Synthesis and properties of biphenyl-containing fluorenonophanes

Article abstract of DOI:10.1007/s11172-008-0224-3

A novel family of crownophanes containing 2,7-dioxyfluorenone and 4,4′-dioxybiphenyl fragments linked by tri- and tetraethylene glycol residues was obtained. The formation of pseudorotaxanes in reactions of these ligands with paraquat hexafluorophosphate

Full text of DOI:10.1007/s11172-008-0224-3

Russian Chemical Bulletin, International Edition, Vol. 57, No. 8, pp. 1697—1702, August, 2008
1697
Synthesis and properties of biphenylꢀcontaining fluorenonophanes
N. G. Luk´yanenko, T. I. Kirichenko, A. Yu. Lyapunov, and E. Yu. Kulygina
A. V. Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine,
86 Lyustdorfskaya Doroga, 65080 Odessa, Ukraine.
Eꢀmail: ngl@farlep.net
A novel family of crownophanes containing 2,7ꢀdioxyfluorenone and 4,4´ꢀdioxybiphenyl
fragments linked by triꢀ and tetraethylene glycol residues was obtained. The formation of
pseudorotaxanes in reactions of these ligands with paraquat hexafluorophosphate was detected
1
by FAB mass spectrometry, H NMR spectroscopy, and electronic absorption spectroscopy.
Key words: crownophanes, fluorenones, biaryls, paraquat, pseudorotaxanes, mass
spectrometry.
plexes with ionic and neutral compounds.1,2 Among such
receptors, an important place is occupied by cyclophanes,
whose macrocyclic molecules contain aromatic fragments.3,4
The development of supramolecular chemistry is
inseparably linked with the design and synthesis of new
molecular receptors capable of selectively forming comꢀ
Scheme 1
O
O
O
O
O
i
n
+
HO
OH
O
O
4
OTs
TsO
n
n
3a,b
O
O
O
O
n
O
O
O
O
O
O
O
O
O
O
n
+
O
O
O
O
n
O
O
1a,b
O
O
O
n
O
O
O
O
n
2a,b
n = 1 (a), 2 (b).
i. K CO /DMF, 80 °C, 40 h.
2
3
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1665—1670, May, 2008.
1066ꢀ5285/08/5708ꢀ1697 © 2008 Springer Science+Business Media, Inc.

1698
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Luk´yanenko et al.
Hc
The selectivity of formation and strength of molecular
cyclophane complexes depend on the distinctive features
of their noncovalent interactions with the substrate,5
including hydrogen bonding,6,7 solvatophobic effects,8
coordination with metals,9,10 and π—πꢀinteractions
between the πꢀelectron poor and πꢀelectron rich aromatic
fragments of the partners.11—16 The latter interaction is
especially valuable for the template synthesis of supramoꢀ
lecular systems, in particular, catenanes and rotaxanes,
which are basic elements of molecular machines, switches,
logic gates, and other nanodevices.17—23
Hb
Me
Me
O
O
Ha
O
5
H6´
H5´
Me
O
O
The strength and nature of noncovalent interactions
of cyclophanes with a guest molecule largely depend on the
nature of their aromatic fragments. Normally, introduction
into cyclophanes of large aromatic subunits enriched with
πꢀelectrons enhances their tendency toward the formation
of inclusion complexes with πꢀelectronꢀdeficient molecules.
Recently, we have described the synthesis and properties
of the first representatives of naphthaleneꢀcontaining
fluorenonophanes.24 Here we describe the synthesis and
properties of new fluorenone crownophanes with the 2,7ꢀ
dioxyfluorenone and 4,4´ꢀdioxybiphenyl fragments linked
by triꢀ and tetraethylene glycol residues.
Me
H3
H2
6
In all cases, the largest upfield shift was observed for
the Hc protons of fluorenone and the 2,2´,6,6´ꢀprotons of
biphenyl. The difference between the shifts decreases with
an increase in the ring size in pairs of monomeric 1a,b and
dimeric cyclophanes 2a,b. In the spectra of cyclophanes
1a,b, the signals for the aromatic protons are noticeably shifted
upfield compared to their positions in the spectra of dimers
2a,b. The greatest shift (–∆δ = 0.1—0.2 ppm) is observed
for the protons of the biphenyl fragment.
