Synthesis and luminescence spectral properties of new 2,7-dihydroxy-9H- fluoren-9-one derivatives

Article abstract of DOI:10.1007/s11176-005-0212-3

A number of new 2,7-dihydroxyfluorenone derivatives containing side-chain oligoethylene glycol fragments with terminal hydroxy, p-tolylsulfonyl, azido, and amino groups were synthesized. When the side chain has a certain length, an interaction between the

Full text of DOI:10.1007/s11176-005-0212-3

Russian Journal of General Chemistry, Vol. 75, No. 2, 2005, pp. 272 277. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005,
pp. 299 304.
Original Russian Text Copyright
2005 by Kirichenko, Meshkova, Topilova, Kiriyak, Lyapunov, Kulygina, Luk’yanenko.
Synthesis and Luminescence Spectral Properties
of New 2,7-Dihydroxy-9H-fluoren-9-one Derivatives
T. I. Kirichenko, S. B. Meshkova, Z. M. Topilova, A. V. Kiriyak,
A. Yu. Lyapunov, E. Yu. Kulygina, and N. G. Luk’yanenko
Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine
Received May 12, 2003
Abstract A number of new 2,7-dihydroxyfluorenone derivatives containing side-chain oligoethylene glycol
fragments with terminal hydroxy, p-tolylsulfonyl, azido, and amino groups were synthesized. When the side
chain has a certain length, an interaction between the terminal group and the fluorenone fragment becomes
possible, which considerably changes photoluminescence properties of the molecule.
Fluorenone derivatives are extensively studied as
potential biomedical agents [1 4], mesomorphic com-
pounds [5, 6], photosensitizers [7, 8], fluorophoric
ligands [9 12], and components of electrooptical
materials [13 15]. Wide application of these com-
pounds is determined mainly by their high photolumi-
nescence quantum yields and thermal stability.
Studies on the absorption and photoluminescence
spectra of fluorenone and its derivatives in solution
showed that their spectral parameters strongly depend
on the substituent and solvent nature [16 19]. Photo-
luminescence properties of fluorenone derivatives in
a solid phase have been studied to a considerably
lesser extent; however, these parameters are important
for the development of solid-phase electrooptical
devices [13 15]. 2,7-Dihydroxyfluorenone derivatives
are the least studied in this respect.
ethylamine afforded bis-p-toluenesulfonates VII X.
Compounds VIII and IX were converted into azides
XI and XII by phase-transfer reaction in the system
water toluene in the presence of tetrabutylammonium
iodide as catalyst. Azides XI and XII were reduced
to the corresponding amines XIII and XIV by the
action of triphenylphosphine in aqueous dioxane.
The electronic absorption spectrum of unsubstitu-
ted fluorenone in methanol contains three groups of
bands in the region 220 350 nm:
250 (log
4.61), 295 (3.92), and 385 nm (2.87). Imnatxroduction of
donor hydroxy or alkoxy groups into positions 2, 7 of
the fluorene system (compounds I XIV) induces a
red shift of all these maxima. Figure 1 shows the
spectrum of diol VI, which is typical of all the ex-
amined compounds.
The largest shift is observed for the weak and dif-
In the present article we describe the synthesis of
new compounds of the 2,7-dihydroxyfluorenone series,
which contain side-chain oligoethylene glycol frag-
ments with various terminal functional groups and the
results of studying their photoluminescence properties.
Substituted fluorenones were synthesized as shown in
Scheme 1.
fuse
* band of fluorenone,
= 79 88 nm. As
compared to the spectrum of fluorenone, the intensity
of the short-wave absorption bands of substituted
fluorenones increases, while the intensity of the long-
wave band decreases.
On the whole, the spectral parameters of com-
pounds I XIV are similar; they almost do not depend
on the nature of substituent and terminal group therein.
