New Arylene-Germylene-Vinylene Compounds: Stereoselective Synthesis, Characterization, and Photophysical Properties

Article abstract of DOI:10.1021/acs.organomet.6b00336

The stereoselective route toward new molecular and macromolecular compounds containing arylene-germylene-vinylene units is described. The reagents for germylative coupling reaction were 1,4-bis(dimethylvinylgermyl)benzene (1) and vinyl- and divinylarenes

Full text of DOI:10.1021/acs.organomet.6b00336

Article
pubs.acs.org/Organometallics
New Arylene−Germylene−Vinylene Compounds: Stereoselective
Synthesis, Characterization, and Photophysical Properties
Monika Ludwiczak,†,‡ Małgorzata Bayda,‡ Michał Dutkiewicz,†,‡ Dawid Frąckowiak,† Mariusz Majchrzak,‡
Bronisław Marciniak,‡ and Bogdan Marciniec*,†,‡
†Center of Advanced Technologies, Adam Mickiewicz University in Poznan, Umultowska 89c, 61-614 Poznan, Poland
‡Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, 61-614 Poznan, Poland
S
* Supporting Information
ABSTRACT: The stereoselective route toward new molecular
and macromolecular compounds containing arylene−germy-
lene−vinylene units is described. The reagents for germylative
coupling reaction were 1,4-bis(dimethylvinylgermyl)benzene
(1) and vinyl- and divinylarenes with ruthenium complexes (2a,
2b) as catalysts. NMR characterization of all isolated products,
results of MS and elemental analysis for molecular compounds
(3−5), and GPC for oligomers (6−8) are presented.
Absorption and luminescence properties of the synthesized
compounds are discussed and compared with those of model
chromophores.
INTRODUCTION
RESULTS AND DISCUSSION
■
■
Monomer Synthesis. 1,4-Bis(dimethylvinylgermyl)-
benzene (1) was obtained in the two-step synthesis shown in
Scheme 1.
Organogermanium compounds have not gained widespread
attention due to the rarity and high price of germanium as well
as the commercially limited availability of starting materials:
halogermanes. Nonetheless, their chemistry is well developed,
and interest in these compounds has increased due to their
interesting properties and low toxicity (a potential alternative to
organostannanes).1,2 Organogermanium derivatives containing
π-conjugated systems have also been found to be attractive
precursors of optoelectronic materials.3
Scheme 1. Preparation of the Monomer 1
Among the many synthetic approaches, catalytic trans-
formations mediated by transition metal complexes are the
most important procedures leading to alkenylgermanes.
Hydrogermylation of alkynes is probably the most recognizable
method for the preparation of substituted vinylgermanes, and,
depending on the properties of applied reagents, this can result
in E, Z, or gem products.4 Dehydrogenative germylation of
olefins with hydrogermanes5 and germylative coupling
(germylation with vinylgermanes)6 have also been reported as
convenient routes to obtain functionalized alkenylgermanes.
The mechanism of the germylative coupling reaction has
already been established, and it shows wide possibilities for its
further application in organometallic synthesis. Therefore, we
employed the above-mentioned process, as well as our previous
experience with silicon compounds,7 in the synthesis of
molecular and macromolecular organogermanium derivatives
containing arylene−germylene−vinylene units with high stereo-
selectivity. Spectroscopic absorption and luminescence proper-
ties have been characterized.
Preparation of chlorodimethylvinylgermane requires a two-
week reaction time, and the conditions applied permitted
minimization of byproduct formation and at the same time
simplification of the isolation procedure.8 A one-pot procedure
employing the Grignard reaction was used to prepare monomer
1. The Grignard reagent was generated “in situ” from the
presence of 1,4-dibromobenzene and Mg in tetrahydrofuran
(THF) in the presence of a 10% excess of chlorodimethyl-
vinylgermane in less than 1 h in good yield (85%). The crucial
point was the rapid initiation of the reaction after addition of all
reagents. The mixture was heated at the beginning to start up
the process. It was observed that when the reaction was left to
initiate itself, byproducts were obtained more frequently, and
the yield of the expected product was drastically lowered
(≤30%). The monomer was purified according to the
Received: April 26, 2016
© XXXX American Chemical Society
A
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procedure presented in the Experimental Section and kept
under an inert atmosphere for further use.
coupling is more favorable than coupling of the monomer with
itself under the given reaction conditions.
