Optimized synthesis of selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives

Article abstract of DOI:10.1080/10426507.2020.1802275

Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives were synthesized via substitution reactions through tailored control. The reactions of cyclotriphosphazene with 4-oxybenzaldehyde and 2,2-dioxybiphenyl gave the following syn

Full text of DOI:10.1080/10426507.2020.1802275

Phosphorus, Sulfur, and Silicon and the Related Elements
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Optimized synthesis of selected 4-
oxybenzaldehyde and 2,2-dioxybiphenyl
cyclotriphosphazene derivatives
Jipeng Chen , Le Wang , Yunxia Yang , Mengsheng Xu , Jinhua Xie & Pan Liu
To cite this article: Jipeng Chen , Le Wang , Yunxia Yang , Mengsheng Xu , Jinhua Xie &
Pan Liu (2020): Optimized synthesis of selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl
cyclotriphosphazene derivatives, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2020.1802275
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2020.1802275
Optimized synthesis of selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl
cyclotriphosphazene derivatives
Jipeng Chen, Le Wang, Yunxia Yang, Mengsheng Xu, Jinhua Xie, and Pan Liu
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai, China
ABSTRACT
ARTICLE HISTORY
Received 5 April 2020
Accepted 24 July 2020
Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives were synthe-
sized via substitution reactions through tailored control. The reactions of cyclotriphosphazene with
4-oxybenzaldehyde and 2,2-dioxybiphenyl gave the following synthesized derivatives: one mono-
substituted open-chain compound, N3P3Cl5(O2C7H5) (1, 69%); mono spiro, N3P3Cl4(O2C12H8) (2,
91.1%); non-gem tri-substituted, N3P3Cl3 (O6C21H15) (3, 17%); dispiro, N3P3Cl2(O4C24H16) (4, 92.3%);
penta-substituted, N3P3Cl(O10C35H25) (5, 92%)； hexa-substituted, N3P3(O12C42H30). Most of these
derivatives (1–6) are obtained with good yield (up to 97%), This work provides a simple and available
approach to obtain versatile cyclotriphosphazene derivatives, which is expected to further promote
the use of HCCP as phosphorus platform for the construction of multi-functional materials.
KEYWORDS
Hexachlorocyclotriphosphaz-
ene (HCCP); tailored control;
31P NMR
GRAPHICAL ABSTRACT
Introduction
coordination chemistry of the cyclotriphosphazene deriva-
tives and focused on its symmetrical structural and terminal
functional groups.[8–12] Many cyclotriphosphazene deriva-
tives were reported and used in the fields of catalysts,[13,14]
flame retardants,[15] biological materials,[16,17] and chemo-
sensor.[18] Recently, the cyclotriphosphazene ring has been
further developed as a versatile ‘phosphorus’ platform for
the preparation of multi-functional materials with specific
properties useful in diverse research areas. For example,
As an important branch of phosphorus chemistry, the hexa-
chlorocyclotriphosphazene ring (N3P3Cl6, HCCP) is a versa-
tile symmetric heterocycle with six active chlorines[1–3]
(Figure 1) which can be easily functionalized via selective
substitutions of the six chlorines to produce many deriva-
tives to showcase a wide range and unique chemical and
biological properties, and has received extensive atten-
tion.[4–7] Phosphorus chemists have paid attention to Majoral’s group have prepared dendrons bearing bi-
CONTACT Le Wang
wangle316@sues.edu.cn
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai,
201620, China.
Supplemental data for this article is available online at https://doi.org/10.1080/10426507.2020.1802275.
