Synthesis of crown-containing and related hetarylphenylacetylenes and acetylenyl dyes

Article abstract of DOI:10.1007/s11172-012-0021-x

New 15(18)-crown-5(6)-containing and model methoxy-substituted 1-hetaryl-2-phenylacetylenes of the 4-pyridine and 2-benzothiazole series were synthesized using the addition of bromine to the ethylene fragment of the corresponding styrylheterocycles follow

Full text of DOI:10.1007/s11172-012-0021-x

Russian Chemical Bulletin, International Edition, Vol. 61, No. 1, pp. 148—157, January, 2012
148
Synthesis of crownꢀcontaining and related hetarylphenylacetylenes
and acetylenyl dyes
A. I. Vedernikov,a N. A. Lobova,a L. G. Kuz´mina,b N. A. Aleksandrova,a S. K. Sazonov,a
J. A. K. Howard,c and S. P. Gromova
aPhotochemistry Centre, Russian Academy of Sciences,
7Aꢀ1 ul. Novatorov, 119421 Moscow, Russian Federation.
Fax: +7 (495) 936 1255. Eꢀmail: spgromov@mail.ru
bN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 954 1279
cChemistry Department, Durham University,
South Road, Durham DH1 3LE, UK
New 15(18)ꢀcrownꢀ5(6)ꢀcontaining and model methoxyꢀsubstituted 1ꢀhetarylꢀ2ꢀphenylꢀ
acetylenes of the 4ꢀpyridine and 2ꢀbenzothiazole series were synthesized using the addition of
bromine to the ethylene fragment of the corresponding styrylheterocycles followed by dehydroꢀ
bromination under the action of potassium tertꢀbutoxide. The quaternization of the pyridylꢀ
phenylacetylenes afforded new acetylenyl dyes. The structures of five synthesized compounds
were determined by Xꢀray diffraction analysis.
Key words: styrylheterocycles, hetarylphenylacetylenes, crown ethers, synthesis, structure,
Xꢀray diffraction analysis.
Neutral hetarylphenylacetylenes, their adducts with
ample, pyridylphenylacetylene with the azaꢀ15ꢀcrownꢀ5
fragment,18 monocrownꢀcontaining bis(phenylterpyridylꢀ
acetylene),19 and bis(15ꢀcrown)ꢀcontaining bis(acetylene)
based on 2,2´ꢀdipyridyl.20 This is associated, to some exꢀ
tent, with poor availability of the starting compounds for
the synthesis.
Hetarylphenylacetylenes were earlier synthesized by the
bromination of 1ꢀhetarylꢀ2ꢀphenylethylenes at the C=C
double bond in CCl4 followed by dehydrobromination with
KOH in ethanol21,22 or by the condensation of diphenyl
1ꢀhalogenꢀ1ꢀhetarylmethanephosphonates with benzaldeꢀ
hydes in the presence of a strong base (Wittig reaction in
the Horner—Emmons).23 The synthesis of hetarylphenylꢀ
acetylenes using crossꢀcoupling (Sonogashira reaction and
its modifications) became especially popular in the recent
time (see, e.g., Refs 2 and 24—27).
The preparation of crownꢀcontaining hetarylphenylꢀ
acetylenes using the Wittig or Sonogashira reactions reꢀ
quires fairly complicated and laborꢀconsuming prelimiꢀ
nary synthesis of the starting compounds (phosphonate
salts, phenylacetylenes, halogenꢀ or ethynylꢀsubstituted
heterocycles), and the influence of the macrocyclic fragꢀ
ment in the occurrence of each stage of the multistage
synthesis is hardly predictable. We assumed that comparꢀ
atively easily accessible hetarylphenylethylenes, whose
synthesis has sufficiently been developed28—32 by us, can
Lewis acids, and quaternary salts (acetylenyl dyes) have
a complex of useful properties. These compounds fluoꢀ
resce rather efficiently,1—3 exhibit promising nonlinear
optical properties,1,4,5 are capable of efficient electroꢀ
luminescing,6 can serve as colorimetric and luminescent
sensors to metal cations7,8 and be used as ligands in lumiꢀ
nescent rareꢀearth metal complexes,9 form liquid crysꢀ
tals,10 and possess biological activity.11—14 Structural fragꢀ
ments of hetarylphenylacetylenes were used for the proꢀ
duction of molecular wires15 and a large series of nanoꢀ
sized macrocyclic compounds.16
The introduction of a macroheterocyclic fragment into
a hetarylphenylacetylene molecule in such a way that at
least one its heteroatom would be conjugated with the
chromophore moiety is considerably interesting from the
viewpoint of development of a new type of optical molecꢀ
ular sensors to metal cations. It can be assumed that, unꢀ
like related crownꢀcontaining hetarylphenylethylenes,17
these compounds would have more promising cationꢀdeꢀ
pendent optical characteristics due to a rigid structure of
the chromogen and the absence of the major part of chanꢀ
nels of excited state relaxation typical of hetarylphenylꢀ
ethylenes (trans—cisꢀisomerization, electrocyclic reaction,
[2+2] photocycloaddition). However, a few crownꢀconꢀ
taining hetarylphenylacetylenes are known to date, for exꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 146—155, January, 2012.
1066ꢀ5285/12/6101ꢀ148 © 2012 Springer Science+Business Media, Inc.