Catalytic Studies. Based on our previous experience with
vinylsilanes7 as well as earlier reports for simple vinylgermane
coupling,6 two catalysts were chosen for the preliminary
experiments: RuHCl(CO)(PCy3)2 (2a) and RuHCl(CO)-
(PPh3)3 (2b). A germylative coupling reaction of the monomer
(1) and styrene was used as a model reaction to optimize
general conditions. Because of the low m/z of the expected
product, we used GC-MS spectra to control the reaction and
identify the reagents. The starting conditions included an open
system with argon flow, toluene as a solvent (1 mol·dm−3),
stoichiometric ratio of reagents, 2−5 mol % of catalysts, and
temperature in the range 80−110 °C. Although the reactivity of
vinylgermanes was expected to be a little lower than that of
analogous vinylsilyl derivatives, it was surprising to obtain little
or no conversion at temperatures below 120 °C. Neither the
addition of styrene in excess nor an increase in the catalyst
content (10 mol %) changed the outcome. The reaction
heating conditions were changed from a dynamic system under
argon to a closed system. The Rotaflo Schlenk vacuum was
used to withstand the increasing pressure of toluene vapors, the
reaction mixture was heated for 24 h at 120 °C, and a change in
the color was observed: the usual yellow solution turned deep
red.
Applying the same conditions as chosen for cross-coupling of
the monomer 1 and styrene, two other molecular germanium
derivatives were synthesized (4 and 5; see Scheme 3). Products
4 and 5 were isolated according to the procedures described in
1
the Experimental Section and characterized via H NMR and
13C NMR spectra.
Characterization and Properties of Products. Figure 1
shows 1H NMR spectra of the monomer 1, 1,4-divinylbenzene,
and compounds 3 and 6 with the presence of signals
characteristic of trans isomers. No traces of homocoupling
were observed. Using terminal vinyl groups seen on NMR
spectra, the numbers of mers from integration were described;
compound 6 had 6 mers that were confirmed by GPC.
According to the literature,5 there is a high possibility of
obtaining mixtures of mono- and dicoupling products in the
presence of divinyl derivatives; however, we proved the
possibility of coupling both of the terminal vinyl groups and
obtaining one product selectively. 1,4-Divinylbenzene, 1,4-
bis[(4-vinylphenyl)-2,3,5,6-tetrafluoro]benzene, and 9,10-bis(4-
vinylphenyl)anthracene were used. We expected to obtain
oligomers instead of polymers, which would be convenient for
photophysical analyses. Figure 2 shows the results of GPC
analysis of the obtained oligomers. An increase in the reaction
time did not significantly change the length of the chain and
results in higher values of polydispersity index (PDI).
Table 2 presents GPC analyses for oligomers obtained via 3-
and 5-day germylative coupling reactions. All oligomers were
analyzed by the thermogravimetric method. A similar
correlation in their thermal stability was expected based on
almost the same number of mers between products of 3- and 5-
day syntheses. Table 3 and Figure 3 show that no significant
differences were noted between oligomers from particular
groups. Oligomers 6−8 lost 1% of mass in the temperature
range 189−242 °C. The final transition ends below 550 °C,
regardless of the chromophore in the structure. At the
beginning of mass loss, oligomer 7 shows higher thermal
stability than 6 and 8, but ultimately all oligomers show similar
residues of samples: 32−39% (at 800 °C).
GC-MS analyses did not show the expected product, but a
small amount (5%) of monocoupling was observed. The
temperature was increased to 140 °C, resulting in a 99%
conversion to the expected product. Table 1 shows
a
Table 1. Germylative Cross-Coupling Conditions
b
c
molar ratio
molarity [mol/L]
T [°C]
conversion of [ViGe] [%]
1:4:0.05
1:4:0.05
1:4:0.05
1:4:0.05
1:2: 0.02
1
80
100
120
140
0
0
0.5
0.125
0.125
0.125
5
>99
140
>99
a
b
c
Toluene, Ar, closed system, 24 h. [ViGe]:[Styrene]:[RuH]. GC-
MS.
Absorption and emission properties of compounds 3−8 were
examined (see Table 4, Figure 4). Due to the presence of 9-(4-
vinylphenyl)anthracene chromophore, compound 4 shows the
highest fluorescence efficiency (φFL = 0.49) and the longest
fluorescence lifetime (3.3 ns) from among molecular
compounds 3−5. Compounds 3 and 5 show very weak
fluorescence, as expected. The absorption and emission
properties of 3 were found to be almost identical to those of
its silicon-based analogue S1.9 Likewise, oligomers 6 and S3
displayed similar photophysical behavior relative to each other.