Exceptions are bis-p-toluenesulfonates VII X which
display in the spectra additional bands due to p-tolyl-
sulfonyl groups. Obviously, the reason is a weak
difference in the donor power of the substituents and
weak sensitivity of the fluorenone electron system to
probable intramolecular interactions with the terminal
2,7-Dimethoxy-9H-fluorenon-9-one (II) as model
compound was obtained by alkylation of 2,7-dihydr-
oxy-9H-fluorenone (I) with dimethyl sulfate in water
in the presence of sodium hydroxide. The reaction of
fluorenone I with 2-chloroethanol in aqueous alkali
gave diol III. Compounds IV VI were prepared by
prolonged heating of fluorenone I with the correspond-
ing oligoethylene glycol derivatives in dimethylform-
amide in the presence of powdered anhydrous potas-
sium carbonate at 80 85 C. Treatment of diols III VI
with p-toluenesulfonyl chloride in the presence of tri-
groups, e.g., to hydrogen bonding or
No luminescence was observed upon photoexcita-
tion of compounds I XIV at 436 nm. A fairly
stacking.
1070-3632/05/7502-0272 2005 Pleiades Publishing, Inc.

SYNTHESIS AND LUMINESCENCE SPECTRAL PROPERTIES
273
Scheme 1.
c
b
c
b
\
/
\
/
O
O
/
O
\
/
O
\
TsCl, Et3N, C4H8O2/CHCl3
a
a
O
O
/
O
O
/
\
\
OTs
OH
TsO
\
n
HO
O
\
n
O
n/
n/
VII X
III VI
Cl(CH2CH2O)nH,
K2CO3,
DMF
NaN3, Bu4NI,
H2O/PhMe
Me2SO4,
NaOH
c
b
HO
O
MeO
OMe
OH
a
O
O
I
II
c
b
c
b
\
/
\
/
O
/
O
\
/
O
\
Ph3P, C4H8O2/H2O
a
a
O
O
/
O
O
\
\
/
N3
N3
NH2
\
n
H2N
O
\
n
O
n/
n/
XI, XII
XIII, XIV
I: Me2SO4, NaOH; II: Cl(CH2CH2O)nH, K2CO3, DMF; III: TsCl, (Et)3N, C4H8O2/CHCl3; IV: NaN3, (Bu)4NI,
H2O/PhMe; V: Ph3P, C4H8O2/H2O; III, VII, n = 0; IV, VIII, XI, XIII, n = 1; V, IX, XII, XIV, n = 2; VI, X, n = 3.
strong luminescence was produced by irradiation with
UV light isolated by the UFS-2 light filter from a
mercury lamp spectrum; this light filter transmits the
indirect support to this assumption is the well-known
luminescence quenching of fluorenones in solution
due to hydrogen bonding with phenols and alcohols
[18, 20].
strongest mercury line with
313 nm and partially
the line with
313 nm).
254 nm (m5ax7% of that with
max
max
In the series of compounds III V which contain
terminal hydroxy groups, the emission intensity in-
creases as the terminal group becomes more distant
Unsubstituted fluorenone is characterized by a
photoluminescence maximum at 520 nm with a re-
lative intensity of 1780 units (recalculated to the con-
ditions of luminescence measurement for derivatives
I XIV). 2,7-Disubstituted fluorenones II XIV give
rise to two broad photoluminescence bands: a weak
band with its maximum at 420 450 nm and a rela-
5
log
4
3
2
tively strong band with its maximum at
610
640 nm (see table). Figure 2 shows typical lumine-
scence spectra of these compounds. Taking into ac-
count that luminescence excitation was effected at
313 nm, the observed weak emission in the region
400 500 nm may be attributed to Sn * and Tn * re-
laxation, and the strong emission at 500 750 nm, to
the transition from the S
to the S0 state.
*
Unlike the other examined compounds, 2,7-dihydr-
oxyfluorenone (I) shows only one very weak lumi-
nescence band at 440 nm. Presumably, this is the
result of formation of strong intermolecular hydrogen
bonds involving the carbonyl and hydroxy groups. An
0
220 280 340 400 460 520 580
, nm
Fig. 1. Electronic absorption spectrum of diol VI.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

274
KIRICHENKO et al.
