G.Y. Çiftçi et al. / Polyhedron 102 (2015) 741–749
743
acid as a MALDI matrix using a nitrogen laser, accumulating 50
laser shots using a Bruker Microflex LT MALDI-TOF mass spectrom-
eter. The mass spectra of some compounds were recorded on a
Bruker MicroTOF LC–MS spectrometer using the electrospray ioni-
sation (ESI) method; Cl values were used for the calculated mass
values. All reactions were monitored using thin-layer chromatog-
raphy (TLC) on Merck silica gel plates (Merck, Kieselgel 60,
2.3.2. Reaction of 2,2,4,4,6-pentaphenoxy-6-chlorocyclotriphosphazene
(5) with 4,4 -(9-fluorenylidene)diphenol (11) in a 1:5 ratio to form
compounds 13 and 14
0
Compound
5 (1.2 g, 1.9 mmol) and compound 11 (0.8 g,
3
5
2.28 mmol) were dissolved in 100 mL of dry THF in a 250 mL
three-necked round-bottomed flask. The mixture was cooled in
an ice-bath and Cs CO (0.62 g, 1.9 mmol) in 20 mL of dry THF
2 3
0
.25 mm thickness) with F254 indicator. Column chromatography
was quickly added to the stirred solution under an argon atmo-
sphere. The reaction mixture was stirred for 4 days under reflux
was performed on silica gel (Merck, Kieselgel 60, 230–400 mesh;
for 3 g crude mixture, 100 g silica gel was used in a column 3 cm
in diameter and 60 cm in length). All reactions were carried out
under an argon atmosphere. Melting points were measured on a
Gallenkamp apparatus using a capillary tube. 1H and P NMR
spectra were recorded in CDCl
5
NMR and 85% H
3
1
and was followed by P NMR and TLC with silica gel plates using
n-hexane:THF (2:1) as the mobile phase. The reaction mixture was
filtered to remove the formed cesium chloride, THF was removed
at reduced pressure and the resulting white solid was subjected
to column chromatography using n-hexane:THF (2:1) as the
mobile phase. The first product was compound 13 (1.5 g,
mp > 250 °C), Rf = 0.70. Compound 13 was re-crystallized from
31
3
solutions on a Varian INOVA
1
00 MHz spectrometer using TMS as an internal reference for H
PO
3 4
as an external reference for 31P NMR. FT-IR
spectra were recorded on a Perkin Elmer Spectrum 100 FT-IR spec-
trometer. Absorption spectra in the UV–Vis region were recorded
with a Shimadzu 2101 UV–Vis spectrophotometer. Fluorescence
excitation and emission spectra were recorded on a Varian Eclipse
spectrofluorometer using 1 cm path length cuvettes at room
temperature.
ethanol–CH
2 2
Cl (3:1) and obtained as white crystals, which were
suitable for single crystal X-ray crystallography. Anal. Calc. for C85
H N O P : C, 65.89; H, 4.29; N, 5.42. Found: C, 65.86; H, 4.25; N,
66 6 12 6
5.40%. MALDI-TOF (m/z) calc.: 1548, found: 1549.8 [M+H] .
-
+
1
H
3
NMR (CDCl
3
, d, ppm): 6.65 (H
a
, 4H, d,
J
H–H = 7.5 Hz), 6.79 (H
1
,
,
3
3
20H, d,
J
H–H = 8.3 Hz), 6.85 (H
b
, 4H, d,
, H , 4H, m,
H–H = 7.6 Hz), 7.29 (H
H–H = 7.6 Hz). FTIR (
JH–H = 7.6 Hz), 6.90 (H
3
0H, t, 3JH–H = 6.8 Hz), 7.03 (H
3
JH–H = 7.3 Hz), 7.05
1
c
d
3
3
(
2
H , 20H, m,
J
e
, 2H, t,
JH–H = 7.5 Hz), 7.71
2.2. X-ray crystallography
3
ꢀ1
(
f
H , 2H, d,
J
m
, cm ): 3060 m((C–H)arom.),
1
485 s(C@C), 1259-1153 s(P@N), 1272 s(P@O). The second product
was compound 14 (0.8 g, oily), Rf = 0.54. Anal. Calc. for C55
C, 65.55; H, 4.46; N, 4.42. Found: C, 65.52; H, 4.45; N,
Intensity data were recorded on a Bruker APEX II QUAZAR
diffractometer. Absorption corrections by multi-scan were applied
35] and space groups were determined using XPREP implemented
42 3 7 3
H N O P :
[
+ 1
4
.40%. MALDI-TOF (m/z) calc.: 949, found 950: [M+H] . H NMR
in APEX2 [36]. The structures were determined using the direct
methods procedure in SHELXS-97 and refined by full-matrix least
3
(
CDCl
J
3
, d, ppm): 6.64 (H
a
, 4H, d,
, 10H, m,
H–H = 8.7 Hz), 7.10–7.18 (H
J
H–H = 8.8 Hz), 6.78 (H
b
, 4H, d,
3
3
H–H = 8.7 Hz), 6.87–6.92 (H
1
JH–H = 8.3 Hz), 6.95–7.05
2
squares on F using SHELXL-97 [37]. All non-hydrogen atoms were
3
3
(
H
3
, 5H, t,
.25 (H , 2H, d,
.37 (H
J
2
, 10H, m,
, 2H, d, 3JH–H = 7.8 Hz),
JH–H = 7.5 Hz), 7.31 (H
c
JH–H = 7.9 Hz),
refined with anisotropic displacement factors and C-H hydrogen
atoms were placed in calculated positions and allowed to ride on
the parent atom. The final geometrical calculations and the molec-
ular drawings were carried out with PLATON [38], MERCURY [39], and
3
7
7
d
3
3
e
, 2H, t, JH–H = 7.5 Hz), 7.78 (H
f
, 2H, d, JH–H = 7.6 Hz), 4.35
ꢀ1
(
1H, s, OH). FTIR (
m
, cm ): 3400–3450 s(OH), 3065 m((C–H)arom.),
1
487 s(C@C), 1200–1155 s(P@N), 1262 s(P@O).
