957 (P-O-Aryl). H NMR  (ppm,
CDCl3): 8.64 ppm (H-C=N), 8.45-7.00 (Aryl H). 31P NMR  (ppm): 8.70.
2.3.2.3.
Hexa[4-(3,4-bischloro-phenyliminomethyl)phenoxy]cyclotriphosphazene
(2c). The compound 2c was prepared from 3,4-dichloroaniline (1.128 g, 6.960 mmol) as
a cream color solid according to general procedure. Yield: 0.80 g (80%): mp:193 ºC.
FTIR (cm-1): 1626 (HC=N), 1201, 1178, 1155 (P=N), 950 (P-O-Aryl). The NMR
analysis of the compound was not performed because insoluble in any solvent, such as
(CD3)2CO, CDCl3, DMSO-D.
2.3.2.4.
Hexa[4-(2-mercapto-phenyliminomethyl)phenoxy]cyclotriphosphazene
(2d). The compound 2d was prepared from 2-mercapto-aniline (0.75 mL, 6.960 mmol)
as a peach color solid according to general procedure. Yield: 0.60 g (69%): mp: 133 ºC.
FTIR (cm-1): 1602 (HC=N), 1202, 1178, 1160 (P=N), 951 (P-O-Aryl). 1H NMR  (ppm,
(CD3)2SO): 8.00-6.00 ppm (protons peaks for imine, thiol, and aromatic protons), 3.45
(H2O), 2.40 ((CH3)2SO). 31P NMR  (ppm):8.75.
2.3.2.5.Hexa[4-(2-mercapto-benzimidazol-5-yl-iminomethyl)phenoxy]
cyclotriphosphazene (2e). The compound 2e was prepared from 5-amino-2-
mercaptobenzimidazole (1.150 g, 6.960 mmol) as a selective yellow color solid
according to general procedure. Yield: 0.55 g (55%): mp: 310 ºC. FTIR (cm-1): 3119
1
cm-1(N-H), 1635 (C=N), 1626 (HC=N), 1199, 1177, 1161 (P=N), 953 (P-O-Aryl). H
NMR  (ppm, (CD3)2SO): 12.6 and 12.0 (N-H ve S-H), 8.55 (H-C=N) 7.8-6.3 (the
protons peaks for aromatic), 3.45 (H2O), 2.40 ((CH3)2SO). 31P NMR  (ppm): 8.25.
2.3.2.6. Hexa[4-(1H-indazol-6-yl-iminomethyl)phenoxy]cyclotriphosphazene (2f).
The compound 2f was prepared from 6-amino-1H-indazole (0.928 g, 6.960 mmol) as a
apricot color solid according to general procedure. Yield: 0.78 g (87%): mp:170 ºC.
FTIR (cm-1): 3231 (OH), 1629 (HC=N ), 1200, 1178, 1157 (P=N),943 (P-O-Aryl). The
NMR analysis of the compound was not performed because insoluble in any solvent,
such as (CD3)2CO, CDCl3, DMSO-D.
2.3.2.7. Hexa[4-(fluoren-2-yl-iminomethyl)phenoxy]cyclotriphosphazene (2g). The
compound 2g was prepared from 2-aminofluorene (1.261 g, 6.960 mmol) as a sunset
color solid according to general procedure. Yield: 0.77 g (72%): mp:302 ºC. FTIR (cm-
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1): 1627 (HC=N), 1205, 1175, 1157 (P=N), 961 (P-O-Aryl). The NMR analysis of the
compound was not performed because insoluble in any solvent, such as (CD3)2CO,
CDCl3, DMSO-D.
2.3.2.8. Hexa[4-(2-hydroxy-phenyliminomethyl)phenoxy]cyclotriphosphazene (2h).
The compound 2h was prepared from 2-hydroxy-aniline (0.760 g, 6.960 mmol) as a
naples yellow color solid according to general procedure. Yield: 0.64 g (78%): mp:154
ºC. FTIR (cm-1): 3414 (O-H), 1625 (HC=N), 1202, 1177 and 1158 (P=N), 955 (P-O-
Aryl). 1H NMR  (ppm, CDCl3): 8.77 (H-C=N), 8.00-6.80(Aryl H). 31P NMR  (ppm):
8.66.
2.3.2.9.Hexa[4-(5-chloro-2-hydroxy-phenyliminomethyl)phenoxy]
cyclotriphosphazene (2i). The compound 2i was prepared from 5-chloro-2-hydroxy-
aniline (0.999 g, 6.960 mmol) as a naples yellow color solid according to general
procedure. Yield: 0.5 g (53%): mp:160 ºC. FTIR (cm-1):3421 (O-H), 1624 (HC=N),
1206, 1174 and 1158 (P=N), 957 (P-O-Aryl). 1H NMR  (ppm, CDCl3): 8.76 (H-C=N),
8.00-6.80 (Aryl H). 31P NMR  (ppm): 8.66.