Synthesis of hetarylphenylacetylenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
149
be the best starting compounds for the preparation of
crownꢀcontaining hetarylphenylacetylenes. In the present
work, we studied the consecutive bromination—dehydroꢀ
bromination reactions of crownꢀcontaining and model
methoxyꢀsubstituted hetarylphenylethylenes 1—3 of the
4ꢀpyridine, 2ꢀbenzothiazole, and 4ꢀquinoline series in orꢀ
der to optimize the synthesis conditions for the correꢀ
sponding hetarylphenylacetylenes.
At first we attempted to synthesize acetylene comꢀ
pounds 4b and 5 by analogy with the synthesis of diꢀ
(4ꢀpyridyl)acetylene, which is readily formed33 on heatꢀ
ing of 1,2ꢀdi(4ꢀpyridyl)ethylene with a bromine soluꢀ
tion in concentrated HBr followed by dehydrobrominaꢀ
tion by ButONa in tertꢀbutyl alcohol. However, according
to the 1H NMR spectroscopy data, poorly separable
mixtures of compounds 4 and 5 and their bromoꢀconꢀ
taining derivatives at position 6´ of the benzene ring
were obtained. Evidently, under these conditions, the
bromination of the electronꢀexcessive dimethoxyꢀsubstiꢀ
tuted benzene fragment of compounds 1b and 2 or in their
bromination products at the C=C bond occurs simultaꢀ
neously.
which quinolylphenylacetylene bromoꢀsubstituted derivꢀ
ative 6 was isolated by crystallization.
The quaternization of pyridylphenylacetylenes 4a,c
afforded new acetylenyl dyes 7a—d in 47—100% yields
(Scheme 2). The longꢀwavelength absorption of dyes 7a—d
(max = 362—379 nm) is bathochromically shifted relative
to the bands of the starting pyridylphenylacetylenes 4a
and 4c (max = 310 and 315 nm, respectively), which unꢀ
ambiguously due to the more favorable intramolecular
charge transfer from the donor benzene fragment to the
acceptor pyridine residue bearing a positive charge comꢀ
pared to the neutral pyridine residue.
Our preliminary studies by spectrophotometric titraꢀ
tion of the complexation properties of 15ꢀcrownꢀ5ꢀconꢀ
taining acetylenyl dye 7d showed that in a 0.01 M solution
of Et4NClO4 in MeCN this ligand formed 1 : 1 complexes
with Na+ and Ca2+ ions (logK = 3.35 0.05 and 4.14 0.05,
respectively). For the formation of complexes 7d•Na+
and 7d•Ca2+, the hypsochromic shift of the longꢀwaveꢀ
length absorption band maximum attains 16 and 32 nm,
respectively. Under these conditions, model methoxyꢀconꢀ
taining dye 7a forms no complexes with these metal
cations.
The side bromination at the benzene fragment was
avoided when the first stage was carried out under milder
conditions: in a CH2Cl2 or CHCl3 solution at ambient
temperature (Scheme 1). The 1,2ꢀdibromoethanes formed
were not purified and treated with a ButOK solution in
boiling tertꢀbutyl alcohol to give target acetylenes 4a—d
and 5 in 35—59% yields. Under these conditions,
4ꢀstyrylquinoline 3 yielded a mixture of products, from
Neutral pyridylphenylacetylenes 4b,d and acetylenyl
dyes 7a,b,d were obtained as single crystals and studied by
Xꢀray diffraction analysis. The structures of these comꢀ
pounds are shown in Figs 1 and 2; the same numeration of
oneꢀtype atoms differed from the IUPAC rules was used
for convenience of comparison of the geometric parameꢀ
ters. Selected bond lengths and angles are listed in Table 1.
Scheme 1
1, 4: R1 = OMe, R2 = H (a), R1 = R2 = OMe (b), R1 + R2 = OCH2(CH2OCH2)nCH2O, n = 3 (c), 4 (d)

150
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Vedernikov et al.
Схема 2
The carbon—carbon triple bond is localized in all comꢀ
of other crystalline pyridylphenylacetylenes (see, e.g.,
Refs 19, 34, and 35). Nevertheless, the conjugation over
the whole chromophore is possible in compounds 4 and 7,
which is indicated by its, as a whole, planar structure: the
dihedral angle between the planes of the pyridine and benꢀ
zene cycles does not exceed 17.6. In spite of the low
accuracy in determination of structures 4d and 7d, the
following general tendencies in bond length distribution in
the benzene rings of the acetylene compounds can be menꢀ
tioned. Compounds 4b, 4d, and 7d are characterized by
the weakly pronounced alternation of the bond lengths in
the half of the C(8)—C(13)—C(12)—C(11) benzene ring,
i.e., the C(8)—C(13) and C(11)—C(12) bonds are slightly
elongated (average values 1.408(4) and 1.416(4) Å) and
the C(12)—C(13) bond length (average value 1.382(4) Å)
is close to the standard value (1.39 Å). In the second half
of the benzene ring of these compounds, C(8)—C(9)—
C(10)—C(11), the bond lengths are more aligned: the
average values are 1.393(4), 1.395(4), and 1.382(4) Å, reꢀ
spectively. A similar bond length distribution in the benꢀ
zene rings of the molecules has earlier been observed30,36,37
in crystals of the styryl and butadienyl dyes and bis(crown)ꢀ
containing stilbenes. The reproducibility of the effect of
nonsymmetrical bond distribution in two halves of the
benzene ring is reflected, most likely, by the inconsistent
electronic influence of two AlkО substituents in the metaꢀ
and paraꢀpositions with respect to the Py—CC group.
This indicates ꢀconjugation over the whole chromophore
pounds: the average value of the C(6)C(7) bond length is
1.191(4) Å, whereas the lengths of the adjacent formally
ordinary C(3)—C(6) and C(7)—C(8) bonds are 1.432(4)
and 1.435(4) Å on the average, which is characteristic
C(10)
C(9)
C(7)
C(14)
O(1)
O(2)
C(1)
C(4)
C(2)
C(6)
C(11)
N(1)
C(5)
C(8)
C(3)
C(13)
C(12)
C(15)
4b
C(14)
C(9)
C(22)
C(21)
C(10)
C(2)
C(3)
C(1)
O(6)
O(4)
C(23)
O(1)
C(8)
C(6)
O(5)
C(20)
N(1)
C(11)
C(12)
O(2)
C(17)
C(7)
C(13)
C(5)
C(19)
C(15)
C(4)
C(18)
O(3)
C(16)
4d
Fig. 1. Structures of compounds 4b and 4d. Thermal ellipsoids
are drawn with 50% probability.

Synthesis of hetarylphenylacetylenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
151
C(1´)
N(1´)
C(15´)
C(2´)
C(6´)
C(9´)
C(7´)
C(5´)
C(3´)
C(10´)
C(11´)
C(14´)
C(4´)
C(8´)
C(13´)
I(2)
C(4S)
C(3S)
C(5S)
C(6S)
C(9)
O(1´)
C(12´)
C(2S)
C(1S)
C(1)
C(2)
N(1)
C(5)
C(10)
C(11)
C(14)
C(7)
C(6)
C(15)
I(1)
C(8)
C(3)
C(4)
O(1)
C(13)
C(12)
7a•0.5C6H6
C(14)
C(10)
C(1)
N(1)
C(9)
C(2)
C(16)
C(7)
C(11)
O(1)
C(6)
C(8)
C(3)
C(15)
C(12)
C(5)
C(13)
C(4)
O(14)
O(12)
C(3S)
C(2S)
C(1S)
Cl(1)
O(11)
O(13)
7b•0.5C6H6
C(10)
C(1)
C(9)
C(2)
C(14)
C(6)
C(7)
N(1)
C(11)
C(21)
C(22)
C(8)
O(1)
C(3)
C(5)
C(13)
C(12)
O(2)
O(5)
O(1W)
C(4)
C(20)
C(19)
C(15)
O(4)
C(18)
O(3)
C(4S)
C(3S)
O(4W)
O(3W)
O(2W)
C(5S)
O(5W)
C(16)
C(17)
I(1)
C(2S)
C(1S)
C(6S)
7d•0.25C6H6•1.75H2O
Fig. 2. Structures of dyes 7a•0.5C6H6 (two independent molecules), 7b•0.5C6H6, and 7d•0.25C6H6•1.75H2O. Thermal ellipsoids are
drawn with 50% probability.