ß 2020 Taylor & Francis Group, LLC

2
J. CHEN ET AL.
Figure 1. Optimized Synthesis of Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives (compounds 1–6).
functional group based on cyclotriphosphazenes;[19] Turkey’s
Results and discussion
groups have systematically looked at substitution reactions
In this paper, the selected substitution reaction of cyclotri-
and the distribution of products;[20–23] We have also shown
phosphazene has been systematically studied, and six well-
defined organic phosphorus derivatives based on cyclotri-
phosphazene ring have been optimized synthesized with 4-
oxybenzaldehyde moieties and 2,2-dioxybiphenyl groups. As
shown in Scheme 1, most of compounds were obtained with
good yield (up to 97%) under mild conditions (Cs2CO3 as
base, room temperature) by employing optimized
that different cyclen/imidazole moieties attached to
a
cyclotriphosphazene
core
have
shown
significant
cooperativity.[24,25]
Therefore, these observations suggest the possibility of
constructing multifunctional phosphorus materials according
to selected synthesis of cyclotriphosphazene derivatives.[26,27]
In this paper, different substituted cyclotriphosphazene
derivatives from one to six were prepared with 4-oxybenzal- design system.
With six actives chlorines, cyclotriphosphazene deriva-
dehyde and 2,2-dioxybiphenylphenol (Figure 1). The opti-
mized synthesis reaction conditions of of selected 4- tives are well known easily to produce multiple substituted
oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene products. Therefore, the selected substitution reaction of
derivatives, especially reaction conditions were followed by cyclotriphosphazene were systematically studied, and six
31P NMR will be described and analyzed.
well-defined organic phosphorus derivatives based on

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Scheme 1. Synthetic route of cyclotriphosphazene derivatives (compounds 1–6) (the yield of this compound was isolated yield).
cyclotriphosphazene ring have been synthesized with 4-oxy-
General procedure. To a stirred solution of base (1
benzaldehyde moieties and 2,2-dioxybiphenyl groups. In this equiv.) and substrate HCCP (1 mmol) dissolved in dry THF
paper, two template compounds were firstly selected to (10 mL), was added 2,2-dioxybiphenyl, then keep 0 ꢀC
investigate reaction conditions, and then six HCCP-based (30 min) then r.t. (10 h). The crude yield of compound 2
derivatives with different modification compounds (1–6) was determined by 31P NMR (Table 2).
were obtained under the optimum condition.
In order to obtain a better yield, the proportion of the
As shown in Table 1, different parameters such as types reaction was also examined. The research show that com-
of base, were firstly investigated in order to optimize the pounds 2 and 4 can be gained with high yield by using the
reaction conditions of compound 1. It is evident that molar ratio of 1:0.9 and 1:4.0 (P3N3Cl6/2,2-dioxybiphenyl).
Cs2CO3 and K2CO3 produced higher yield of 1 than other While that was 1:5.0 for compound 5. However, the yield of
bases (e.g., NaH and Et3N) (entries 1–4). Therefore, the compound 3 was still as low as 17% with K2CO3 as base
influence on yield of compound 1 by bases (K2CO3 and with regardless of the regulatory response ratio. That should
Cs2CO3) were further invested by 31P NMR spectra and was be related to various geometrical and positional isomers
shown in Figure S1 (Supplementary material). According to results in the difficulty in separation of the isomeric mix-
31P NMR spectra, it was found that the yield of 1 was higher tures.[28,29] More details were provided in the
with K2CO3 as the base than that of Cs2CO3 with the time Experimental section.
increased. It was speculative that high activity of Cs2CO3
All the pure products were separated and shown in
induce multiple substituted products form, and that reduce Figure 2 and the yield were shown in Figure 1. Due to the
the yield of compound
Figure S2).
1
(Supplementary material symmetric structure, compounds 3 and 6 showed a singlet
at 17.39 ppm and 7.08 ppm in 31P NMR spectrum,

4
J. CHEN ET AL.
Table 1. The optimization of reaction conditions of compound 1 which containing with 4-hydroxybenzaldehyde.a
Entry
Base
Solvents
Temp. (ꢀC)
Time (h)
Yield of 1a (%)
1
2
3
4
(Et)3N
NaH
K2CO3
THF
THF
THF
THF
r.t.
r.t.
r.t.
r.t.