3.3.2.10.Hexa[4-(4-hydroxy-phenyliminomethyl)phenoxy]cyclotriphosphazene (2j).
The compound 2j was prepared from 4-hydroxy-aniline (0.760 g, 6.960 mmol) as a
peach yellow color solid according to general procedure. Yield: 0.80 g (97%): mp: 185
ºC. FTIR (cm-1): 3414 (O-H), 1623 (HC=N), 1205, 1178, 1159 (P=N), 959 (P-O-Aryl).
1H NMR  (ppm, CDCl3): 8.55 (H-C=N), 7.80-6.50 (Aryl H). 31P NMR  (ppm): 9.14.
2.3.2.11.Hexa[4-(4-mercapto-phenyliminomethyl)phenoxy]cyclotriphosphazene
(2k). The compound 2k was prepared from 4-mercapto-aniline (0.871 g, 6.960 mmol)
as a peach yellow color solid according to general procedure. Yield: 0.74 g (85%):
mp:330 ºC. FTIR (cm-1): 1624 (HC=N), 1190, 1178, 1158 (P=N), 953 cm-1(P-O-Aryl).
The NMR analysis of the compound was not performed because insoluble in any
solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.3.2.12. Hexa[4-(4-methoxy-benzyliminomethyl)phenoxy]cyclotriphosphazene (2l).
The compound 2l was prepared from 4-methoxy-benzylamine (0.91 mL, 6.96 mmol) as
a white color solid according to general procedure. Yield: 0.80 g (88%): mp:88 ºC.
1
FTIR (cm-1): 1640 (HC=N), 1204, 1172, 1156 (P=N), 952 cm-1(P-O-Aryl). H NMR 
(ppm, CDCl3): 8.33 (H-C=N), 7.70-6.80 (Aryl H), 4.69 (-CH2-), 3.77 (CH3O-). 31P
NMR  (ppm): 8.89.
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2.3.2.13. Hexa[4-(isoquinolin-5-yl-iminomethyl)phenoxy]cyclotriphosphazene (2m).
The compound 2m was prepared from 5-aminoisoquinoline (1.00 g, 6.960 mmol) as a
atomic trangerine color solid according to general procedure. Yield: 1.0 g (100%):
1
mp:145 ºC. FTIR (cm-1): 1625 (HC=N), 1198, 1176, 1155 (P=N), 953 (P-O-Aryl). H
NMR  (ppm, CDCl3): 9.3 (H-C=N for 5-amino-isoquoniline), 8.67 (H-C=N), 8.53-7.20
(the peaks of aromatic protons). 31P NMR  (ppm): 8.62.
2.3.2.14. 6,6-di(4-(4-cyano-phenyliminomethyl)phenoxy)-2,2,4,4-tetra(4-formyl-
phenoxy)cyclotriphosphaze (2n). The compound 2n was prepared from 4-cyano-
aniline (0.820 g, 6.960 mmol) as a white color solid according to general procedure.
Yield: 0.50 g (80%): mp: 115 ºC. FTIR (cm-1): 2225 (C≡N), 1699 (HC=O), 1630
1
(HC=N), 1200, 1176, 1157 (P=N), 953 (P-O-Aryl). H NMR  (ppm, CDCl3): 9.98(H-
C=O, integral area:100), 8.58 (H-C=N, integral area:38.68), 8.00-6.80 (Aryl H). 31P
NMR  (ppm): 8.20-7.70 (multiple).
2.3.2.15. 2,2,4-tri(4-(4-carboxy-phenyliminomethyl)phenoxy)-4,6,6-tri(4-formyl-
phenoxy)cyclotriphosphazene (2o). The compound 2o was prepared from 4-carboxy-
aniline (0.954 g, 6.960 mmol) as a white color solid according to general procedure.
Yield: 0.5 g (70%): mp:357 ºC. FTIR (cm-1): 1683 (HOC=O and HC=O), 1631
(HC=N), 1202, 1175, 1159 cm-1 (P=N), 953 cm-1(P-O-Aryl). 1H NMR  (ppm, DMSO):
12.35 (-COOH), 9.88 (H-C=O, integral area: 98.73), 8.52 (H-C=N, integral area:100),
8.00-6.00 (Aryl H). 31P NMR  (ppm): 8.38-7.58 (multiple).