Crownophanes 1a,b and 2a,b were obtained as shown
in Scheme 1.
Reactions of ditosylates 3a,b (see Ref. 24) with 4,4´ꢀdiꢀ
hydroxybiphenyl (4) were carried out in their highly diluted
solutions in DMF in the presence of K2CO3. After workup
of the reaction mixture and separation by column chroꢀ
matography, we obtained fluorenone crownophanes 1a,b
in moderate yields and their dimers 2a,b as minor products.
Obviously, the aforementioned spectroscopic features
provide evidence for the structural similarity of compounds
1a,b and 2a,b in solutions; i.e., either macrocycle mainly
exists in the conformations in which the fluorenone and
biphenyl fragments are stacked sufficiently close.
A great number of pseudorotaxanes and rotaxanes
(complexes of salts of the paraquat dication [7]2+ with
benzocrown ethers, cryptands, cyclophanes, and other
macrocyclic molecules) have been documented.25—29
Fluorenone crownophanes 1a,b containing two πꢀelecꢀ
1
The H NMR spectra of fluorenone crownophanes 1a,b
and 2a,b show a set of signals at δ 3.64—4.16 typical of
oligo(ethylene glycol) fragments. The fluorenone protons
are manifested as a characteristic set of two doublets and a
doublet of doublets and the biphenyl protons, as two
doublets (Fig. 1, a). Apparently, because of the mutual
shielding by the opposite aromatic fragments, the signals
for all the protons in the aromatic fragments of fluorenone
crownophanes 1a,b and 2a,b are shifted upfield compared
to their positions in the spectra of the model compounds
2,7ꢀdimethoxyfluorenone (5) and 4,4´ꢀdimethoxybiphenyl
(6) (Table 1).
+
N
+
Me
N
Me •2PF6–
Hβ
Hα
7•2PF6
Table 1. Absolute (δ) and relative (∆δ) chemical shifts of the aromatic protons in crownophanes 1a,b and 2a,b
and model compounds 5 and 6 in CDCl3
Comꢀ
pound
Ha
–∆δ
Hb
–∆δ
Hc
H(3,3´,5,5´)
H(2,2´,6,6´)
–∆δ
δ
δ
δ
–∆δ
δ
–∆δ
δ
1a
1b
2a
2b
5
7.02 0.14
7.10 0.06
7.03 0.13
7.10 0.06
6.89
6.88
6.84
6.89
6.94
—
0.05
0.06
0.10
0.05
—
7.05
7.11
7.00
7.14
7.28
—
0.23
0.17
0.28
0.14
—
6.75
6.87
6.78
6.89
—
0.21
0.09
0.18
0.07
—
7.14 0.34
7.33 0.15
7.23 0.25
7.35 0.13
7.16
—
—
—
—
—
—
6
—
—
6.96
—
7.48

Biphenylꢀcontaining fluorenonophanes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1699
H(2),H(6)
Ha
H(3),H(5)
Hс
a
Hb
b
Hα
Hβ
c
8.5
8.0
7.5
7.0
δ
1
Fig. 1. Fragments of the H NMR spectra of crownophane 1a (a), its equimolar mixture with paraquat 7•2PF6 (b), and paraquat
7•2PF6 (c) in CD3CN—CDCl3 (4 : 3).
tronꢀdonating aromatic fragments are also supposed to
form inclusion complexes with the paraquat dication [7]2+
seems to yield a more stable complex than crownophane 1a
.
under the conditions of the MS experiment.