10
10
10
10
<10
22
67
Cs2CO3
63
aGeneral procedure: To a stirred solution of base (1 equiv.) and substrate HCCP (1 mmol) dissolved in dry THF (10 mL), was added 4-hydroxybenzaldehyde, then
keep 0 ꢀC (30 min) then r.t. (10 h); The crude yield of compound 1 was determined by 31P NMR.
Table 2. The optimization of reaction conditions of compound 2 which containing with 2,2-dioxybiphenyl.
Time/h
2
94
75
4
94
87
6
96
88
8
94
96
10
96
97
Yielda/%
Yieldb/%
separately. Differently, compounds 1, 2, 4, and 5 showed Typical procedure for synthesis of compounds 1–6
two typical coupling signals in 31P NMR spectrum. For
example, compound 1 showed a triplet at 11.74 ppm that
Synthesis of [N3P3Cl5(O2C7H5)] (compound 1)
A mixture of K2CO3 (1.69 g, 5.18 mmol) and 4-oxybenzalde-
hyde (316.16 mg, 2.59 mmol) in anhydrous tetrahydrofuran
(10 mL) was stirred at 0 ꢀC for 30 min. Then HCCP (1.00 g,
2.88 mmol) in anhydrous tetrahydrofuran (20 mL) was added
dropwise in ice bath, and the reaction mixture was stirred at
room temperature. The progress of the reaction was moni-
tored by 31P NMR until the phosphorus spectrum signal
(d ¼ 20.43 ppm) of the raw material HCCP disappeared.
Twenty-four hours later, the reaction was completed, and
the salt was removed by centrifugation and the supernatant
was collected. The solvent was removed in vacuo and the
crude product was purified by column chromatography (sil-
ica gel, petroleum ether/ethyl acetate (V:V ¼ 20:1)). The pro-
cedure gave the compound 1 (0.86 g, 69.1%) as a colorless,
crystalline solid. The NMR spectra was confirmed by litera-
ture.[30] White solid. 1H NMR (400 MHz, CDCl3)
d/ppm10.01(s, 1H), 7.95 (d, 2H, J ¼ 8.2 Hz), 7.44 (d, 2H,
J ¼ 8.2 Hz); 31P NMR (162 MHz, CDCl3) d/ppm 20.81(d, 2 P,
PCl2, AB2 System, J ¼ 63.2 Hz); 11.74 (t, 1 P, P(O2C12H8,
J ¼ 63.2 Hz)); 13C NMR(100 MHz, CDCl3) d/ppm 190.34,
153.60, 134.51, 131.60, 122.06.
was attributed to the two PCl2 phosphine, and doublets at
22.50 ppm were ascribed to the 4-hydroxybenzaldehyde-sub-
stituted phosphine, while compound 5 displays two different
signal at 20.50 ppm and 5.04 ppm. It is clear that these com-
pounds exhibit significant difference in 31P NMR chemical
shift, and thus the progress of the reaction can be monitored
by 31P NMR.
Experimental
Method and apparatus
All chemical reagents and solvents were obtained commer-
cially and used as received without further purification
unless otherwise stated. Ultrapure water was purified from
Millipore. Silica gel (100–200 mesh) was used for flash col-
umn chromatography. NMR spectra were recorded on a
Bruker AV II 400 MHz; chemical shifts are quoted relative
to SiMe4 (TMS, 1H and 13C, external) and H3PO4 (85%)
(31P, external). Coupling constants (J) were given in Hertz
(Hz). The term m, q, t, d, s referred to multiple, quartet,
triplet, doublet, singlet. Mass spectra were carried out on a
Finnigan LCQDECA spectrometer and Agilent 1100 LC/
MSD with ESI mode. The Supplemental Materials contains
Synthesis of [N3P3Cl4(O2C12H8)](compound 2) and
[N3P3Cl2(O4C24H16)] (compound 4)
These two molecules were synthesized according to our pre-
vious report with some modification. To a cooled suspen-
sion (0 ꢀC) of HCCP (1.00 g, 2.88 mmol) and Cs2CO3
1
sample H, 13C and 31P NMR spectra for the products 1–6
(Supplementary material Figures S3–S24)

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Figure 2. 31P NMR spectrum of compounds 1–6 and HCCP.