However, further extension of the side chain (com-
Ilum
rel. units
,
100
90
pound VI, Fig. 2) leads to sharp decrease in the
emission intensity. According to the molecular-
mechanics computer simulation (Spartan’02 software
package, MMFF force field, Monte Carlo method
[21]), one of the most favorable conformation of
molecule VI is that in which the terminal hydroxy
groups are involved in intramolecular hydrogen bonds
with the oxygen atoms contiguous to the fluorenone
fragment. Analogous conformations for compounds
III V with shorter side chains are unfavorable from
the viewpoint of energy. As we already noted, hydro-
gen bonding favors effective nonradiative decay of
both singlet and triplet excited states [18], which is
likely to be responsible for luminescence quenching of
compound VI.
II
80
70
60
50
40
30
20
10
V
Similar variations of the spectral pattern were also
observed in the series of bis-p-toluenesulfonates
VII X. The luminescence intensity initially increases
in parallel with the length of the side chain (com-
pounds VII IX), and it sharply falls down in going
to compound X. However, in this case the mechanism
of luminescence quenching is likely to be different.
Sulfonates VII X contain two kinds of aromatic
fragments: -electron-rich fluorenone nucleus and
-electron-deficient p-tolylsulfonyl groups. These
VI
fragments could give rise to
stacking which is
especially pronounced in the excited state [22]. Such
interactions generally favor luminescence quenching
via nonradiative transitions [23, 24]. Effective
interactions require that the aromatic moieties be in a
close spatial contact. Computer simulation showed
0
500
600
700
, nm
Fig. 2. Luminescence spectra of crystalline compounds
II, V, and VI.
that structures ensuring
stacking interactions are
possible only for compound X with the most extended
side chains. Presumably, this is the reason for sharp
decrease of the luminescence intensity of bis-p-to-
luenesulfonate X.
from the fluorenone aromatic system; probably, these
terminal groups act as fluorescence quenchers toward
the fluorenone nucleus (via radiationless decay).
Luminescence parameters (relative intensity Ilum and
emission maximum max) of 2,7-disubstituted fluorenones
I XIV
Weak luminescence of azides XI and XII may be
rationalized in terms of
interaction between the
azido groups and the fluorenone fragment, which is
not forbidden from the symmetry considerations.
Diamines XIII and XIV also showed a weak emission,
obviously due to the strong ability of protonated
amino groups form hydrogen bonds with ether and
carbonyl oxygen atoms.
Ilum
(
)
Ilum
(
)
max
max
I
1.25(440)
VIII 8.95(450), 85.07(620)
Thus we were the first to demonstrate the possibi-
II
7.46(440), 97.01(620) IX 7.46(430), 100.00(620) lity for controlling luminescence properties of a fluo-
III 2.98(450), 29.85(630) X
IV 2.98(450), 35.82(640) XI 2.98(440), 28.36(640)
7.46(430), 1.49(620)
rophoric fragment in a molecule by introduction of
appropriate terminal functional groups into the side
V
4.48(450), 52.24(620) XII 14.92(440), 16.42(620) chain. It should also be noted that the synthesized
VI 1.49(450), 2.98(620) XIII 5.97(420), 13.43(640) compounds are excellent synthons for the preparation
VII 1.49(450), 82.09(610) XIV 19.40(430), 28.36(620) of fluorophoric oligomers and macrocyclic acceptors
like crownophanes.
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SYNTHESIS AND LUMINESCENCE SPECTRAL PROPERTIES
275
1
EXPERIMENTAL
orange red crystals. Yield 78%, mp 165 166 C. H
NMR spectrum (DMSO-d6), , ppm (J, Hz): 3.71 q
(4H, CH2O, J 11.78), 4.04 t (4H, CH2O, J 4.83),
4.87 br.t (2H, OH, J 5.45), 7.03 7.10 m (4H, Ha, Hb),
7.52 d (2H, Hc, J 9.03). Found, %: C 67.84; H 5.60.