1
The possibility of the formation of such complexes
was verified and their relative stability was qualitatively
estimated by FAB mass spectrometry, which allows their
detection.30,31 Mass spectra were recorded for solutions
containing equimolar amounts of crownophanes 1a,b and
four equivalents of paraquat 7•2PF6 in 3ꢀnitrobenzyl alꢀ
cohol. The mass spectrum exhibits the peaks [M – PF6]+
corresponding to elimination of the hexafluorophosphate
anion from 1 : 1 complexes of these crownophanes with
salt 7•2PF6. The peak of the complex [1b•7]•2PF6 is
2.5 times more intense than the corresponding peak of the
complex [1a•7]•2PF6. A similar spectral pattern is charꢀ
acteristic of most pseudorotaxanes, suggesting the formaꢀ
tion of stable complexes of these crownophanes with
salt 7•2PF6 (see Refs 17, 32—34). Since the ratio of the peak
intensities for the complex ions of structurally similar comꢀ
plexes should correlate with their stabilities, crownophane 1b
In the H NMR spectra of equimolar mixtures of the
resulting crownophanes with paraquat 7•2PF6, the sigꢀ
nals for all the protons in the aromatic fragments of
crownophanes 1a,b and paraquat 7•2PF6 are shifted
upfield compared to their positions in the spectra of the
individual compounds (Fig. 1).
This is a reliable indication of the formation of incluꢀ
sion complexes of the pseudorotaxane type. The shift of
the signals for the Hα and Hβ protons in paraquat 7•2PF6
for structurally similar complexes is, to a first approximaꢀ
tion, proportional to their stabilities.17 The great absolute
∆δc values of the signals for the protons of paraquat 7•2PF6
in the spectrum of its mixture with crownophane 1b sugꢀ
gest that its complex is more stable than the complex of
compound 1a (Table 2). The 1H NMR data for the
stabilities of the complexes of paraquat 7•2PF6 with
crownophanes 1a,b agree well with the FAB MS data.
Table 2. Upfield shifts of the signals for the aromatic protons in crownophanes 1a,b and paraquat 7•2PF6 in
1
the H NMR spectra of their equimolar mixtures (–∆δ ) (CD3CN—CDCl3, 4 : 3)
c
Compound
–∆δc
Ha
Hb
Hc
H(3,3´,5,5´) H(2,2´,6,6´)
Ηα
Hβ
[1a•7]•2PF6
[1b•7]•2PF6
0.08
0.12
0.02
0.02
0.02
0.01
0.03
0.05
0.02
0.04
0.08
0.12
0.13
0.19

1700
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
Luk´yanenko et al.
1a
1b
Fig. 2. Calculated structures and energies of stabilization (∆E) of the complexes of crownophanes 1a and 1b with the paraquat dication [7]2+. The
difference between the energy of the complex and the sum of the energies of the free host and guest is ∆E = Ecomplex – Ehost – Eguest = 121
(1a) and 209 kJ mol–1 (1b).
When a solution of paraquat 7•2PF6 is added to soluꢀ
tions of crownophanes 1a,b in acetonitrile, the initial
orange solutions turn red. The intensities of the bands in
the UV region of the spectrum of the resulting mixtures
are lower than the sum of the band intensities in the
spectra of the individual compounds, which is characterꢀ
istic of pseudorotaxanes, rotaxanes, and catenanes.17,35
Simultaneously, the visible region of the spectrum shows
an additional band superimposed on the absorption band of
the fluorenone fragment. The appearance of this band is due to
the formation of pseudorotaxanes stabilized by donorꢀ
acceptor chargeꢀtransfer interactions of the πꢀdonating
aromatic subunits of cyclophanes with the πꢀwithdrawing
dipyridinium fragment of paraquat 7•2PF6, which is in
the cavity of the macrocycle.35—37 The intensity of this
band increases with the molar ratio paraquat : crownophane.
A greater relative change in the intensity of this band for
the complex of crownophane 1b is probably due to its
higher stability.
Obviously, the differences in the spectroscopic behavꢀ
ior and stability of the complexes of cyclophanes 1a,b
with paraquat 7•2PF6 are associated with their structures.