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Vedernikov et al.
Table 1. Selected bond lengths (d) and bond (), torsion (), and dihedral () angles in compounds 4b,d
and 7a,b,d
Parameter
4b
4d
7a*
7b
7d
Bond length
d/Å
C(3)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
C(8)—C(13)
C(9)—C(10)
C(10)—C(11)
C(11)—C(12)
C(12)—C(13)
O(1)—C(11)
O(1)—C(14)
O(2)—C(12)
O(2)—C(15)
1.4320(13)
1.2010(14)
1.4367(13)
1.3903(14)
1.4077(14)
1.3953(13)
1.3836(13)
1.4141(13)
1.3845(13)
1.3635(11)
1.4365(12)
1.3612(11)
1.4328(12)
1.458(7)
1.155(6)
1.446(6)
1.390(6)
1.411(6)
1.409(5)
1.381(6)
1.410(6)
1.390(6)
1.363(5)
1.454(5)
1.365(5)
1.426(5)
1.425(3), 1.427(3)
1.194(3), 1.192(3)
1.436(3), 1.428(3)
1.393(3), 1.396(3)
1.400(3), 1.396(3)
1.385(3), 1.387(3)
1.383(3), 1.390(3)
1.396(3), 1.390(4)
1.370(3), 1.385(4)
1.368(3), 1.364(3)
1.422(3), 1.435(4)
—
1.426(3)
1.203(3)
1.427(3)
1.399(3)
1.410(3)
1.379(3)
1.399(3)
1.399(3)
1.382(3)
1.368(2)
1.442(3)
—
1.426(6)
1.200(6)
1.433(6)
1.399(6)
1.404(5)
1.382(6)
1.381(5)
1.424(5)
1.372(5)
1.353(4)
1.443(4)
1.364(4)
1.436(4)
—
—
Bond angle
/deg
C(11)—O(1)—C(14)
C(12)—O(2)—C(15)
O(1)—C(11)—C(10)
O(1)—C(11)—C(12)
O(2)—C(12)—C(11)
O(2)—C(12)—C(13)
117.01(7)
117.17(8)
124.84(8)
115.34(8)
114.86(8)
125.16(9)
116.0(4)
119.2(4)
125.5(4)
115.1(4)
115.0(4)
124.5(4)
117.8(2),117.4(2)
117.67(18)
117.8(3)
118.3(3)
126.7(3)
113.9(3)
114.6(3)
125.3(3)
—
—
124.6(2)
115.02(18)
—
124.3(2),124.2(2)
115.9(2),115.6(2)
—
—
—
Torsion angle
/deg
C(14)—O(1)—C(11)—C(10)
C(15)—O(2)—C(12)—C(13)
7.1
–3.7
9.6
–10.1
4.0, –1.3
—
3.6
—
11.0
–14.2
Dihedral angle
/deg
N(1),C(1)...C(5)/C(8)...C(13)
17.6
12.2
10.1, 6.7
2.6
5.7
* For two independent molecules.
involving the preferentially half of the C(8)—C(9)—
C(10)—C(11) benzene ring. In dyes 7a,b containing only
one methoxy substituent in the benzene ring in the paraꢀ
position to the Py—CC group, the electronic influence of
the substituents is consistent and, as a consequence, the
bond length distribution in the benzene ring corresponds
to the contribution to the symmetrical quinoid strucꢀ
ture: the C(8)—C(9), C(8)—C(13), C(10)—C(11), and
C(11)—C(12) bonds are slightly elongated (the average
value is 1.396(3) Å), whereas the C(9)—C(10) and
C(12)—C(13) bonds are slightly shortened (average value
1.381(3) Å). This bond length distribution in the benzene
ring also confirms the conjugation in the chromophore
fragment of 7a,b.
In spite of the steric repulsion between the orthoꢀarꢀ
ranged alkoxyl substituents in compounds 4b,d and 7d, the
exocyclic (towards the benzene ring and macrocycle) bond
angles at the C(11) and C(12) atoms are considerably enꢀ
larged (the O(1)—C(11)—C(10) and O(2)—C(12)—C(13)
are 125.3(3) on the average), whereas the conjugated are
smaller (the O(1)—C(11)—C(12) and O(2)—C(12)—C(11)
angles are 114.8(3) on the average) (see Table 1). This
deformation of the bond angles relative to the ideal value
of 120 characteristic of the most part of 1,2ꢀdialkoxybenꢀ
zene should result in bringing together of the orthoꢀarꢀ
ranged oxygen atoms, i.e., in the enhancement of their
steric repulsion, and can be explained only in terms of
electronic effects. Earlier37—39 we ascribed this phenomeꢀ
non to the efficient conjugation of lone electron pairs
(LEP) of the indicated O atoms lying on the pꢀorbitals
with the benzene ring. Similar deformation of the exoꢀ
cyclic bind angles at the C(11) atom is observed in dyes
7a,b having only one methoxy group in the benzene ring,
which also indicates the efficient conjugation of the LEP
of the oxygen atom with the benzene ring. This conjugaꢀ
tion is favored by the conformation of the C(14)—O(1)—
C(11)—C(10) and C(15)—O(2)—C(12)—C(13) fragꢀ
ments, when the indicated torsion angles are fairly small
(from –14.2 to 11.0), i.e., close to the value of 0 necesꢀ
sary for the maximum conjugation to occur. Conjugation
is also indicated by the close to sp2ꢀhybrid state of the
O atoms attached to the benzene ring, which is characterꢀ