(2.06 g, 6.33 mmol) in anhydrous THF (50 mL), 2,2-dihy- Synthesis of [N3P3Cl3(O6C21H15)] (compound 3)
droxybiphenyl (0.59 g, 3.16 mmol ) was added drop by drop. A solution of 4-oxybenzaldehyde (1.05 g, 8.63 mmol) in THF
The mixture was stirred at room temperature until the raw
material HCCP disappeared, then the mixture was filtered
and the organic phase was evaporated under vacuum. The
product was recrystallized with petroleum ether and
dichloromethane. White crystal. (1.21 g, 91.1%). 1H NMR
(10 mL) was added to a suspension of K2CO3 (1.79 g,
12.94 mmol) in anhydrous tetrahydrofuran (10 mL) at 0 ꢀC,
then HCCP (1.00 g, 2.88 mmol, in 20 mL of THF) was added
dropwise and the mixture was stirred at room temperature.
The progress of the reaction was monitored by 31P NMR,
until the phosphorus spectrum signal (d ¼ 20.43 ppm) of the
raw material HCCP disappeared. After removal of salts by
centrifugation, the clear solution was concentrated under
reduced pressure and subjected to flash chromatography (sil-
ica gel, petroleum ether/ethyl acetate (V:V ¼ 15:1) to afford
compound 3 as a colorless, crystalline solid. The NMR spec-
tra was confirmed by literature.[31]
(400 MHz, CDCl3)
d
7.33–7.59 (m, 8 H). 31P NMR
(162 MHz, CDCl3) d 24.78(d, 2 P, PCl2, AB2 System,
J ¼ 71.3 Hz), 12.87 (t, 1 P, P (O2C12H8, J ¼ 71.3 Hz)); 13C
NMR (100 MHz, CDCl3)
126.48, 121.83.
d
147.76, 129.84, 128.59,
Compound 4 were prepared by following a procedure
similar to that used for 2. The quantities involved are as fol-
lows: HCCP (1.00 g, 2.88 mmol), Cs2CO3 (4.69 g,
14.38 mmol), 2,2-dihydroxybiphenyl (1.18 g, 6.33 mmol).
1
White solid (0.30 g, 17.4%). H NMR (400 MHz, CDCl3)
d 10.03 (d, 3H, J ¼ 8.8 Hz), 7.95 (d, 6H, J ¼ 8.5 Hz), 7.49 (d,
2H, J ¼ 8.2 Hz), 7.40 (d, 4H, J ¼ 8.4 Hz). 31P NMR
(162 MHz, CDCl3)) d 18.14. 13C NMR (100 MHz, CDCl3) d
190.46, 153.82, 134.44, 131.56, 122.01. MALDI-TOF-MS (m/
z): [M þ H]þ, 603.9312 (calcd. 603.9098).
1
White crystal. (1.52 g, 92.3%), H NMR (400 MHz, CDCl3)
d/ppm 7.37–7.58 (m, 16H). 31P NMR (162 MHz, CDCl3)) d
1
29.22 (dd, P, PCl2), 19.44 [d, 2 P, P (O2C12H8)]; 13C NMR
(100 MHz, CDCl3) d 147.80, 129.85, 128.59, 126.48, 121.83.
White crystal. (1.21 g, 91.1%). 1H NMR (400 MHz,
CDCl3) d/ppm 7.33–7.59 (m, 8 H). 31P NMR (162 MHz,
CDCl3) d/ppm, 24.78(d, 2 P, PCl2, AB2 System, J ¼ 79.4 Hz),
12.87 (t, 1 P, P (O2C12H8, J ¼ 79.4 Hz)); 13C NMR (100 MHz,
CDCl3) d/ppm 147.76, 129.84, 128.59, 126.48, 121.83.