However, we obtained no single crystals of these comꢀ
plexes suitable for Xꢀray diffraction analysis. For this
reason, we searched for the optimum structures of these
complexes using the Monte Carlo method of statistical
mechanics (MMFF94 force field, Spartan´06 program
package)38 followed by refinement of the geometries of
the thermodynamically most favorable conformations with
the semiempirical PM3 method.
[1a•7]2+ (–∆E = 209 and 121 kJ mol–1, respectively). In
the 1H NMR spectra of both pseudorotaxanes, the signals
for the Hβ protons of the paraquat dication [7]2+ are shifted
upfield more considerably than the signals for the Hα
protons (see Table 2). In pseudorotaxane [1a•7]2+, the
phenyl rings of the biphenyl in cyclophane 1a and the
pyridinium rings of the paraquat dication [7]2+ are nearly
parallel, the distance between their centroids being ~3.9 Å.
This allows them to take an active part in donor—accepꢀ
tor π—πꢀinteractions of the faceꢀtoꢀface type.39 In pseudoꢀ
rotaxane [1b•7]2+, such interactions occur only between
one phenyl ring of the biphenyl in cyclophane 1b and one
pyridinium ring of the paraquat dication [7]2+. The greater
cavity size in compound 1b allows edgeꢀtoꢀface interacꢀ
tions for the second pair of these rings, which is thermoꢀ
dynamically more favorable.40,41 In both pseudorotaxanes,
the structure is stabilized42 by the C—H...O contacts
between the Hα atoms of the paraquat dication [7]2+ and
the ether O atoms of the polyether chains in the cycloꢀ
phanes. However, the decisive factor for the stability of
pseudorotaxanes [1a•7]2+ and [1b•7]2+ is probably a
charge—dipole interaction of the paraquat dication [7]2+
with the carbonyl group of fluorenone. In complex
[1b•7]2+, this interaction is substantially stronger than
that in [1a•7]2+ (C=O...N 2.92 and 3.05 Å, respectively).
To sum up, we obtained new biphenylꢀcontaining
fluorenonophanes, which form pseudorotaxanes in reacꢀ
tions with paraquat hexafluorophosphate 7•2PF6 and can
be used for the synthesis of rotaxanes and catenanes.
The sought structures of complexes [1a•7]2+ and
[1b•7]2+ are generally similar. In either structure, the
paraquat dication 72+ “pierces” the intramolecular cavity of
the cyclophane to form a typical pseudorotaxane (Fig. 2).
However, the energy of stabilization of pseudorotaxane
[1b•7]2+ is substantially higher than that of pseudorotaxane
Experimental
1H and 13C NMR spectra were recorded in CDCl3 on a
Varian VXRꢀ300 instrument (300 and 75.5 MHz, respectively).
The 1H NMR spectra of the complexes were recorded in
CDCl3—CD3CN (3 : 4, v/v). Mass spectra (EI, 70 eV, direct

Biphenylꢀcontaining fluorenonophanes
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 8, August, 2008
1701
1
inlet probe) were recorded on an MXꢀ1321 mass spectrometer.
FAB mass spectra were recorded on a VG 7070EQ mass specꢀ
trometer (Xe, 8 kV) in the 3ꢀnitrobenzyl alcohol matrix. IR
spectra were recorded on a Shimadzuꢀ8400S spectrophotometer
(KBr pellets). UV spectra were recorded on a Specord M40
spectrophotometer. Preparative column chromatography was
carried out on Kieselgel 60 silica gel (0.063—0.100 mm, Merck).
The purity of all the compounds obtained was checked by TLC
(Sorbfil UFꢀ254). Melting points were measured in open capilꢀ
laries and are given uncorrected. Compounds 3a,b (see Ref. 24),
5 (see Ref. 43), and 7•2PF6 (see Ref. 44) were prepared accordꢀ
ing to known procedures. Commercial compounds 4 and 6
(Acros) were used as purchased.