Synthesis of hetarylphenylacetylenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
153
rich) were used without additional purification. Styrylheterocyꢀ
cles 1a—d, 2, and 3 were synthesized according to known proceꢀ
dures.28—30,32,40
ized by the increased values of the C(11)—O(1)—C(14)
and C(12)—O(2)—C(15) bond angles (on the average,
117.6(2)) compared to the CAlk—O—CAlk angles (on the
average, 113.6(3) in compounds 4d and 7d), and by the
shortened O(1)—C(11) and O(2)—C(12) bonds (average
value 1.363(3) Å) compared to the O(1)—C(14) and
O(2)—C(15) bonds (average value 1.436(3) Å).
In structure 7d•0.25C6H6•1.75H2O, the H2O(1W)
water molecule forms the weak forked hydrogen bond with
the O(1) and O(2) oxygen atoms of the macrocycle. The
hydrogen bond is characterized by the following parameꢀ
ters: the O(1W)—H...O(1) and O(1W)—H...O(2) bond
lengths are 2.38(4) and 2.20(3) Å, the angles at the H atom
are 138(5) and 155(6). The second hydrogen atom of this
water molecule is not located.
Thus, the synthesis of new 1ꢀ(4ꢀpyridyl)ꢀ2ꢀphenylꢀ
acetylenes and 1ꢀ(2ꢀbenzothiazolyl)ꢀ2ꢀphenylacetylene
bearing the crown fragment or methoxy groups in the benzꢀ
ene ring was developed, which includes the addition of
bromine to the ethylene fragment of the corresponding
styrylheterocycles followed by dehydrobromination under
the action of a strong base. It was shown that the obtained
pyridylphenylacetylenes can be used for the synthesis of
new acetylenyl dyes. The crownꢀcontaining acetylenyl dyes
can serve as efficient molecular sensors to alkaline and
alkalineꢀearth metal cations.
Synthesis of acetylenes 4a—d and 5 (general procedure).
A solution of bromine (51 mg, 0.32 mmol) in CHCl3 (1.5 mL)
in the case of 1a,b and 2 or in CH2Cl2 (1.5 mL) in the case of
1c,d was added to a solution of styrylheterocycle 1a—d or 2
(0.3 mmol) in CHCl3 (5—7 mL) in the case of 1a,b and 2 or in
CH2Cl2 (15—20 mL) in the case of 1c,d, and the mixture was
kept for 3—4 days at ~20 C in the dark until the initial styrylꢀ
heterocycle disappeared (TLC monitoring). Chloroform or
CH2Cl2 (30 mL) was added to the reaction mixture, the mixture
was washed with a 2% aqueous solution of Na2SO3, and the
organic solvent was thoroughly evaporated in vacuo. Potassium
tertꢀbutoxide (0.56 g, 5 mmol) in absolute ButOH (10 mL) was
added to the dry residue, and the mixture was heated with stirꢀ
ring for 3—4 h at 80 C. Water (0.2 mL) was added to the reacꢀ
tion mixture, the solvent was evaporated in vacuo, water (50 mL)
was added to the residue, and the organics was extracted with
benzene (2×30 mL) in the case of synthesis of compounds 4a,b,
5 or CH2Cl2 (3×20 mL) for the synthesis of compounds 4c,d.
The organic extracts were evaporated in vacuo, and the residue
was chromatographed on SiO2, using the following eluents: benzꢀ
ene—EtOAc (5 : 1) in the case of 4a, a gradient benzene—EtOAc
mixture to 60% of the latter in the case of 4b, a gradient benzꢀ
ene—MeCN mixture to 50% of the latter in the case of 4c, benzꢀ
ene—EtOAc (1 : 1) and then benzene—PriOH (4 : 1) in the case
of 4d, and benzene—EtOAc (9 : 1) in the case of 5.
4ꢀ[(4ꢀMethoxyphenyl)ethynyl]pyridine (4a) was obtained in
59% yield as a slightly yellowish substance with m.p. 96—98 C
(from hexane) (cf. Ref. 22: m.p. 104.5—105.5 C). Found (%):
C, 80.03; H, 5.10; N, 6.39. C14H11NO. Calculated (%): C, 80.36;
H, 5.30; N, 6.69. 1H NMR (23 C), : 3.82 (s, 3 H, MeO); 7.03
(d, 2 H, H(3´), H(5´), J = 8.8 Hz); 7.50 (d, 2 H, H(3), H(5),
J = 6.0 Hz); 7.57 (d, 2 H, H(2´), H(6´), J = 8.8 Hz); 8.61
(d, 2 H, H(2), H(6), J = 6.0 Hz). 13C NMR (30 C), : 55.22
(MeO); 85.48 (CCPy); 93.90 (CCPy); 112.96 (C(1´)); 114.42
(C(3´), C(5´)); 125.03 (C(3), C(5)); 130.48 (C(4)); 133.30 (C(2´),
C(6´)); 149.75 (C(2), C(6)); 160.11 (C(4´)). UV (MeCN,
C = 5•10–5 mol L–1), max/nm (): 310 (23000), 298 (23100),
248 (10200). MS, m/z (Irel (%)): 209 [M]+ (42), 194 (20), 166 (30),
140 (8), 139 (25), 71 (8), 59 (15), 58 (100), 57 (8), 55 (8).
4ꢀ[(3,4ꢀDimethoxyphenyl)ethynyl]pyridine (4b) was syntheꢀ
sized in 57% yield as a slightly yellowish substance with m.p.
113—114 C (from hexane). Found (%): C, 75.36; H, 5.37;
N, 5.71. C15H13NO2. Calculated (%): C, 75.30; H, 5.48; N, 5.85.
1H NMR (27 C), : 3.80 (s, 6 H, 2 MeO); 7.00 (d, 1 H, H(5´),
J = 8.3 Hz); 7.16 (d, 1 H, H(2´), J = 1.7 Hz); 7.19 (dd, 1 H, H(6´),
J = 8.3 Hz, J = 1.7 Hz); 7.47 (d, 2 H, H(3), H(5), J = 6.0 Hz);
8.60 (d, 2 H, H(2), H(6), J = 6.0 Hz). 13C NMR (27 C), : 55.43
(MeO); 55.50 (MeO); 85.25 (CCPy); 94.32 (CCPy); 111.71
(C(5´)); 112.98 (C(1´)); 114.45 (C(2´)); 125.05 (C(3), C(5));
125.20 (C(6´)); 130.53 (C(4)); 148.57 (C(3´)); 149.77 (C(2),
C(6)); 150.20 (C(4´)). UV (MeCN, C = 5•10–5 mol L–1),
Experimental
Melting points (uncorrected) were measured in capillaries
on a MelꢀTemp II instrument. Mass spectra were recorded on
a Varian MAT 311A instrument at an ionization energy of 70 eV
with direct sample injection into the ionization region. Elemenꢀ
tal analyses were carried out at the Laboratory of Microanalysis
of the A. N. Nesmeyanov Institute of Organoelement Comꢀ
pounds, Russian Academy of Sciences (Moscow, Russia). TLC
monitoring was performed on the DCꢀAlufolien Kieselgel 60 F254
plates (Merck). Column chromatography was carried out on SiO2
(Kieselgel 60, 0.063—0.100 mm, Merck or Kieselgel 60,
0.035—0.070 mm, Fluka). 1Н and 13C NMR spectra were recordꢀ
ed on a Bruker DRXꢀ500 spectrometer (500.13 and 125.76 MHz,
respectively) in DMSOꢀd6 using the signal from the solvent as
an internal standard ( 2.50,  39.43). Chemical shifts were
H
C
measured with the accuracy to 0.01 ppm, and spinꢀspin coupling
(SSC) constants were determined with the accuracy to 0.1 Hz.
The 2D homonuclear 1H—1H ROESY and heteronuclear
1H—13C COSY (HSQC and HMBC) spectra were used for the
assignment of signals from protons and carbons. The 2D experiꢀ
ments were carried out using standard parameters from the Brukꢀ
er program package. The duration of mixing in the ROESY exꢀ
periment was 300 s, and the HMBC experiment was optimized
for the constant JH,C = 8 Hz. UV spectra were recorded on
a Shimadzu UVꢀ3101PC spectrophotometer in the range from
200 to 600 nm with an increment of 1 nm (MeCN or water,
1ꢀcm quartz cell, room temperature).