2.3.3. Hexa(4-formyl-2-methoxy-phenoxy)cyclotriphosphazene (3). 4-hydroxy-3-
methoxy-benzaldehyde (vanilline) (15.76 g, 103.55 mmol) was added to a mixture of
N3P3Cl6 (1) (3.00 g, 8.63 mmol) and K2CO3 (14.40 g, 103.55 mmol) in acetonitrile (300
mL) at room conditions. The reaction was stirred for 24 h at room temperature. After
acetonitrile was removed under vacuum, CH2Cl2 (350 mL) was poured into the residual
solid. The mixture was filtered and the solvent was evaporated to about 30 mL. Then
solution of the mixture was slowly added to ethanol (400 mL) and a white solid
precipitated out. The resulting white solid was filtered, washed with hexane and dried at
room temperature. The yield of the compound 3 was 6.74 g (75%): mp: 182 ºC. FTIR
1
(cm-1): 1692 (HC=O), 1186, 1147, 1116 (P=N), 947 (P-O-Aryl). H NMR  (ppm,
(CD3)2SO): 9.40 (H-C=O), 7.20-7.60 (Aryl H), 3.80 (H3CO-). 31P NMR  (ppm): 8.00.
2.3.4. General Procedure for synthesis of the compounds 3a-3o from the compound
3. A solution of the compound 3 (0.4 g, 0.384 mmol) and primary amine derivatives
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(4.608 mmol) in THF (50 mL) was stirred for 24 h at room temperature. THF was
removed under vacuum. After CH2Cl2 (5 mL) was poured into the residual mixture, the
solution was slowly added to ethanol (80 mL) and a solid precipitated out. The resulting
solid was filtered, washed with hexane and then dried at room temperature. (The name
of the color of the compounds was mentioned in the web site: http://en.wikipedia.org.)
2.3.4.1. Hexa[2-methoxy-4-(phenyliminomethyl)phenoxy]cyclotriphosphazene (3a).
The compound 3a was prepared from aniline (0.42 mL, 4.608 mmol) as a champagne
solid according to general procedure. Yield: 0.37 g (64%): mp: 109 ºC. FTIR (cm-1):
1627 (HC=N), 1215, 1181, 1147 (P=N), 949 (P-O-Aryl). 1H NMR  (ppm, (CD3)2SO):
8.49 (H-C=N), 7.60-7.20 (Aryl H), 3.98 (H3CO-). 31P NMR  (ppm): 9.14.
2.3.4.2. Hexa[2-methoxy-4-(1-naphthyliminomethyl)phenoxy]cyclotriphosphazene
(3b). The compound 3b was prepared from 1-naphthylamine (0.660 g, 4.608 mmol) as a
buff solid according to general procedure. Yield: 69% (0.81 g), mp.:134 ºC. FTIR (cm-
1
1): 1625 (HC=N), 1185, 1155 (P=N), 950 (P-O-Aryl). H NMR  (ppm, (CD3)2SO):
8.60 (H-C=N), 8.35-7.00 (Aryl H), 3.98 (H3CO-). 31P NMR  (ppm): 9.14.
2.3.4.3.Hexa[2-methoxy-4-(3,4-bischloro-pheyliminomethyl)phenoxy]
cyclotriphosphazene (3c). The compound 3c was prepared from 3,4-dichloro-aniline
(0.747 g, 4.608 mmol) as a jasmine solid according to general procedure. Yield: 0.76 g
(100%): mp.:115 ºC. FTIR (cm-1): 1627 (HC=N ), 1184, 1150 (P=N), 949 (P-O-Aryl).
1H NMR  (ppm, (CD3)2SO): 8.28 (H-C=N), 7.60-7.20 (the peaks of aromatic protons),
3.97 (H3CO-). 31P NMR  (ppm): 9.00.
2.3.4.4.Hexa[2-methoxy-4-(2-mercapto-pheyliminomethyl)phenoxy]
cyclotriphosphazene (3d). The compound 3d was prepared from 2-mercapto-aniline
(0.50 mL, 4.608 mmol) as a peache-orange solid according to general procedure. Yield:
0.60 g (91%): mp:120 ºC. FTIR (cm-1): 1624 (HC=N), 1199, 1181, 1171, 1156 (P=N),
1
957 (P-O-Aryl). H NMR  (ppm, (CD3)2SO): 8.40 (HC=N), 7.78-6.30 (the peaks of
aromatic protons), 5.37 (H-S-), 3.98 (H3CO-). 31P NMR  (ppm): 8.50.
2.3.4.5.Hexa[2-methoxy-4-(2-mercapto-benzimidazol-5-yl-iminomethyl)phenoxy]
cyclotriphosphazene (3e). The compound 3e was prepared from 5-amino-2-
mercaptobenzimidazole (0.761 g, 4.608 mmol) as a pumpkin solid according to general
procedure. Yield: 1g (100%): mp.:280 ºC. FTIR (cm-1): 1636 (C=N), 1613 (HC=N),
1186, 1158, 1114 (P=N), 953cm-1(P-O-Aryl). 1H NMR  (ppm, (CD3)2SO): 12.5 (N-H
8

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and SH), 8.55 (H-C=N), 7.5-7.0 (the peaks of aromatic protons), 3.80 (H3CO-). 31P
NMR  (ppm): 8.54.