C17H16O5. Calculated, %: C 67.99; H 5.37.
The melting points were determined in an open
capillary and were not corrected. The 1H NMR spectra
were recorded on a Varian VXR-300 spectrometer
(300 MHz) in CDCl3 or DMSO-d6 using tetramethyl-
silane as internal reference. The mass spectra (electron
impact, 70 eV) were obtained on an MKh-1321 in-
strument with direct sample admission into the ion
source. The electronic absorption spectra were
Compounds IV VI (general procedure). Bis-
phenol I, 80 mmol, was added under argon to a sus-
pension of freshly calcined potassium carbonate,
480 mmol, and sodium iodide, 160 mmol, in 400 ml
of anhydrous DMF. The mixture was stirred for 1 h at
80 C, 240 mmol of the corresponding oligoethylene
glycol derivative was added, and the mixture was
heated for 35 h at that temperature. The mixture was
then filtered, the filtrate was evaporated to dryness
under reduced pressure, and the residue was dissolved
in chloroform. The solution was washed with a 5%
aqueous solution of sodium hydroxide and two por-
tions of water, dried over anhydrous MgSO4, and
evaporated under reduced pressure. The residue was
purified by recrystallization from 2-propanol to obtain
the corresponding product as orange red crystals.
measured in the
range from 200 to 600 nm on
Specord M-40 and Lambda-9 UV-Vis-NIR spectro-
photometers using methanol or dioxane as solvent.
The luminescence spectra of solid samples in the
range from 370 to 700 nm were recorded on a SDL-1
luminescence spectrometer; luminescence excitation
was effected with a DRSh-250 mercury lamp using a
UFS-2 light filter to isolate radiation with 313 nm.
Samples were placed in a 1-cm quartz cell or in a
solid-sample cell with a pocket diameter of 9 mm.
The elemental compositions were determined at the
Analytical Laboratory, Physicochemical Institute,
National Academy of Sciences of Ukraine. Thin-layer
chromatography was performed on Silufol UV-254
plates (Kavalier). All commercial chemicals were used
without additional purification unless otherwise stated.
2,7-Bis[2-(2-hydroxyethoxy)ethoxy]-9H-fluoren-
9-one (IV). Yield 78%, mp 117 119 C. H NMR
1
spectrum (CDCl3), , ppm (J, Hz): 1.97 br.s (2H, OH),
3.65 3.72 m (4H, CH2O), 3.74 3.82 m (4H, CH2O),
3.84 3.92 m (4H, CH2O), 4.14?4.21 m (4H, CH2O),
6.97 d.d (2H, Hb, J 8.09), 7.17 d (2H, Ha, J 2.18),
7.29 d (2H, Hc, J 8.09). Found, %: C 65.19; H 6.29.
C21H24O7. Calculated, %: C 64.94; H 6.23.
2,7-Dihydroxy-9H-fluoren-9-one (I) was syn-
thesized as described in [25].
2,7-Dimethoxy-9H-fluorenon-9-one (II). Bis-
phenol I, 2.12 g, was added to a solution of 1 g of
sodium hydroxide in 9 ml of water, the mixture was
stirred for 30 min, and 2.52 g of dimethyl sulfate was
added dropwise over a period of 40 min. The mixture
was stirred for 1 h, maintaining it slightly boiling, and
cooled, and the precipitate was filtered off and washed
with water. The product was purified by recrystalliza-
tion from ethanol. Yield 1.4 g (58%), mp 127 128 C;
2,7-Bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}-
9H-fluoren-9-one (V). Yield 77%, mp 91 92 C.
1H NMR spectrum (CDCl3), , ppm (J, Hz): 2.18 br.s
(2H, OH), 3.63 t (4H, CH2O, J 4.2), 3.68 3.82 m
(12H, CH2O), 3.87 t (4H, CH2O, J 4.5), 4.17 t (4H,
CH2O, J 4.5), 6.98 d.d (2H, Hb, J 8.09), 7.17 d (2H,
Ha, J 2.18), 7.28 d (2H, Hc, J 8.09). Found, %: C
62.82; H 6.65. C25H32O9. Calculated, %: C 63.01;
H 6.77.