max/nm (): 316 (19 400), 292 (15 400), 241 (15 400). MS, m/z
(Irel (%)): 239 [M]+ (100), 224 (18), 196 (30), 168 (10), 167 (14),
166 (6), 153 (17), 127 (17), 126 (8), 58 (18).
4ꢀ(2,3,5,6,8,9,11,12ꢀOctahydroꢀ1,4,7,10,13ꢀbenzopentaoxꢀ
acyclopentadecinꢀ15ꢀylethynyl)pyridine (4c) was synthesized in
39% yield as a slightly yellowish substance with m.p. 126—128 C
(from hexane). Found (%): C, 68.17; H, 6.14; N, 3.71. C21H23NO5.
Potassium tertꢀbutoxide, methyl iodide, ethyl pꢀtolueneꢀ
sulfonate, 70% perchloric acid, and 1,3ꢀpropane sultone (Aldꢀ

154
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Vedernikov et al.
Calculated (%): C, 68.28; H, 6.28; N, 3.79. 1H NMR (25 C),
: 3.62 (m, 8 H, 4 CH2O); 3.77 (m, 4 H, 2 CH2CH2OAr); 4.09
(m, 4 H, 2 CH2OAr); 7.01 (d, 1 H, H(5´), J = 8.2 Hz); 7.16 (d, 1 H,
H(2´), J = 1.9 Hz); 7.18 (dd, 1 H, H(6´), J = 8.2 Hz, J = 1.9 Hz);
7.48 (d, 2 H, H(3), H(5), J = 5.8 Hz); 8.61 (d, 2 H, H(2), H(6),
J = 5.8 Hz). 13C NMR (23 C), : 68.23 (CH2OAr); 68.44
(CH2CH2OAr); 68.55 (CH2OAr); 68.62 (CH2CH2OAr); 69.56
(CH2O); 69.61 (CH2O); 70.45 (2 CH2O); 85.26 (CCPy); 94.26
(CCPy); 113.07 (C(1´)); 113.25 (C(5´)); 116.22 (C(2´)); 125.06
(C(3), C(5)); 125.43 (C(6´)); 130.48 (C(4)); 148.23 (C(3´));
149.80 (C(2), C(6)); 149.98 (C(4´)). UV (MeCN, C =
= 5•10–5 mol L–1), max/nm (): 315 (23 000), 293 (18 500),
242 (17 000). MS, m/z (Irel (%)): 369 [M]+ (14), 238 (12), 237 (100),
111 (13), 101 (16), 98 (31), 77 (19), 57 (32), 56 (25), 53 (21).
4ꢀ(2,3,5,6,8,9,11,12,14,15ꢀDecahydroꢀ1,4,7,10,13,16ꢀbenzoꢀ
hexaoxacyclooctadecinꢀ18ꢀylethynyl)pyridine (4d) was syntheꢀ
sized in 35% yield as a slightly yellowish substance with m.p.
118—120 C (from hexane). Found (%): C, 66.60; H, 6.54; N, 3.20.
C23H27NO6. Calculated (%): C, 66.81; H, 6.58; N, 3.39.
1H NMR (23 C), : 3.53 (s, 4 H, 2 CH2O); 3.56 (m, 4 H, 2 CH2O);
3.62 (m, 4 H, 2 CH2O); 3.76 (m, 4 H, 2 CH2CH2OAr); 4.14
(m, 4 H, 2 CH2OAr); 7.03 (d, 1 H, H(5´), J = 8.1 Hz); 7.17 (br.s,
1 H, H(2´)); 7.18 (dd, 1 H, H(6´), J = 8.1 Hz, J = 1.8 Hz); 7.50
(d, 2 H, H(3), H(5), J = 6.0 Hz); 8.61 (d, 2 H, H(2), H(6),
J = 6.0 Hz). 13C NMR (30 C), : 68.09 (CH2OAr); 68.15
(CH2OAr); 68.44 (CH2CH2OAr); 68.49 (CH2CH2OAr); 69.63
(2 CH2O); 69.71 (2 CH2O); 69.81 (2 CH2O); 85.22 (CCPy);
94.29 (CCPy); 112.83 (C(5´)); 112.96 (C(1´)); 115.63 (C(2´));
125.02 (C(3), C(5)); 125.24 (C(6´)); 130.48 (C(4)); 147.90
(C(3´)); 149.62 (C(4´)); 149.76 (C(2), C(6)). UV (MeCN,
C = 5•10–5 mol L–1), max/nm (): 320 (21 500), 293 (16 300),
243 (16 400). MS, m/z (Irel (%)): 413 [M]+ (42), 325 (45), 237 (100),
222 (88), 210 (85), 181 (76), 152 (60), 111 (61), 73 (57), 71 (50).
2ꢀ[(3,4ꢀDimethoxyphenyl)ethynyl]ꢀ1,3ꢀbenzothiazole (5) was
synthesized in 53% yield as a slightly yellowish substance with
m.p. 91—93 C (from hexane). Found (%): C, 69.16; H, 4.32;
N, 4.62. C17H13NO2S. Calculated (%): C, 69.13; H, 4.44;
N, 4.74. 1H NMR (30 C), : 3.83 (s, 6 H, 2 MeO); 7.06 (d, 1 H,
H(5´), J = 8.3 Hz); 7.27 (d, 1 H, H(2´), J = 1.6 Hz); 7.31 (dd, 1 H,
H(6´), J = 8.3 Hz, J = 1.6 Hz); 7.53 (m, 1 H, H(6)); 7.59
(m, 1 H, H(5)); 8.05 (d, 1 H, H(4), J = 8.1 Hz); 8.13 (d, 1 H,
H(7), J = 7.7 Hz). 13C NMR (30 C), : 55.53 (MeO); 55.60
(MeO); 81.35 (CCHet); 96.47 (CCHet); 111.46 (C(1´));
111.86 (C(5´)); 114.59 (C(2´)); 122.05 (C(7)); 122.91 (C(4));
125.79 (C(6´)); 126.27 (C(6)); 126.88 (C(5)); 134.60 (C(7a));