DIAMOND [40] programs.
2
.3.3. Reaction of 2,2,4,4,6-pentanaphthoxy-6-chlorocyclotriphosphazene
2.3. Synthesis
0
(7) with 4,4 -(9-fluorenylidene)diphenol (11) in a 1:5 ratio to form
compound 15
Compounds 5, 6, 7 and 8 were prepared and purified according
Compound 7 (1.2 g, 1.9 mmol) was dissolved in 100 mL of dry
THF in a 250 mL three-necked round-bottomed flask. The mixture
to the literature procedures [41–43].
2 3
was cooled in an ice-bath and Cs CO (0.62 g, 1.9 mmol) in 10 mL
2
.3.1. Reaction of the trimer (1) with 1-hydroxypyrene (4) in a 1:5
of dry THF was quickly added to the stirred solution under an
argon atmosphere. Compound 11 (0.8 g, 2.28 mmol) in 20 mL
dry THF was added dropwise over 1 h to the stirred mixture.
The resulting reaction mixture was stirred for 4 days under reflux
and followed by P NMR and TLC with silica gel plates using
n-hexane:THF (2:1) as the mobile phase. The reaction mix-
ture was filtered to remove the formed cesium chloride, THF
was removed at reduced pressure and the resulting white
solid was subjected to column chromatography using n-hexane:
THF (2:1) as the mobile phase. The eluate was compound 15
ratio to form compounds 9 and 10
Compound 1 (1 g, 2.8 mmol) was dissolved in 100 mL of dry
THF in a 500 mL three-necked round-bottomed flask. The mixture
3
1
was cooled in an ice-bath and Cs
2
CO
3
(4.7 g, 14.4 mmol) in 10 mL
of dry THF was quickly added to the stirred solution under an
argon atmosphere. Compound 4 (3.14 g, 14.4 mmol) in 50 mL dry
THF was added dropwise over 1 h to the stirred mixture. The
resulting reaction mixture was stirred for 3 days at room temper-
ature and followed by 31P NMR and TLC with silica gel plates using
dichloromethane:n-hexane (1:2) as the mobile phase. The reaction
mixture was filtered to remove the formed cesium chloride, THF
was removed at reduced pressure and the resulting white solid
was subjected to column chromatography using dichloro-
methane:n-hexane as the mobile phase. The first eluate was com-
pound 9 (2.5 g, mp > 250 °C, powder), Rf = 0.35. Anal. Calc. for
86 6 12 6
(0.27 g, oily), Rf = 0.57. Anal. Calc. for C125H N O P : C, 73.24;
H, 4.23; N, 4.10. Found: C, 73.22; H, 4.20; N, 4.6%. MALDI-TOF
+
1
3
(m/z) calc.: 2049, found: 2050.3 [M+H] . H NMR (CDCl , d,
3
ppm): 6.43 (H
a
,
4H, d,
J
H–H = 8.8 Hz), 6.48 (H
b
,
4H, d,
, 2H, d,
3
, 2H, d, 3JH–H = 8.5 Hz), 7.30 (H
, 2H, d,
, 10H, d,
H–H = 7.5 Hz), 7.08-7.23 (H4,5,8, 30H, m,
H–H = 7.0 Hz), 7.55 (H
, cm ): 3058 m((C–H)arom.), 1460 s(C@C), 1231 s(P@N),
J
H–H = 8.8 Hz), 6.82 (H
c
d
3JH–H = 7.0 Hz), 7.50 (H
3
JH–H = 8.0 Hz), 7.67 (H
f
, 2H,
, 10H,
H–H = 8.3–8.9 Hz),
, 10H, d, 3JH–H = 7.8 Hz).
e
3
3
C
3
80
3
H45ClN O
5 3
P : C, 76.46; H, 3.61; N, 3.34. Found: C, 76.42; H,
d,
d,
J
H–H = 7.7 Hz), 6.96 (H
1
JH–H = 7.5 Hz), 7.08 (H
3
3
3
.59; N, 3.32%. MALDI-TOF (m/z) calc.: 1255, found: 1256 [M
J
J
+
1
3
+
H] . H NMR (CDCl
3
, d, ppm): 6.90–8.10 (m, ArCH). FTIR (
cm ): 3040 m((C–H)arom.), 1500 s(C@C), 1210 s(P@N), 1183 s
P@O). The second eluate was compound 10 [44].
m,
7.30 (H
FTIR (
6
, 10H, d,
J
7
ꢀ1
ꢀ1
m
(
1194 s(P@O).