Synthesis of [N3P3Cl(O10C35H25)] (compound 5)
To a vigorously stirred solution of 4-oxybenzaldehyde
(1.76 g, 14.38 mmol) in anhydrous THF (30 mL) was added
K2CO3 (2.98 g, 21.57 mmol) and the mixture was stirred at
0 ꢀC under nitrogen atmosphere for 30 min, then HCCP
MALDI-TOF-MS
(calcd. 578.9856).
(m/z):
[M þ H]þ,
578.9803

6
J. CHEN ET AL.
Rev. 1999, 190–192, 3–18. DOI: 10.1016/S0010-8545(99)
00060-0.
[3] Bullen, G. J. An Improved Determination of the Crystal
Structure of Hexachlorocyclotriphosphazene (Phosphonitrilic
Chloride). J. Chem. Soc, A. 1971, 1450–1453. DOI: 10.1039/
j19710001450.
[4] Chandrasekhar, V.; Thilagar, P.; Pandian, B. M.
Cyclophosphazene-Based Multi-Site Coordination Ligands.
Coord. Chem. Rev. 2007, 251, 1045–1074. DOI: 10.1016/j.ccr.
2006.07.005.
[5] Lakshmi, S.; Katti, D. S.; Laurencin, C. T. Biodegradable
Polyphosphazenes for Drug Delivery Applications. Adv. Drug.
Deliver. Rev. 2003, 55, 467–482. DOI: 10.1016/S0169-
409X(03)00039-5.
(1.00 g, 2.88 mmol) in anhydrous THF (20 mL) was slowly
added with stirring, allowed to warm to room temperature,
and stirred for about 24 h. The progress of the reaction was
monitored by 31P NMR. The reaction mixture was centri-
fuged, filtered and evaporated. The solvent was removed in
vacuo then the resultant crude product was purified by col-
umn chromatography (silica gel, petroleum ether /ethyl acet-
ate (V:V ¼ 10:1)). The procedure gave the compound 5 as a
white solid. The spectra was in agreement with that reported
in the literature.[32] White solid (2.05 g, 92.1%). 1H NMR
(400 MHz, CDCl3) d 9.99 (t, 5H, J ¼ 8.0 Hz), 7.82 (t, 10H,
J ¼ 8.0 Hz), 7.25 (s, 10H). 31P NMR (162 MHz, CDCl3)
d/ppm 20.74 (t, 1 P, P1, AB2 System, J ¼ 85.8 Hz), 5.25 (d,
2 P, P0 , J ¼ 85.8 Hz ). 13C NMR (100 MHz, CDCl3) d/ppm
190.22, 154.16, 134.06, 121.27. MALDI-TOF-MS (m/z):
[M þ H]þ, 776.0514 (calcd. 776.0332).
[6] Caminade, A. M.; Ouali, A.; Laurent, R.; Turrin, C. O.; Majoral,
J. P. Coordination Chemistry with Phosphorus Dendrimers.
Applications as Catalysts, for Materials, and in Biology. Coord.
Chem. Rev. 2016, 308, 478–497. DOI: 10.1016/j.ccr.2015.06.007.
€
€
€ €
[7] Gorgulu, A. O.; Koran, K.; Ozen, F.; Tekin, S.; Sandal, S.
Synthesis, Structural Characterization and Anti-Carcinogenic
Activity
of
New
Cyclotriphosphazenes
Containing
Dioxybiphenyl and Chalcone Groups. J. Mol. Struct. 2015,
1087, 1–10. DOI: 10.1016/j.molstruc.2015.01.033.
Synthesis of [N3P3(O12C42H30)] (compound 6)
A mixture of N3P3Cl6 (1.00 g, 2.88 mmol), K2CO3 (3.94 g,
28.48 mmol) and 4-oxybenzaldehyde (2.32 g, 18.99 mmol)
was stirred in anhydrous THF (100 mL) under nitrogen
atmosphere at room temperature for 24 h. The reaction was
monitored by 31P NMR until a new single appeared. The
reaction mixture was centrifuged and the solvent was
removed under reduced pressure, the crude product was
purified by recrystallized with petroleum ether and dichloro-
methane. The spectra is consistent with that in the litera-
ture.[33] White solid (1.63 g, 96.9%). 1H NMR (400 MHz,
CDCl3) d/ppm 9.96 (s, 6H), 7.76 (d, 12H, J ¼ 8.4 Hz), 7.17
(d, 12H, J ¼ 8.4 Hz). 31P NMR (162 MHz, CDCl3): d 7.08.