147.84 (C(2)); 148.65 (C(3´)); 150.93 (C(4´)); 152.48 (C(3a)).
UV (MeCN, C = 5•10–5 mol L–1), max/nm (): 348 (24 000),
336 (25 900). MS, m/z (Irel (%)): 295 [M]+ (100), 280 (75), 252 (69),
237 (41), 224 (49), 223 (58), 209 (34), 183 (40), 147 (34), 69 (48).
4ꢀ[(2ꢀBromoꢀ4,5ꢀdimethoxyphenyl)ethynyl]quinoline (6).
A solution of bromine (83 mg, 0.52 mmol) in CHCl3 (1.1 mL)
was added to a solution of styrylquinoline 3 (50 mg, 0.17 mmol)
in CHCl3 (5 mL), and the mixture was kept for 4 days at ~20 C
in the dark. Chloroform (10 mL) was added to the mixture,
which was washed with a 2% aqueous solution of Na2SO3 (5 mL),
and the organic solvent was thoroughly evaporated in vacuo.
A solution of ButOK (0.76 g, 6.8 mmol) in absolute ButOH
(10 mL) was added to the dry residue (103 mg), and the mixture
was heated for 3 h with stirring at 80 C. Water (0.5 mL) was
added to the reaction mixture, the solvent was evaporated
in vacuo, and the residue was chromatographed on SiO2, using
as an eluent a gradient benzene—EtOAc mixture to 50% of the
latter. One fraction (43 mg) containing a mixture of the comꢀ
pounds was collected (1H NMR monitoring) and crystallized by
the slow evaporation of the solution in a hexane—CHCl3 mixꢀ
ture at ~20 C. Compound 6 was obtained in a yield of 19 mg
(30%) as yellowish spherulites with m.p. 105—107 C. Found (%):
C, 61.74; H, 3.85; N, 3.74. C19H14BrNO2. Calculated (%):
C, 61.97; H, 3.83; N, 3.80. 1H NMR (27 C), : 3.85 (s, 3 H,
5´ꢀMeO); 3.87 (s, 3 H, 4´ꢀMeO); 7.36 (s, 1 H, H(3´)); 7.41
(s, 1 H, H(6´)); 7.74 (d, 1 H, H(3), J = 4.5 Hz); 7.78 (m, 1 H,
H(6)); 7.87 (m, 1 H, H(7)); 8.10 (d, 1 H, H(8), J = 8.5 Hz); 8.51
(d, 1 H, H(5), J = 8.8 Hz); 8.95 (d, 1 H, H(2), J = 4.5 Hz).
13C NMR (25 C), : 55.92 (5´ꢀMeO); 56.09 (4´ꢀMeO); 87.42
(CCHet); 97.38 (CCHet); 114.68 (C(1´)); 115.47 (C(3´));
115.84 (C(6´)); 116.76 (C(2´)); 123.51 (C(3)); 125.72 (C(5));
126.58 (C(4a)); 127.71 (C(6)); 128.23 (C(4)); 129.51 (C(8));
130.21 (C(7)); 147.51 (C(8a)); 148.17 (C(5´)); 150.10 (C(2));
150.90 (C(4´)). UV (MeCN, C = 5•10–5 mol L–1), max/nm ():
352 (21 500), 340 (21 300), 256 (17 700), 239 (29 400). MS, m/z
(Irel (%)): 369 [M]+ with 81Br (100), 367 [M]+ with 79Br (98),
245 (35), 230 (11), 202 (16), 185 (10), 175 (30), 101 (14),
83 (9), 59 (15).
1ꢀMethylꢀ4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinium iodide
(7a). Methyl iodide (47 L, 0.75 mmol) was added to a solution
of compound 4a (31 mg, 0.15 mmol) in CH2Cl2 (1 mL), and the
mixture was kept for 6 days at ~20 C. The solvent was evaporatꢀ
ed in vacuo, and the residue was triturated in benzene (3 mL),
filtered off, washed with benzene (2×3 mL), and dried in air.
Dye 7a was obtained in a yield of 52 mg (100%) as a yellowishꢀ
green powder with m.p. 188—190 C (from MeCN—benzene).
Found (%): C, 51.48; H, 4.01; N, 3.97. C15H14INO. Calculatꢀ
ed (%): C, 51.30; H, 4.02; N, 3.99. 1H NMR (28 C), : 3.84
(s, 3 H, MeO); 4.30 (s, 3 H, MeN); 7.10 (d, 2 H, H(3´), H(5´),
J = 8.8 Hz); 7.67 (d, 2 H, H(2´), H(6´), J = 8.8 Hz); 8.18 (d, 2 H,
H(3), H(5), J = 6.6 Hz); 8.94 (d, 2 H, H(2), H(6), J = 6.6 Hz).
13C NMR (28 C), : 47.54 (MeN); 55.47 (MeO); 84.92 (CCPy);
103.17 (CCPy); 111.46 (C(1´)); 114.78 (C(3´), C(5´)); 128.34
(C(3), C(5)); 134.36 (C(2´), C(6´)); 138.61 (C(4)); 145.22 (C(2),
C(6)); 161.32 (C(4´)). UV (MeCN, C = 5•10–5 mol L–1),