1
published data [26]: mp 123 125 C. H NMR spec-
trum (CDCl3), , ppm (J, Hz): 3.84 s (6H, Me),
6.94 d.d (2H, Hb, J 8.09), 7.16 d (2H, Ha, J 2.49),
7.29 d (2H, Hc, J 8.09). Found, %: C 75.28; H 4.93.
C15H12O3. Calculated, %: C 74.99; H 5.03.
2,7-Bis(2-{2-[2-(2-hydroxyethoxy)ethoxy]eth-
oxy}ethoxy)-9H-fluoren-9-one (VI). 2Yield 80%,
mp 61 63 C. H NMR spectrum (CDCl3), , ppm (J,
1
2,7-Bis(2-hydroxyethoxy)-9H-fluoren-9-one (III).
A solution of 14.4 g of sodium hydroxide in 75 ml of
water was added to a mixture of 31.8 g of bis-phenol
I, 24 ml of 2-chloroethanol, and 100 ml of water at
such a rate that the temperature of the mixture did not
exceed 30 C. The temperature was raised to 70 C
over a period of 2 h, and the mixture was stirred for
2 h at that temperature. After cooling, the precipitate
was filtered off and washed with water until colorless
washings. The precipitate was dried in air and recrys-
tallized from 2-propanol. Diol III was isolated as
Hz): 2.07 br.s (2H, OH), 3.61 t (4H, CH2O, J 4.51),
3.65 3.77 m (20H, CH2O), 4.17 t (4H, CH2O, J 4.67),
4.28 t (4H, CH2O, J 4.67), 6.97 d.d (2H, Hb, J 8.09),
7.17 d (2H, Ha, J = 2.49), 7.28 d (2H, Hc, J 8.10).
Found, %: C 61.87; H 6.94. C29H40O11. Calculated,
%: C 61.69; H 7.14.
Bis-p-toluenesulfonates VII X (general proce-
dure). A solution of 75 mmol of p-toluenesulfonyl
chloride in 30 ml of dry dioxane was added dropwise
over a period of 2 h to a solution of 30 mmol of diol
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

276
KIRICHENKO et al.
III VI and 90 mmol of triethylamine in 120 ml of
chloroform, maintaining the temperature at 0 5 C.
The mixture was then stirred for 30 h at room tem-
perature, diluted with an equal volume of chloroform,
washed in succession with 5% hydrochloric acid, 10%
aqueous ammonia, water, and a saturated solution of
sodium chloride, and dried over anhydrous MgSO4.
The solvent was distilled off under reduced pressure,
and the residue was purified by recrystallization from
2-propanol. Compounds VII X were isolated as
orange crystalline substances.
Harom, J 8.10). Found, %: C 58.98; H 5.83. C43H52
O15S2. Calculated, %: C 59.16; H 6.00.
Diazides XI and XII (general procedure). A solu-
tion of 50 mmol of sodium azide in 10 ml of water
was added to a mixture of 5 mmol of bis-p-toluenesul-
fonate VIII or IX and 1 mmol of tetrabutylammonium
iodide in 50 ml of toluene, and the mixture was stirred
for 4 h at 80 85 C. The organic layer was separated,
and the aqueous phase was extracted with toluene
(3 10 ml). The extracts were combined with the
organic phase, the solvent was removed under reduced
pressure, and the residue was recrystallized from
2-propanol. Diazides XI and XII were isolated as
orange red crystals.
2,7-Bis[2-(4-methylphenylsulfonyloxy)ethoxy]-
9H-fluoren-9-one (VII). A solution of 1.92 g of
p-toluenesulfonyl chloride in 4 ml of anhydrous di-
oxane was added dropwise over a period of 2 h to a
solution of 0.8 g of diol III and 1.44 ml of triethyl-
amine in a mixture of 15 ml of dioxane ans 3 ml of
chloroform, maintaining the temperature at 0 5 C.