2.3.4.6.Hexa[2-methoxy-4-(1H-indazol-6-yl-iminomethyl)phenoxy]
cyclotriphosphazene (3f). The compound 3f was prepared from 5-amino-1H-indazole
(0.614 g, 4.608 mmol) as an apricot solid according to general procedure. Yield: 0.78 g
(54%): mp:195 ºC. FTIR (cm-1): 1636 (HC=N), 1625 (HC=N), 1187, 1154, 1119 (P=N),
943 (P-O-Aryl). The NMR analysis of the compound was not performed because
insoluble in any solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.3.4.7.Hexa[2-methoxy-4-(fluoren-2-yl-iminomethyl)phenoxy]
cyclotriphosphazene (3g). The compound 3g was prepared from 2-aminofluorene
(0.835 g, 4.608 mmol) as a tangerine solid according to general procedure. Yield: 0.77 g
(97%): mp.:112 ºC. FTIR (cm-1): 1626 (HC=N), 1183, 1150 (P=N), 950 (P-O-Aryl). 1H
NMR  (ppm, (CD3)2SO): 8.56 (HC=N), 7.7-7.0 (the peaks of aromatic protons), 3.97
(H3CO-), 3.60 (-H2C-). 31P NMR  (ppm): 8.99.
2.3.4.8.Hexa[2-methoxy-4-(2-hydroxy-phenyliminomethyl)phenoxy]
cyclotriphosphazene (3h). The compound 3h was prepared from 2-hydroxy-aniline
(0.503 g, 4.608 mmol) as a pumpkin solid according to general procedure. Yield: 0.78 g
(85%) mp: 142 ºC. FTIR (cm-1): 3425 (-O-H), 1625 (HC=N), 1190, 1177 and 1152
1
(P=N), 952 cm-1(P-O-Aryl). H NMR  (ppm, CDCl3): 8.80 (H-C=N), 7.90-6.50 (Aryl
H), 3.65 (CH3O-). 31P NMR  (ppm): 8.88.
2.3.4.9.Hexa[2-methoxy-4-(5-chloro-2-hydroxy-phenyliminomethyl)phenoxy]
cyclotriphosphazene (3i). The compound 3i was prepared from 5-chloro-2-hydroxy-
aniline (0.662 g, 4.608 mmol) as a peach yellow solid according to general procedure.
Yield: 0.68 g (79%): mp:115 ºC. FTIR (cm-1): 3345 (-O-H), 1625 (HC=N), 1190, 1168
1
and 1151 (P=N), 954 cm-1(P-O-Aryl). H NMR  (ppm, CDCl3): 8.80 (H-C=N), 7.90-
6.50 (Aryl H), 3.94 (CH3O-). 31P NMR  (ppm): 8.87.
2.3.4.10.Hexa[2-methoxy-4-(4-hydroxy-phenyliminomethyl)phenoxy]
cyclotriphosphazene (3j). The compound 3j was prepared from 4-hydroxy-aniline
(0.503 g, 4.608 mmol) as a peach yellow solid according to general procedure. Yield:
0.78 g (85%): mp: 185 ºC. FTIR (cm-1): 1623 (HC=N), 1191, 1180, 1148 (P=N), 954
1
cm-1(P-O-Aryl). H NMR  (ppm, CDCl3): 8.49 (H-C=N), 7.60-6.60 (Aryl H), 3.89
(CH3O-). 31P NMR  (ppm): 9.38.
9

ACCEPTED MANUSCRIPT
2.3.4.11.Hexa[2-methoxy-4-(4-mercapto-phenyliminomethyl)phenoxy]
cyclotriphosphazene (3k). The compound 3k was prepared from 4-mercapto-aniline
(0.577 g, 4.608 mmol) as an amber solid according to general procedure. Yield: 0.64 g
(%65): mp:218 ºC. FTIR (cm-1): 1618 (HC=N), 1188, 1180, 1151 (P=N), 953 cm-1(P-O-
Aryl). The NMR analysis of the compound was not performed because insoluble in any
solvent, such as (CD3)2CO, CDCl3, DMSO-D.
2.3.4.12.Hexa[2-methoxy-4-(4-methoxy-benzyliminomethyl)phenoxy]
cyclotriphosphazene (3l). The compound 3l was prepared from 4-methoxy-
benzylamine (0.60 mL, 4.608 mmol) as a white solid according to general procedure.
Yield: 0.65 g (54%): mp:105 ºC. FTIR (cm-1): 1643 (HC=N), 1181, 1150, 1119 (P=N),
947 cm-1(P-O-Aryl). 1H NMR  (ppm, CDCl3): 8.31 (H-C=N), 7.40-6.60 (Aryl H), 4.69
(-CH2-), 3.65 (CH3O-). 31P NMR  (ppm): 9.00.
2.3.4.13.Hexa[2-methoxy-4-(isoquinolin-5-yl-iminomethyl)phenoxy]
cyclotriphosphazene (3m). The compound 3m was prepared from 5-aminoisoquinoline
(0.664 g, 4.608 mmol) as an atomic tangerine solid according to general procedure.