max/nm (): 363 (28 200), 247 (27 500).
1ꢀEthylꢀ4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinium perchlorate
(7b). A mixture of compound 4a (40 mg, 0.19 mmol) and ethyl
pꢀtoluenesulfonate (115 mg, 0.57 mmol) was heated for 4 h at
90 C (oil bath). The resulting mixture was triturated with benzꢀ
ene (2×5 mL) at ~20 C and then heated at 80 C with 10 mL of
benzene. The undissolved yellow substance was separated by
decantation and dissolved in MeOH (2 mL). Then 70% perꢀ
chloric acid (33 L, 0.38 mmol) was added, and the mixture was
cooled to –10 C. The precipitate formed was rapidly filtered
off, washed with benzene (2×5 mL), and dried in air. Dye 7b was
obtained in a yield of 31 mg (47%) as a yellow powder with m.p.
136—138 C (from MeOH). Found (%): C, 58.30; H, 4.60;
N, 4.15. C16H16ClNO5•0.15C6H6. Calculated (%): C, 58.08;
H, 4.87; N, 4.01. 1H NMR (30 C), : 1.54 (t, 3 H, MeCH2,
J = 7.3 Hz); 3.85 (s, 3 H, MeO); 4.58 (q, 2 H, MeCH2, J = 7.3 Hz);
7.10 (d, 2 H, H(3´), H(5´), J = 8.6 Hz); 7.68 (d, 2 H, H(2´),
H(6´), J = 8.6 Hz); 8.20 (d, 2 H, H(3), H(5), J = 6.7 Hz); 9.05
(d, 2 H, H(2), H(6), J = 6.7 Hz).
Betaine 3ꢀ{4ꢀ[(4ꢀmethoxyphenyl)ethynyl]pyridinioꢀ1ꢀyl}ꢀ
propaneꢀ1ꢀsulfonate (7c). 1,3ꢀPropane sultone (37 L, 0.42 mmol)
was added to a solution of compound 4a (59 mg, 0.28 mmol) in

Synthesis of hetarylphenylacetylenes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
155
MeCN (2 mL), and the mixture was kept for 5 days at ~20 C.
The precipitate formed was filtered off, washed with MeCN
(2 mL) and benzene (2×2 mL), and dried in air. Dye 7c was
obtained in a yield of 50 mg (53%) as a creamꢀyellow powder
with m.p. >265 C (with decomp.) (MeCN—water—benzene).
Found (%): C, 60.35; H, 5.03; N, 4.09. C17H17NO4S•0.4H2O.
C, 51.51; H, 5.07; N, 2.75. C22H26INO5. Calculated (%):
C, 51.67; H, 5.13; N, 2.74. H NMR (26 C), : 3.62 (m, 8 H,
1
4 CH2O); 3.79 (m, 4 H, 2 CH2CH2OAr); 4.10 (m, 2 H,
3ꢀCH2OAr); 4.13 (m, 2 H, 4ꢀCH2OAr); 4.29 (s, 3 H, MeN);
7.08 (d, 1 H, H(5´), J = 8.3 Hz); 7.25 (d, 1 H, H(2´), J = 1.8 Hz);
7.31 (dd, 1 H, H(6´), J = 8.3 Hz, J = 1.8 Hz); 8.16 (d, 2 H, H(3),
H(5), J = 6.7 Hz); 8.94 (d, 2 H, H(2), H(6), J = 6.7 Hz).
13C NMR (27 C), : 47.53 (MeN); 68.24 (4ꢀCH2OAr);
68.41 (CH2CH2OAr); 68.53 (3ꢀCH2OAr, CH2CH2OAr); 69.46
(CH2O); 69.54 (CH2O); 70.41 (CH2O); 70.43 (CH2O); 84.71
(CCPy); 103.60 (CCPy); 111.49 (C(1´)); 113.22 (C(5´));
116.63 (C(2´)); 126.79 (C(6´)); 128.32 (C(3), C(5)); 138.64
(C(4)); 145.27 (C(2), C(6)); 148.25 (C(3´)); 151.30 (C(4´)). UV
(MeCN, C = 5•10–5 mol L–1), max/nm (): 379 (26 700),
248 (26 800).
1
Calculated (%): C, 60.30; H, 5.30; N, 4.14. H NMR (25 C),
: 2.23 (quintet, 2 H, CH2CH2SO3, J = 7.0 Hz); 2.45 (t, 2 H,
CH2SO3, J = 7.0 Hz); 3.84 (s, 3 H, MeO); 4.69 (t, 2 H, CH2N,
J = 6.9 Hz); 7.10 (d, 2 H, H(3´), H(5´), J = 8.7 Hz); 7.68 (d, 2 H,
H(2´), H(6´), J = 8.7 Hz); 8.19 (d, 2 H, H(3), H(5), J = 6.6 Hz);
9.04 (d, 2 H, H(2), H(6), J = 6.6 Hz). 13C NMR (25 C), : 27.15
(CH2CH2SO3); 46.87 (CH2SO3); 55.50 (MeO); 59.20 (CH2N);
85.14 (CCPy); 103.35 (CCPy); 111.57 (C(1´)); 114.84 (C(3´),
C(5´)); 128.79 (C(3), C(5)); 134.45 (C(2´), C(6´)); 139.04 (C(4));
144.70 (C(2), C(6)); 161.41 (C(4´)). UV (water,
C
=
Xꢀray diffraction experiments. Crystals of pyridylphenylacetylꢀ
enes 4b,d were obtained by the slow evaporation of their soluꢀ
tions in a CH2Cl2—hexane mixture at ~20 C, and crystals of
dyes 7a,b,d were grown by the slow saturation of their solutions
in MeCN with benzene vapors at ~20 C.
Single crystals were placed on a Bruker SMARTꢀCCD difꢀ
fractometer under a cooled nitrogen flow (T = 120.0(2) K), where
the crystallographic parameters and experimental reflection inꢀ
tensities on MoꢀK radiation were measured ( = 0.71073 Å,
graphite monochromator,  scan mode). Experimental data were
= 5•10–5 mol L–1), max/nm (): 362 (29 600), 247 (15 500).
1ꢀMethylꢀ4ꢀ(2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀbenzoꢀ
pentaoxacyclopentadecinꢀ15ꢀylethynyl)pyridinium iodide (7d).
Methyl iodide (40 L, 0.64 mmol) was added to a solution of
compound 4c (11.0 mg, 29.8 mol) in anhydrous THF (1 mL),
and the mixture was kept for 4 days at ~20 C. The precipitate
formed was filtered off, washed with benzene (2×1 mL), and
dried in air. Dye 7d was obtained in a yield of 12.8 mg (84%) as
a yellow powder with m.p. >230 C (with decomp.). Found (%):
Table 2. Parameters for crystals 4b,d and Xꢀray diffraction experiments
Parameter
4b
4d
Molecular formula
Molecular weight/g mol–1
C15H13NO2
239.26
C23H27NO6
309.35
Crystal system
Monoclinic
Orthorhombic
Space group
P21/c
P212121
a/Å
8.7887(2)
4.4952(5)
b/Å
7.7121(2)
16.1797(17)
c/Å
18.8813(4)
28.966(3)
/deg
90
90
/deg
95.0130(10)
90
/deg
90
90
V/Å3
1274.87(5)
2106.7(4)
Z
4
4
dcalc/g cm–3
F(000)
1.247
504
1.304
880
(MoꢀK)/mm–1
Crystal size/mm
Scan mode
0.083
0.26×0.22×0.18