The subsequent procedure was the same as the above
given general procedure. Yield 92%, mp 140 142 C.
1H NMR spectrum (CDCl3), , ppm (J, Hz): 2.44 s
(6H, Me), 4.13 4.19 m (4H, CH2O), 4.34 4.41 m (4H,
CH2O), 6.84 d.d (2H, Hb, J 8.09), 6.96 d (2H, Ha, J
2.18), 7.25 d (2H, Hc, J 8.41), 7.35 d (4H, Harom, J
8.41), 7.82 d (4H, Harom, J 8.41). Found, %: C 61.11;
H 4.56. C31H28O9S2. Calculated, %: C 61.17; H 4.64.
2,7-Bis[2-(2-azidoethoxy)ethoxy]-9H-fluoren-9-
1
one (XI). Yield 95%, mp 85 87 C. H NMR spec-
trum (CDCl3), , ppm (J, Hz): 3.43 t (4H, CH2N, J
4.82), 3.76 t (4H, CH2O, J 4.82), 3.87 t (4H, CH2O,
J 4.51), 4.17 t (4H, CH2O, J 4.51), 6.98 d.d (2H, Hb,
J 8.10), 7.16 d (2H, Ha, J 1.86), 7.29 d (2H, Hc, J
8.15). Found, %: C 57.46; H 4.95; N 19.28. C21H22
N6O5. Calculated, %: C 57.53; H 5.06; N 19.17.
2,7-Bis{2-[2-(2-azidoethoxy)ethoxy]ethoxy}-9H-
1
fluoren-9-one (XII). Yield 91%, mp 24 25 C. H
NMR spectrum (CDCl3), , ppm (J, Hz): 3.40 t (4H,
CH2N, J 4.98), 3.66 3.78 m (12H, CH2O), 3.87 t (4H,
CH2O, J 4.67), 4.16 t (4H, CH2O, J 4.67), 6.97 d.d
(2H, Hb, J 8.09), 7.16 d (2H, Ha, J 2.49), 7.28 d (2H,
Hc, J 8.09). Found, %: C 56.88; H 5.72; N 16.98.
C25H30N6O7. Calculated, %: C 57.03; H 5.74;
N 15.96.
2,7-Bis{2-[2-(4-methylphenylsulfonyloxy)eth-
oxy]ethoxy}-9H-fluoren-9-one (VIII). Yield 88%,
1
mp 109 112 C. H NMR spectrum (CDCl3), , ppm
(J, Hz): 2.42 s (6H, Me), 3.73 3.83 m (8H, CH2O),
4.07 t (4H, CH2O, J 4.52), 4.21 t (4H, CH2O, J 4.82),
6.95 d. d (2H, Hb, J 8.10), 7.12 d (2H, Ha, J 2.18),
7.27 7.36 m (6H, Harom, Hc), 7.80 d (4H, Harom, J
8.09). Found, %: C 60.47; H 5.41. C35H36O11S2.
Calculated, %: C 60.33; H 5.21.
Diamines XIII and XIV (general procedure). Tri-
phenylphosphine, 6 mmol, was added in portions over
a period of 10 h to a suspension of 2.5 mmol of di-
azide XI or XII in aqueous dioxane (20 ml of dioxane
and 0.8 ml of water) under stirring at 20 C. The mix-
ture was then stirred for 10 h and diluted with dioxane
(30 40 ml) to dissolve the precipitate. The undis-
solved material was filtered off, and the filtrate was
acidified to pH 2 with concentrated hydrochloric acid
under stirring and cooling with ice water. The solvent
was separated from the oily material by decanting,
and the product was washed with dioxane (3 30 ml).
The residue was dissolved in a minial amount of
ethanol, and diethyl ether was added in small portions
to the solution under stirring until an oily material no
longer separated. The oily product crystallized on
cooling. It was filtered off and dried under reduced
pressure to isolate dihydrochloride XIII or XIV as
pink or light orange crystals.