Yield: 0.74 g (85%): mp:138 ºC. FTIR (cm-1): 1624 (HC=N), 1186, 1163, 1148 (P=N),
950 (P-O-Aryl). 1H NMR  (ppm, CDCl3): 9.19 (HC=N for 5-aminoisoquoniline), 8.30
(HC=N), 8.5-7.0 (the peaks of aromatic protons), 3.94 (H3CO-). 31P NMR  (ppm):
8.54.
2.3.4.14. 2,2,4,4-tetra(2-methoxy-4-(4-cyano-phenyliminomethyl)phenoxy)-6,6-
tri(2-methoxy-4-(4-cyano-phenyliminomethyl)phenoxy)cyclotriphosphazene (3n).
The compound 3n was prepared from 4-cyano-aniline (0.544 g, 4.608 mmol) as a white
solid according to general procedure. Yield: 0.5 g (60%): mp:115 ºC. FTIR (cm-1): 2225
1
(C≡N), 1699 (HC=O), 1630 (HC=N), 1200, 1176, 1157 (P=N), 953 (P-O-Aryl). H
NMR  (ppm, CDCl3): 9.98(H-C=O, integral area:180.93), 8.58 (H-C=N, integral
area:372.82), 8.00-6.80 (Aryl H), 3.98 (H3CO-). 31P NMR  (ppm): 8.20-7.70
(multiple).
2.3.4.15.2,2,4-tri(2-methoxy-4-(4-carboxy-phenyliminomethyl)phenoxy)-4,6,6-tri(2-
methoxy-4-formyl-phenoxy)cyclotriphosphazene (3o). The compound 3o was
prepared from 4-carboxy-aniline (0.632 g, 4.608 mmol) as a white solid according to
general procedure. Yield: 0.57 g (70%): mp:357 ºC. FTIR (cm-1): 1683 (HOC=O), 1631
(HC=N), 1202, 1175, 1159 cm-1 (P=N), 953 cm-1(P-O-Aryl). 1H NMR  (ppm, DMSO):
10

ACCEPTED MANUSCRIPT
12.40 (-COOH) 9.86 (H-C=O, integral area:100), 8.49 (H-C=N, integral area:110),
8.00-6.50 (Aryl H), 3.80 (CH3O-). 31P NMR  (ppm): 8.38-7.58 (multiple).
3. Results and Discussion
Carriedo et al. and Tümer et al. reported firstly that hexa(4-formyl-
phenoxy)cyclotriphosphazene(2)
and
hexa(4-formyl-2-methoxy-
phenoxy)cyclotriphosphazene(3) were derived with 91% and 74% yields in refluxing
solvent under N2 atmosphere, respectively [10,12]. In the present study, the compounds
2 and 3 were obtained again with 81% and 75% yields at room temperature without
using Ar or N2 atmosphere according to Schemes 1. These compounds were prepared
via the reactions of hexachlorocyclotriphosphazene (1) with 12 equiv of 4-formyl-
phenol and 4-formyl-2-hydroxy-phenol in the presence of K2CO3 (12 equiv). Both 2 and
3 were successfully purified by precipitation method which is the easiest and the most
economical. In addition, the reagents and solvents used in the reactions were not
purified before we used. When these reactions are carried out under N2 atmosphere or
without using Ar or N2 atmosphere, the compounds 2 and 3 forms in very high yields.
Ar
Cl
Cl
O
O Ar
Ar
N
N
Cl
P
P
Cl
O
P
P
O
acetonitrile
6 K2CO3
6 Ar OH
Ar
+
+
N
N
N
N
room condition,
24 h
P
P
Cl Cl
Ar
O
O
OCH3
OH
1
( )
Ar
CH3
O
Ar:
O
2
( )
3
( )
Scheme 1. Structure and synthesis route for the compounds 2 and 3
An equivalent of the compounds 2 and 3 were treated with 12 equivalent of some
primary amines for the obtained of organocyclotriphosphazene derivatives containing
six Schiff base groups. Selected primary amines are aniline (a), 1-naphthylamine (b),
3,4-dichloroaniline (c), 2-mercapto-aniline (d), 5-amino-2-mercapto-1H-benzimidazole
(e), 5-amino-1H-indazole (f), 2-aminofluorene (g), 2-hydroxy-aniline (h), 5-chloro-2-
hydroxy-aniline (i), 4-hydroxy-aniline (j), 4-mercapto-aniline (k), 4-methoxy-
benzylamine (l), 5-aminoisoquinoline (m), 4-cyano-aniline (n) and 4-carboxyaniline
(o). We determined that the organocyclotriphosphazenes bearing six Schiff base
11

ACCEPTED MANUSCRIPT
moieties derived from aniline (a), 4-methoxy-benzylamine (l) and some aniline
derivatives (b-m), expect for 4-cyano-aniline (n) and 4-carboxyaniline (o) (Scheme 2).