13C NMR (100 MHz, CDCl3) d 190.29, 154.51, 133.82,
131.95, 131.35, 121.22.
[8] Tu€may, S. O.; Sarıkaya, S. Y.; Ye¸silot, S. Novel Iron(III)
Selective Fluorescent Probe Based on Synergistic Effect of
Pyrene-Triazole Units on a Cyclotriphosphazene Scaffold and
Its Utility in Real Samples. J. Lumin. 2018, 196, 126–135. DOI:
10.1016/j.jlumin.2017.12.019.
[9] C¸iftc¸i, G. Y.; S¸enkuytu, E.; Bulut, M.; Durmu¸s, M. Novel
Coumarin Substituted Water Soluble Cyclophosphazenes as
“Turn-Off” Type Fluorescence Chemosensors for Detection of
Fe(3þ) Ions in Aqueous Media. J. Fluoresc. 2015, 25,
1819–1830. DOI: 10.1007/s10895-015-1672-4.
[10] Caminade, A. M.; Hameau, A.; Majoral, J. P. The Specific
Functionalization of Cyclotriphosphazene for the Synthesis of
Smart Dendrimers. Dalton Trans. 2016, 45, 1810–1822. DOI:
10.1039/C5DT03047A.
[11] Franc, G.; Mazꢀeres, S.; Turrin, C. O.; Vendier, L.; Duhayon, C.;
Caminade, A. M.; Majoral, J. P. Synthesis and Properties of
Dendrimers Possessing the Same Fluorophore(s) Located Either
Peripherally or off-Center. J. Org. Chem. 2007, 72, 8707–8715.
DOI: 10.1021/jo701462f.
Conclusion
[12] Rolland, O.; Griffe, L.; Poupot, M.; Maraval, A.; Ouali, A.;
In summary, the substitution reaction of cyclotriphospha-
zene was studied and its 4-oxybenzaldehyde and 2,2-dioxy-
biphenyl cyclotriphosphazene derivatives also were selected
prepared under mild conditions. All of these compounds
were separated and obtained in good yield. We believe that
the strategy presented in this work will be useful in the field
of cyclotriphosphazene even phosphorus chemistry, which
providing possibilities of multi-functionalization of cyclotri-
phosphazene materials in the future.
ꢁ
Coppel, Y.; Fournie, J. J.; Bacquet, G.; Turrin, C. O.; Caminade,
A. M.; et al. Multiplication of Human Natural Killer Cells by
Nanosized Phosphonate-Capped Dendrimers. Chem. Eur. J.
2008, 14, 4836–4850. DOI: 10.1002/anie.200604651.
[13] Astruc, D.; Boisselier, E.; Ornelas, C. Dendrimers Designed for
Functions: From Physical, Photophysical, and Supramolecular
Properties to Applications in Sensing, Catalysis, Molecular
Electronics, Photonics, and Nanomedicine. Chem. Rev. 2010,
110, 1857–1959. DOI: 10.1021/cr900327d.
[14] Caminade, A. M.; Ouali, A.; Laurent, R.; Turrin, C. O.; Majoral,
J. P. The Dendritic Effect Illustrated with Phosphorus
Dendrimers. Chem. Soc. Rev. 2015, 44, 3890–3899. DOI: 10.
1039/C4CS00261J.
[15] Qiu, S.; Xing, W.; Feng, X.; Yu, B.; Mu, X.; Yuen, R. K. K.; Hu,
Y. Self-Standing Cuprous Oxide Nanoparticles on Silica@
Polyphosphazene Nanospheres: 3D Nanostructure for
Enhancing the Flame Retardancy and Toxic Effluents
Elimination of Epoxy Resins via Synergistic Catalytic Effect.