(2.48). IR, ν/cm–1: 1712 (C=O). H NMR, δ: 3.73 (s, 16 H,
CH2O); 3.85—3.92, 3.98—4.06 (both m, 8 H each, CH2O); 6.78
(d, 4 H, H(3), H(5), J = 8.7 Hz); 6.84 (dd, 2 H, Hb, J = 8.1 Hz,
J = 2.5 Hz); 7.00 (d, 2 H, Hc, J = 8.1 Hz); 7.03 (d, 2 H, Ha,
J = 2.5 Hz); 7.23 (d, 4 H, H(2), H(6), J = 8.7 Hz). 13C NMR, δ:
67.5, 68.0, 69.5, 69.7, 70.6, 70.7, 70.8, 70.9, 110.1, 114.6, 120.5,
120.9, 127.3, 133.0, 135.8, 137.4, 157.7, 159.1, 193.3. MS (EI),
m/z (Irel (%)): 714 [M]+ (100), 357 (4), 212 (5), 186 (8), 45 (21).
6,9,12,15,18,30,33,36,39,42,51,54,57,60,63,75,78,81,
84,87ꢀIcosaoxaundecacyclo[86.2.2.22,5.243,46.247,50.119,23.125,29
.
1
64,68.170,74.022,26.067,71]dohectaꢀ1(90),2,4,19(100),20,22,
25(99),26,28,43,45,47,49,64(94),65,67,70(93),71,73,88,91,
95,97,101ꢀtetracosaeneꢀ24,69ꢀdione (2b), orange crystals.
Yield 0.17 g (2.4%), m.p. 153 °C (from C6H6). Found (%):
C, 69.02; H, 6.78. C82H92O22. Calculated (%): C, 68.89; H,
6.49. UV (MeCN), λmax/nm (logε): 271 (5.21), 473.5 (2.74).
Synthesis of crownophanes 1 and 2 (general procedure).
A solution of 4,4´ꢀdihydroxybiphenyl (4) (1.86 g, 0.01 mol) and
ditosylate 3a,b (0.01 mol) in anhydrous DMF (400 mL) was
added dropwise for 10 h to a stirred suspension of dry K2CO3
(8.28 g, 0.06 mol) in anhydrous DMF (600 mL). The reaction
temperature was maintained at 80 °C. After the addition was
completed, the reaction mixture was stirred at this temperature
for an additional 40 h. On cooling, the mixture was filtered and
concentrated in vacuo. The residue was refluxed with toluene
(500 mL). The toluene solution was cooled to room temperature
and filtered. All solid residues were repeatedly washed with
toluene to extract the product completely. The combined toluene
extracts were concentrated in vacuo. After purification by column
chromatography on SiO2 in CHCl3—MeOH (100 : 1), the products
were recrystallized, if required, from an appropriate solvent.
IR, ν/cm–1: 1715 (C=O). H NMR, δ: 3.65—3.78 (m, 32 H,
1
CH2O); 3.80—3.90, 4.04—4.15 (both m, 16 H each, CH2O);
6.85—6.93 (m, 12 H, Hb, H(3), H(5)); 7.10 (d, 4 H, Ha, J = 2.5 Hz);
7.14 (d, 4 H, Hc, J = 8.1 Hz); 7.35 (d, 8 H, H(2), H(6), J = 8.7 Hz).
13C NMR, δ: 67.5, 68.0, 69.6, 69.7, 70.7, 70.8, 110.3, 114.8,
120.5, 120.9, 127.5, 133.4, 135.9, 137.5, 157.8, 159.2, 193.5. MS
(FAB), m/z (Irel (%)): 1429 [M + H]+ (100).
Molecular modeling. A search for the optimum structures of
fluorenone crownophanes 1a,b and their complexes with the
paraquat dication [7]2+ was carried out in two steps. First, we
found thermodynamically favorable conformations for
compounds 1a,b, [1a•7]2+, and [1b•7]2+ using the Monte
Carlo method of statistical mechanics (MMFF94 force field,
Spartan´06 program package).38 Out of the resulting 100 strucꢀ
6,9,12,15,27,30,33,36ꢀOctaoxahexacyclo[35.2.2.22,5.116,20
.