O
N
Ar
O
Ar
N
X
X
X
X
O
N Ar
O
O
X
O
O
N
P
N
X
O
P
P
O
THF
O
P
P
O
X
X
Ar NH
6
+
2
N
N
room condition,
24 h
N
N
Ar
P
N
O
O
O
O
O
X
N
O
X
Ar
X
2
Comp. : -H
X
X
3
Comp. : -OCH3
2a-2m
3a-3m
2
3
Comp. and
N
O
Ar
CH
CH
CH
CH
3
3
3
3
H N
N
SH
2
N
SH
Ar(R):
N
N
H
H3C
Cl
NH
2
H
Cl
c
b
a
g
d
f
e
CH3
NH
Cl
HO
NH2
NH
HS
NH2
2
2
H3CO
CH2
NH2
N
OH
OH
j
l
k
i
m
h
Scheme 2. Structure and synthetic route for the organocyclotriphosphazenes with six
imine groups
The reactions of both 2 and 3 with these two aniline derivatives led to the
formation of the organocyclotriphosphazenes carrying both formyl and Schiff base
moieties (Scheme 3, 4). On para position of 4-cyano-aniline (n) and 4-carboxyaniline
(o) have electron-withdrawing group such as -CN, -COOH.
12

ACCEPTED MANUSCRIPT
O
O
O
O
O
O
X
X
X
X
O
O
O
O
N
N
O
O
P
P
O
O
P
P
O
THF
X
X
H2N
6
+
N
N
N
N
room. temp.
X
X
X
OH
X
P
P
O
O
O
O
O
X
X
N
O
N
O
OH
X
X
2 :
3 :
Comp.
Comp.
-H
N
O
2o :
3o :
Comp.
Comp.
-H
-OCH3
HO
-OCH3
O
O
HO
Scheme 3. Structure and synthetic route for the organocyclotriphopshazenes carrying
both imine and formyl groups from p-carboxy-aniline
O
O
O
O
O
O
O
O
O
O
N
N
O
P
P
O
THF
O
P
P
O
6
H N
2
C N
+
N
N
N
N
room. temp.
P
P
O
O
O
O
O
O
O
N
O
N
(2)
C
N
C
(2n)
N
N
C
O
O
O
O
H CO
3
H CO
H CO
3
3
H CO
3
O
N
O
O
O
O
N
H CO
N
3
H CO
N
3
O
P
P
O
THF
OCH
O
P
P
O
3
OCH
3
C
H N
C N
6
+
2
N
N
room. temp.
N
N
P
P
O
O
O
O
O
O
N
N
OCH
H CO
3
3
OCH
3
OCH
3
O
N
(3)
C
N
(3n)
C
N
Scheme 4. Structure and synthetic route for the organocyclotriphopshazenes(2n and 3n)
carrying both imine and formyl groups from p-cyano-aniline
13

ACCEPTED MANUSCRIPT
While the organocyclotriphosphazenes (2o and 3o) bearing the same number of
formyl and Schiff base groups occur from the reactions of both the compound 2 and the
compound 3 with 4-carboxyaniline (o), the organocyclotriphosphazenes (2n and 3n)
bearing different number of formyl and Schiff base moieties consist from 4-cyano-
aniline (n). The structures of all the prepared compounds were confirmed using FT-IR,
1H NMR, and 31P NMR.
The FT-IR spectra of all the synthesized compounds (2, 3, 2a-2o and 3a-3o)
exhibit characteristic strong bands in the range of 1220-1150 cm−1 and 980-940 cm−1,
which can be assigned to -P=N− and P-O-Aryl, respectively. These bands confirm
distinctly the presence of phosphazene and phenoxy bounded of phosphazene ring. In
the IR spectra of the compounds (2, 3), the strong peak observed at 1703 and 1695 cm−1
were attributed to the presence of aldehyde groups. But, in the IR spectra of the
compounds (2a-2m, 3a-3m) which have six imine groups, no peak was found at 1705-
1680 cm-1 illustrating the presence of the carbonyl group. Imine (C=N) stretching
vibrations in the spectra of these compounds appear in the range of 1645–1610 cm-1. As
shown in the Fig. 1 and Fig. 2, the peaks at 1705-1680 cm-1 and 1645–1610 cm-1 in the
spectra of the compounds (2n-2o, 3n-3o) proved the existence of both Schiff base and
formyl units. The IR spectra of organocyclotriphosphazenes bearing Schiff base
moieties showed no signals due to the -NH2.
14

ACCEPTED MANUSCRIPT
Fig. 1. FTIR spectra of the compounds 2n and 3n
15

ACCEPTED MANUSCRIPT
Fig. 2. FTIR spectra of the compounds 2o and 3o
1
The H and 31P NMR data of all the compounds were given in experimental
section. All these spectral analyses confirm the proposed structure of all the compounds.