Chem. Eng. J. 2017, 309, 802–814. DOI: 10.1016/j.cej.2016.10.
100.
Acknowledgment
We thank the Innovation Program of University students of Shanghai
Higher Education Institutions (cs1804002) and the Sino-French Cai
Yuanpei Program.
References
[16] De Jong, E. R.; Deloch, N.; Knoll, W.; Turrin, C. O.; Majoral,
[1] Allcock, H. R. Recent Advances in Phosphazene
(Phosphonitrilic) Chemistry. Chem. Rev. 1972, 72, 315–356.
DOI: 10.1021/cr60278a002.
€
J. P.; Caminade, A. M.; Koper, I. Synthesis and Characterization
of Bifunctional Dendrimers: Preliminary Use for the Coating of
Gold Surfaces and the Proliferation of Human Osteoblasts
(HOB). New J. Chem. 2015, 39, 7194–7205. DOI: 10.1016/j.jor-
ganchem.2012.07.048.
[2] Majoral, J. P.; Larre, C.; Laurent, R.; Caminade, A. M.
Chemistry in the Internal Voids of Dendrimers. Coord. Chem.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
7
[17] Caminade, A. M.; Hameau, A.; Majoral, J. P. Multicharged and/
or Water-Soluble Fluorescent Dendrimers: Properties and Uses.
Chemistry 2009, 15, 9270–9285. DOI: 10.1002/chin.200950250.
[18] Rolland, O.; Griffe, L.; Poupot, M.; Maraval, A.; Ouali, A.;
Biomedical Applications: An Update on Recent Advances. J.
Mater. Chem. B. 2018, 6, 884–895. DOI: 10.1039/C7TB03081A.
[26] L.; Chen, B.; Hu, X.; Kirchon, P.; Zhao, A.; Pang, Y. M.; Zhang,
J. D.; and Zhou, T. H, Facile Fabrication of a Multifunctional
Metal–Organic Framework-Based Sensor Exhibiting Exclusive
Solvochromic Behaviors toward Ketone Molecules. ACS Appl.
Mater. Inter. 2019, 11, 8227–8233. DOI: 10.1021/acsami.
8b19815.
[27] Baranska, J. K.; Pietkiewicz, A.; Janicka, M.; Wei, Y. Q.; Turrin,
C. O.; Majoral, J. P.; Nawrot, B.; Caminade, A. M. Synthesis of
a Fluorescent Cationic Phosphorus Dendrimer and Preliminary
Biological Studies of Its Interaction with DNA. Nucleosides
Nucleotides Nucleic Acids 2010, 29, 155–167. DOI: 10.1080/
15257771003708462.
ꢁ
Coppel, Y.; Fournie, J.-J.; Bacquet, G.; Turrin, C.-O.; Caminade,
A.-M.; et al. Tailored Control and Optimisation of the Number
of Phosphonic Acid Termini on Phosphorus-Containing
Dendrimers for the Ex-Vivo Activation of Human Monocytes.
Chemistry 2008, 14, 4836–4850. DOI: 10.1002/chem.200701063.
[19] Goodman, C. K.; Wolfenden, M. L.; Nangia-Makker, P.; Michel,
A. K.; Raz, A.; Cloninger, M. J. Multivalent Scaffolds Induce
Galectin-3 Aggregation into Nanoparticles. Beilstein J. Org.
Chem. 2014, 10, 1570–1577. DOI: 10.3762/bjoc.10.162.
ꢂ
[20] Su€zen, Y.; Metinoglu, S.; Ashoor, S. E.-T. Synthesis of New
Bis-Bidendate N/Ospiro-Bino-Spiro-Cyclotriphosphazenes:
[28] McBee, E. T.; Okuhara, K.; Morton, C. J. Reactions of Hexachloro-
Structural Investigations and DFT Studies. Phosphorus Sulfur
Silicon Relat. Elem. 2017, 192, 118–128. DOI: 10.1080/
10426507.2016.1236103.
and
2,2,4,4-Tetrachloro-6,6-Diphenylcyclotriphosphazatrienes
with Sodium Phenoxide. Inorg. Chem. 1966, 5, 450–457. DOI: 10.