1
22,26.019,23]pentatetracontaꢀ1(39),2,4,16(43),17,19,22(42),
23,25,37,40,44ꢀdodecaenꢀ21ꢀone (1a), orange crystals. Yield
1.72 g (28%), m.p. 166.5 °C (from MeCN). Found (%):
C, 71.16; H, 6.40. C37H38O9. Calculated (%): C, 70.91; H, 6.11.
tures of each compound in an energy gap of 10 kcal mol–1
,
we selected the most favorable one to three structures so that
their total population exceeded 90%. Each of these conformaꢀ
tions was optimized by the semiempirical PM3 method to find a
structure with the minimum energy. The energies of stabilizaꢀ
tion of pseudorotaxanes [1a•7]2+ and [1b•7]2+ (∆E)5 were
calculated as the differences between the energies of their
most favorable structures (Ecomplex) and the energies of the optiꢀ
mized conformations of the corresponding free cyclophanes
(Ehost) and the paraquat dication [7]2+ (Eguest) by the formula
UV (MeCN), λmax/nm (logε): 271 (4.88), 472 (2.40). IR, ν/cm–1
:
1713 (C=O). 1H NMR, δ: 3.76 (s, 8 H, CH2O); 3.83—3.89,
4.00—4.09 (both m, 8 H each, CH2O); 6.75 (d, 4 H, H(3), H(5),
J = 8.7 Hz); 6.89 (dd, 2 H, Hb, J = 8.1 Hz, J = 2.5 Hz); 7.02 (d,
2 H, Ha, J = 2.5 Hz); 7.05 (d, 2 H, Hc, J = 8.1 Hz); 7.14 (d, 4 H,
H(2), H(6), J = 8.7 Hz). 13C NMR, δ: 67.6, 67.9, 69.6, 69.7,
71.0, 71.1, 110.3, 114.9, 120.4, 120.9, 127.1, 132.9, 135.8, 137.4,
157.7, 159.2, 193.2. MS (EI), m/z (Irel (%)): 626 [M]+ (100),
313 (2), 212 (7), 186 (11), 45 (36).
∆E = Ecomplex – Ehost – Eguest
.
6,9,12,15,27,30,33,36,45,48,51,54,66,69,72,75ꢀHexadecaꢀ
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oxaundecacyclo[74.2.2.22,5.237,40.241,44.116,20.122,26.155,59
1
.
61,65.019,23.058,62]nonacontaꢀ1(78)2,4,16(88),17,19,22(87),
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0.044 g (0.7%), m.p. 197.5—198 °C. Found (%): C, 71.19; H,
6.04. C74H76O18. Calculated (%): C, 70.91; H, 6.11. IR, ν/cm–1
:
1
1712 (C=O). H NMR, δ: 3.76 (s, 16 H, CH2O); 3.82—3.91,
4.07—4.15 (both m, 16 H each, CH2O); 6.84—6.92 (m, 12 H,
Ha, H(3), H(5)); 7.08—7.15 (m, 8 H, Hb, Hc); 7.33 (d, 8 H,
H(2), H(6), J = 8.7 Hz). 13C NMR, δ: 67.5, 68.0, 69.7, 69.8,
70.9, 71.0, 110.4, 114.8, 120.5, 120.9, 127.4, 133.3, 135.8, 137.5,
157.8, 159.1, 193.4. MS (FAB), m/z (Irel (%)): 1253 [M + H]+ (100).
6,9,12,15,18,30,33,36,39,42ꢀDecaoxahexacyclo[41.2.2.
2
2,5.119,23.125,29.022,26]henpentacontaꢀ1(45),2,4,19(49),20,22,
25(48),26,28,43,46,50ꢀdodecaenꢀ24ꢀone (1b), orangeꢀred
crystals. Yield 2.38 g (34%), m.p. 148—149 °C (from C6H6).
Found (%): C, 69.03; H, 6.59. C41H46O11. Calculated (%):
C, 68.89; H, 6.49. UV (MeCN), λmax/nm (logε): 272 (4.97), 478
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Received March 12, 2008;
in revised form May 23, 2008