1H NMR spectra of the compounds 2 and 3 show a peak at around 10.0 ppm, belonging
to the aldehyde proton. However, this aldehyde proton peak disappears in
organocyclotriphosphazenes derivatives containing six Schiff base groups (2a-2m, 3a-
3m). The imine proton for the compounds was observed at about 8.30 ppm as singlet in
the spectra. The methoxy protons attached to the phenoxy ring was observed at about
3.80 ppm in the spectra of the compounds 3 and its derivatives. Two peaks
corresponding to formyl proton at about 10.0 ppm (HC=O) and imine proton at 8,30
1
ppm(HC=N) were present in the H NMR spectra of organocyclotriphosphazenes
16

ACCEPTED MANUSCRIPT
carrying both formyl and Schiff base moieties (2n-3n, 20-3o) (Fig. 3 and Fig. 4).
1
According to the integral areas supplied by H NMR data, the molar ratios of the two
functional groups were calculated. While the molar ratios of formyl to imine were
indeed 1:1(integral area ratio:100:98.73) and 1:1 (integral area ratio:110:100) for 2o and
3o, the molar ratios are 4:2 (integral area ratio:100:38.68) and 2:4 (integral area
ratio:180.93:372.82) for 2n and 3n, respectively. As in the FT-IR spectra, the signal due
to the -NH2 protons relating to primary amine were not appears in the region 5.0 ppm in
the 1H NMR spectra.
Fig. 3. 1H NMR spectra of the compounds 2n and 3n
Fig. 4. 1H NMR spectra of the compounds 2o and 3o
31
The proton-decoupled P NMR spectra of the compounds (2, 3, 2a-2mand 3a-
3m) exhibit A3 type spin systems due to same phosphors environments within the
molecule as expected. The signal of all the phosphor atoms in these compounds was
observed in the range of 9.0-6.0 ppm as single. But, the signal of the phosphorus atoms
in the compounds (2n, 2o, 3n, 3o) was observed in the range of 8.50-7.50 ppm as
multiple (Fig. 5 and Fig. 6). Because the multiple peaks were observed very small
chemical shift (1 ppm), the chemical environment of the phosphorus is not determined
from 31P NMR spectra.
17

ACCEPTED MANUSCRIPT
Fig. 5. 31P NMR spectra of the compounds 2n and 3n
Fig. 6. 31P NMR spectra of the compounds 2o and 3o
UV–vis absorption and photoluminescence spectra of the compound 1 and all the
synthesized compounds were recorded in THF medium in the range 200–900 nm. Table
1 and Table 2 summarize UV–Vis, excitation and maximum fluorescence wavelengths
of all the compounds. The UV–vis absorption spectra of organocyclotriphosphazene
derivatives shows absorption wavelengths between 220 nm and 360 nm assigned to the
π→π* transitions. The absorption spectra for the compounds 2 and 3 presented two
peaks. Allcock reported that the UV-vis. spectrum of the compound 1 exhibited only
one absorption bands at 175 nm [9]. But, we observed one peak at 287 nm (log:3) in
the UV-vis. spectrum of the compound 1 in THF.
Fluorescence spectra of the compound 1 and the prepared compounds show
emission peak. Therefore, the compound 1 and the prepared compounds are
fluorescence. The excitation wavelengths were detected at 220-350 nm for all the
compounds. While emission peak of the compounds 2 and 3 show in the ultraviolet
region, the majority of the compounds derived from the compounds 2 and 3 exhibited
18

ACCEPTED MANUSCRIPT
emission peak in the visible region. Among all the compounds, the compounds 1, 2j and
3g are the most fluorescence compounds. They have shown intense emission band at
608, 745 and 753 nm and the largest Stoke’s shift. The emission values of some
organocyclotriphospahazene obtained from the same aniline derivatives are quite
different.
4. Conclusions
At the end of this study, we have achieved very interesting results. The
organocyclotriphosphazenes involving six formyl groups were obtained in very high
yield from hexachlorocyclotriphosphazene and formyl substituted phenols derivatives in
the presence of K2CO3 at room temperature without Ar or N2 atmosphere. The reactions
of these compounds with aniline derivatives cause to the formation of
organocyclotriphosphazenes bearing non-conjugated six Schiff base units. However,
organocyclotriphosphazenes bearing non-conjugated six Schiff base units are not
prepared from all of the aniline derivatives. If there is an electron withdrawing group on
aniline derivatives, like cyano, carboxyl, organocyclotriphosphazenes containing both
formyl
and
Schiff
base
units
derive
from
theirs.
Furthermore,
organocyclotriphosphazenes bearing non-conjugated six Schiff base units are also
produce
from
aniline
derivatives
carrying
heterocyclic
Many
group.
of
Organocylotriphosphazenes
are fluorescent
compounds.
organocyclotriphosphazenes containing formyl or Schiff base groups can exhibit
fluorescence emission peak in visible region. Such phosphazenes have the potential to
be used as fluorescence.