2,7-Bis(2-{2-[2-(4-methylphenylsulfonyloxy)-
ethoxy]ethoxy}ethoxy)-9H-fluoren-9-one (IX). Yield
1
84%, mp 68 70 C. H NMR spectrum (CDCl3),
,
ppm (J, Hz): 2.43 s (6H, Me), 3.57 3.75 m (12H,
CH2O), 3.79 3.87 m (4H, CH2O), 4.08 4.21 m (8H,
CH2O), 6.97 d.d (2H, Hb, J 8.10), 7.15 d (2H, Ha, J
2.49), 7.29 d (2H, Hc, J 8.10), 7.33 d (4H, Harom, J
8.25), 7.80 d (4H, Harom, J 8.35). Found, %: C 59.56;
H 5.47. C39H44O13S2. Calculated, %: C 59.68; H 5.65.
2,7-Bis[2-(2-{2-[2-(4-methylphenylsulfonyloxy)-
ethoxy]ethoxy}ethoxy)ethoxy]-9H-fluoren-9-one
1
(X). Yield 70%, oily substance. H NMR spectrum
(CDCl3), , ppm (J, Hz): 2.43 s (6H, Me), 3.60 s (8H,
CH2O), 3.62 3.76 m (12H, CH2O), 3.85 t (4H,
CH2O, J 4.67), 4.11 4.20 m (8H, CH2O), 6.97 d.d
(2H, Hb, J 8.09), 7.15 d (2H, Ha, J 2.18), 7.28 d (2H,
Hc, J 8.10), 7.33 d (4H, Harom, J 8.11), 7.79 d (4H,
2,7-Bis[2-(2-aminoethoxy)ethoxy]-9H-fluoren-9-
one dihydrochloride (XIII). Yield 74%, mp >200 C
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SYNTHESIS AND LUMINESCENCE SPECTRAL PROPERTIES
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1
(decomp.). H NMR spectrum (DMSO-d6), , ppm
9. Lewis, J., Raithby, P.R., and Wong, W.-Y., J. Orga-
nomet. Chem., 1998, vol. 556, nos. 1 2, p. 219.
(J, Hz): 2.91 3.05 m (4H, CH2N), 3.70 t (4H, CH2O,
J 5.29), 3.79 t (4H, CH2O, J 4.21), 4.20 t (4H, CH2O,
J 4.20), 7.07 7.17 m (4H, Ha, Hb), 7.59 d (2H, Hc, J
9.03), 8.11 br.s (6H, NH+3). Found, %: C 54.82; H
6.23; N 6.17. C21H28Cl2N2O5. Calculated, %: C 54.91;
H 6.14; N 6.10.
10. Akinchan, N.T., Drozdzewski, P.M., and Akinchan, R.,
Pol. J. Chem., 2000, vol. 74, no. 9, p. 1221.
11. Szafert, S., Haquette, P., Falloon, S.B., and Gla-
dysz, J.A., J. Organomet. Chem., 2000, vol. 604,
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2,7-Bis{2-[2-(2-aminoethoxy)ethoxy]ethoxy}-9H-
fluoren-9-one dihydrochloride (XIV). Yield 80%,
mp >130 C (decomp.). 1H NMR spectrum (CDCl3), ,
ppm (J, Hz): 2.95 t (2H, CH2N, J 5.13), 3.10 3.20 m
(1H, CH2N), 3.35 3.45 m (1H, CH2N), 3.47 3.70 m
(12H, CH2O), 3.76 br.s (4H, CH2O), 4.14 br.s (4H,
CH2O), 6.01 br.s (1H, NH+3), 6.98 7.11 m (4H, Ha,
Hb), 7.50 t (2H, Hc, J 7.63), 8.15 br.s (5H, NH+3).
Found, %: C 54.60; H 6.56; N 5.09. C25H36Cl2N2O7.
Calculated, %: C 54.85; H 6.63; N 5.12.
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