1021/ic50037a026.
[21] Elmas, G. The Reactions of 2-Trans-6-Bis(4-Fluorobenzyl)
ꢁ
ꢁ
[29] Jimenez, J.; Callizo, L.; Serrano, J. L.; Barbera, J.; Oriol, L.
Mixed-Substituent Cyclophosphazenes with Calamitic and
Polycatenar Mesogens. Inorg. Chem. 2017, 56, 7907–7921. DOI:
10.1021/acs.inorgchem.7b00612.
Spirocyclotetraphosphazene
with
Primary
Amines:
Spectroscopic and Crystallographic
Characterizations.
Phosphorus Sulfur Silicon Relat. Elem. 2017, 192, 1224–1232.
DOI: 10.1080/10426507.2017.1359595.
ꢁ
ꢀ
[30] Martınez-Ferrero, E.; Franc, G.; Mazeres, S.; Turrin, C.-O.;
[22] Ture, S.; Gurbanov, R.; Tuna, M. Reactions of
ꢀ
Boissiere, C.; Caminade, A.-M.; Majoral, J.-P.; Sanchez, C.
Cyclochlorotriphosphazatriene
with
2-Mercaptoethanol.
Optical Properties of Hybrid Dendritic-Mesoporous Titania
Nanocomposite Films. Chemistry 2008, 14, 7658–7669. DOI: 10.
1002/chem.200800606.
Calorimetric and Spectroscopic Investigations of the Derived
Products. Phosphorus Sulfur Silicon Relat. Elem. 2018, 193,
600–610. DOI: 10.1080/10426507.2018.1487437.
[31] Cho, S. Y.; Allcock, H. R. Novel Highly Fluorinated
€
[23] Ture, S.; Darcan, C.; Tu€rkyılmaz, O.; Kaygusuz, O. Synthesis,
Perfluorocyclobutane-Based
Phosphazene
Polymers
for
Structural Characterization and Antimicrobial Activities of
Cyclochlorotriphosphazene Derivatives Derived from N-(1-
Naphthyl)Ethylenediamine. Phosphorus Sulfur Silicon Relat.
Elem. 2020, 195, 507–515. DOI: 10.1080/10426507.2020.
1723096.
Photonic Applications. Chem. Mater. 2007, 19, 6338–6344.
DOI: 10.1021/cm702066k.
€
[32] Ozcan, E.; Tu€may, S. O.; Alidaꢂgı, H. A.; C¸o¸sut, B.; Ye¸silot, S. A
New Cyclotriphosphazene Appended Phenanthroline Derivative
as
a Highly Selective and Sensitive off–on Fluorescent
[24] Wang, L.; Ye, Y.; Lykourinou, V.; Yang, J.; Angerhofer, A.;
Zhao, Y.; Ming, L. J. Catalytic Cooperativity, Nuclearity, and
O2/H2O2 Specificity of Multi-Copper(II) Complexes of
Cyclen–Tethered Cyclotriphosphazene Ligands in Aqueous
Media. Eur. J. Inorg. Chem. 2017, 2017, 4899–4908. DOI: 10.
1002/ejic.201700811.
Chemosensor for Al3þ Ions. Dyes Pigments 2016, 132, 230–236.
DOI: 10.1016/j.dyepig.2016.05.006.
[33] Bing, B.; Li, B. Synthesis, Thermal Property and Hydrolytic
Degradation
of
a
Novel
Star-Shaped
Hexa
[p-
(Carbonylglycinomethylester)Phenoxy]Cyclotriphosphazene. Sci.
China Ser. B-Chem. 2009, 52, 2186–2194. DOI: 10.1007/s11426-
009-0159-z.
[25] Wang, L.; Yang, Y. X.; Shi, X.; Mignani, S.; Caminade, A. M.;
Majoral, J. P. Cyclotriphosphazene Core-Based Dendrimers for