Acknowledgements
The authors would like to thanks the Harran University Research Fund for support
(Project No: 13125) and Scientific and Technical Council of Turkey (107T407) for
support.
References
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Table 1. Photophysical and Stoke’s Shift data of the compounds 1, 2 and 2a-2o
Comp.
Cons.
Excitatio Emission Stoke’s
Absorption max.
nm (log)
,
Shift
ΔST
(nm)
n, Ex.,
nm (log)

Em., nm
(log)
(mol/L)
1
2
8.63x10-5
3.87x10-5
3.60x10-5
175(4.0)a, 287(3)
250(4.8), 329(3.2)
268(7.0)
307(7.5)
307(7.3)
608(6.0)
341(7.5)
400(7.3)
340
34
2a
238(4.7), 259(4.9), 290(4.8),
315(4.7)
93
2b
2c
2.27x10-5
2.51x10-5
3.10x10-5
239(5.0), 257(5.0), 290(4.9),
349(4.8)
285(7.0)
307(7.5)
267(7.5)
331(7.3)
401(7.5)
401(7.5)
46
94
241(4.9), 263(5.0), 290(5.0),
316(5.0)
2dc
241(4.9), 271(4.8), 297(5.0),
307(5.0)
134
2ec
2fb
2gb
2h
2.10x10-5
269(5.0), 325(4.9)
336(7.7)
374(7.7)
38
-
-
-
-
-
-
-
-
-
-
2.37x10-5
241(4.8), 265(5.0), 288(5.0),
352(5.0)
308(7.5)
407(7.6)
99
2i
2.27x10-5
2.37x10-5
241(4.9), 265(4.9), 287(4.9),
360(4.8)
238(7.1)
330(7.0)
92
2j
242(4.9), 269(4.7), 285(4.7),
329(4.7)
309(7.3)
745(7.4)
436
2kb
2l
-
-
-
-
-
2.75x10-5
2.68x10-5
251(5.0)
307(7.6)
262(7.6)
339(7.5)
436(7.6)
32
2m
236(4.92),
264(4.95),
174
287(4.88), 342(4.65)
260(4.9), 292(4.9)
239(4.2), 284(4.5)
2n
3.45x10-5
3.83x10-5
255(7.3)
326(7.4)
351(7.2)
355(7.4)
96
29
2oc
a[9]
b
Optical properties of the compound could not be analyzed because of insoluble in any
solvent.
c The spectra were recorded in DMSO

ACCEPTED MANUSCRIPT
Table 2. Photophysical and Stoke’s Shift data of the compounds 3 and 3a-3o
Comp.
Cons.
Excitation Emission Stoke’s
Absorption max.
nm (log)
,
Shift
, Ex., nm
(log)

Em., nm
(mol/L)
ΔST
(log)
3
3.20x10-5
2.90x10-5
258(4.9), 304(4.6)
240(7.5)
336(7.5)
96
3a
238(4.8), 264(4.9), 287(4.9),
315(50)
246(7.4),
398(7.4)
134
3b
3c
1.90x10-5
2.27x10-5
2.37x10-5
240(5.1), 262(5), 294(5.0),
315(5.0), 343(4.9)
285(6.9)
250(7.5)
304(7.5)
338(6.5)
401(7.5)
406(7.6)
53
240(4.9), 269(4.9), 290(4.9),
324(5.1)
151
102
3dc
241(5.0), 267(4.9), 287(4.9),
315(4.9)
3ec
3fb
3g
3h
1.73x10-5
270(5.2), 322(5.1), 360(5.2)
336(7.0)
-
413(7.0)
-
77
-
-
-
1.65x10-5
2.31x10-5
239(5.0), 289(4.9), 356(4.8)
300(7.6)
293(7.1)
753(7.6)
328(7.1)
453
55
238(4.9), 271(4.9), 286(4.9),
350(4.9)
3i
3j
1.67x10-5
239(5.0), 289(4.9), 356(4.8)
239(5.0), 274((4.8), 330(4.9)
-
254(7.8)
264(7.5)
-
409(7.8)
305(7.5)
-
155
41
1.88x10-5
3kb
3l
-
-
1.90x10-5
2.04x10-5
258(4.9), 296(4.6)
245(7.6)
332(7.6)
399(7.6)
512(7.7)
154
180
3m
239(5.0), 269(4.8), 286(4.8),
322(4.9), 342(4.9)
3n
2.54x10-5
2.62x10-5
242(5.0), 262(5.0), 294(5.1),
309(5.1)
294(7.6)
366(7.7)
72
3oc
276(5.1), 291(5.1), 340(4.8)
324(7.6)
338(7.5)
14
b
Optical properties of the compound could not be analyzed because of insoluble in any
solvent.
c The spectra were recorded in DMSO