2.17—29.00
–11  h  11, –10  k  9,
–25  l  25
0.094
0.36×0.06×0.04

1.41—26.00
–2  h  5, –19  k  16,
–35  l  35
/deg
Ranges of reflection indices
Number of measured reflections
Number of independent reflections
9623
3375
10271
4069
[Rint = 0.0170]
2847
[Rint = 0.2279]
1686
Number of reflections with I > 2(I)
Number of refinement variables
R Factors for I > 2(I )
Factors for all reflections
Goodnessꢀofꢀfit for F2
215
271
R1 = 0.0400, wR2 = 0.1111
R1 = 0.0485, wR2 = 0.1168
1.069
R1 = 0.0750, wR2 = 0.0804
R1 = 0.2387, wR2 = 0.1005
0.871
Residual electron density
–0.193/0.626
–0.223/0.315
/e•Å3, min/
max

156
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
Vedernikov et al.
Table 3. Parameters for crystals 7a•0.5C6H6, 7b•0.5C6H6 and 7d•0.25C6H6•1.75H2O and for Xꢀray diffraction experiments
Parameter
7a•0.5C6H6
7b•0.5C6H6
7d•0.25C6H6•1.75H2O
Molecular formula
Molecular weight/g mol–1
C18H17INO
390.23
C19H19ClNO5
C23.5H31INO6.75
376.80
562.39
Crystal system
Space group
Monoclinic
Triclinic
Monoclinic
P21/c
P–1
P21/c
a/Å
10.0687(2)
6.6448(3)
20.0437(7)
b/Å
32.5910(7)
8.8221(5)
6.8511(3)
c/Å
10.5017(2)
16.5298(9)
19.4292(7)
/deg
90
100.596(2)
90
/deg
100.0660(10)
92.142(2)
106.611(2)
/deg
90
107.251(2)
905.25(8)
90
V/Å3
3393.08(12)
2556.70(17)
Z
8
2
4
dcalc/g cm–3
F(000)
1.528
1544
1.886
1.382
394
0.241
1.461
1144
1.292
0.48×0.22×0.01

(MoK)/mm–1
Crystal size/mm
Scan mode
0.30×0.18×0.07

2.05—29.00
0.15×0.12×0.10

2.47—28.00
5  h  8, 11  k  8,
21  l  21
/deg
2.12—29.00
27  h  26, 9  k  9,
25  l  26
Ranges of reflection indices
13  h  13, 44  k  44,
14  l  14
Number of measured reflections
Number of independent reflections
29041
9017
4885
3731
19179
6781
[Rint = 0.0326]
7364
[Rint = 0.0256]
2610
[Rint = 0.0656]
4714
Number of reflections with I > 2(I)
Number of refinement variables
R Factors for I > 2(I )
R Factors for all reflections
Goodnessꢀofꢀfit for F2
515
311
303
R1 = 0.0272, wR2 = 0.0573
R1 = 0.0389, wR2 = 0.0599
1.009
R1 = 0.0484, wR2 = 0.1008
R1 = 0.0804, wR2 = 0.1092
1.016
R1 = 0.0451, wR2 = 0.1068
R1 = 0.0765, wR2 = 0.1165
0.956
Residual electron density
–0.402/1.057
–0.327/0.247
–1.195/1.249
/e•Å3, min/
max
processed according to the SAINT program.41 An Xꢀray absorpꢀ
tion (by crystals of iodides 7a,b) correction was applied using
the SADABS method. All structures were solved by direct
methods and refined by least squares in the fullꢀmatrix anisoꢀ
tropic approximation for F2 for nonꢀhydrogen atoms (except for
the atoms of the disordered solvate molecules in structure
7d•0.25C6H6•1.75H2O, which were isotropically refined). Solꢀ
vate benzene molecules were found in the independent part of
the crystal cells of dyes 7a,b (in structure 7b the solvate benzene
molecule lies in the symmetry center of the crystal). Five solvate
water molecules and one benzene molecule were found in the
independent part of the crystal cell of dye 7d, and this benzene
molecule and water molecules O(2W), O(3W), O(4W), and
O(5W) alternatively occupy the same site in the cell with site
occupancies of 0.25 : 0.30 : 0.15 : 0.15 : 0.15, respectively. The
position of hydrogen atoms at carbon atoms were calculated
geometrically and refined in the isotropic approximation for
structures 4b, 7a•0.5C6H6 and 7b•0.5C6H6 or by the riding model
for structures 4d and 7d•0.25C6H6•1.75H2O. The hydrogen
atoms of the water molecules in structure 7d•0.25C6H6•1.75H2O
were not localized, except for one H atom of the H2O(1W) molꢀ
ecule. This hydrogen atom was refined in the isotropic approxiꢀ
mation with restraint on the O(1W)—H bond length.
characteristics of Xꢀray diffraction experiments are given in
Tables 2 and 3. The coordinates of atoms and other experimenꢀ
tal data were deposited with the Cambridge Crystallographic
Data Centre (CCDC)* with the numbers 776884 (4b), 776885 (4d),
776886 (7a•0.5C6H6), 776887 (7b•0.5C6H6), and 776888
(7d•0.25C6H6•1.75H2O).
This work was financially supported by the Division of
Chemistry and Materials Science of the Russian Academy
of Sciences (Program No. 6), the Photochemistry Centre
of the Russian Academy of Sciences, and the Royal Chemꢀ
ical Society of Great Britain (personal grants for L. G.
Kuz´mina and J. A. K. Howard).
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Received June 9, 2010;
in revised form June 28, 2011