The presence of germanium and silicon in these compounds
introduced a large, 20 nm red shift in absorption and emission
spectra of both of the compounds relative to the DVB
chromophore. Silicon shifted the spectra to the longer
wavelengths than germanium. Both germanium- and silicon-
based analogues exhibited very similar absorption and emission
properties, i.e., similar molar absorption coefficients, quantum
yields, and fluorescence lifetimes.
representative results for different reaction conditions. The
temperature of the process was high, but it was still possible to
obtain the expected product using the stoichiometric ratio of
reagents. Radical polymerization was prevented by using diluted
solutions (0.1 mol·dm−3). Although only cross-coupling was
observed, germylative coupling of 1,4-bis(dimethylvinyl)-
germane itself was possible as well. Scheme 2 shows
homocoupling of monomer 1. It was proven that only 50%
of substrate was consumed after 24 h. The results were
promising for further experiments in which co-oligomers A-B-
A-B were expected to be obtained. This is possible only if cross-
Scheme 2. Germylative Coupling of 1,4-
Bis(dimethylvinylgermyl)benzene
Germanium-based polymer 7, containing the 9,10-bis(4-
vinylphenyl)anthracene chromophore, displayed absorption
properties nearly identical to those of the S5 chromophore
itself. Similarly, the presence of germanium did not significantly
affect the emission properties. The red shift observed in the
B
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Scheme 3. Germylative Cross-Coupling of 1,4-Bis(dimethylvinylgermyl)benzene and Olefins
1
Figure 1. H NMR spectra of 1,4-bis(dimethylvilnylgermyl)benzene, 1,4-divinylbenzene, 3, and 6 in CDCl3.
emission of the polymer was rather small (8 nm). The
fluorescence efficiency and lifetimes are only slightly lower than
those of the olefin S5.
The absorption spectra of 1,4-bis(4-vinylphenyl)benzene
(S7), 1,4-bis[(4-vinylphenyl)-2,3,5,6-tetrafluoro]benzene (S8),
and 8 exhibited one maximum characterized by similar values of
their molar absorption coefficients. The first of these absorbed
with a maximum at 312 nm. The introduction of four fluorine
atoms shifted the absorption spectrum by 23 nm toward the
blue. The absorption spectrum of oligomer 8 was 9 nm shifted
to longer wavelengths compared to that of the chromophore.
This observation is consistent with the general tendency of
germanium to lower the transition energy. Similar behavior was
observed for the emission spectra. The blue shift (referenced
S7) was larger for S8 (20 nm) than for 8 (3 nm). Only the S7
fluorescence spectrum had vibronic structure, whereas the
C
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yields and fluorescence lifetimes decreased in the order S7 > S8
> 8.
CONCLUSIONS
■
New arylene−vinylene−germylene derivatives with strictly
defined structure were successfully synthesized via germylative
coupling condensation. All products obtained were isolated and
fully characterized via NMR. The molecular compounds were
subjected to GC-MS and elemental analyses. Oligomers were
characterized via GPC, and their thermal stability was
discussed. Photophysical properties of the synthesized com-
pounds were described. The emission properties of chromo-
phores were not significantly affected by the presence of
germanium. Moreover, the similarity of compounds 3 and 6 to
their silicon analogues was described.
Figure 2. GPC chromatogram of 6a−8a.
a
EXPERIMENTAL SECTION
Table 2. GPC Results
■
1. Materials. The chemical reagents were obtained from the
following sources: hexane, pentane, toluene, diethyl ether, tetrahy-
drofuran (THF), and acetone were purchased from Fluka, CDCl3 was
from Dr Glaser A. G. Basel, tetrakis(triphenylphosphine)palladium(0),
1,4-dibromobenzene, terephtalic aldehyde, methyltriphenylphospho-
nium bromide, 4-vinylphenylboronic acid, bromopentafluorobenzene,
1,4-dibromotetrafluorobenzene, 9-bromoanthracene, 9,10-dibromoan-
thracene, potassium tert-butoxate, styrene, 1,2-dibromoethane, ethanol,
methanol, magnesium sulfate, calcium hydride, sodium hydride, and
potassium hydroxide were from Aldrich, and chlorodimethylvinylsilane
was from Gelest. The solvents were distilled (tetrahydrofuran, toluene,
and diethyl ether from sodium and hexane from calcium hydride)
under argon and stored over type 4 Å molecular sieves. Dichloro-
methane (DCM) used for photophysical measurements was of
spectroscopic grade from Merck and was used as received. 1,4-
Divinylbenzene was dried and degassed, and chlorodimethyl vinyl-
silane was purified by “bulb-to-bulb” distillation and stored under
argon. All the syntheses of monomers and macromolecular
compounds and catalytic tests were carried out under an inert argon
atmosphere. 2,3,4,5,6-Pentafluoro-4′-vinylbiphenyl, 9-(4-vinylphenyl)-
anthracene, 1,4-bis[(4-vinylphenyl)-2,3,5,6-tetrafluoro]benzene (S8),
and 9,10-bis(4-vinylphenyl)anthracene (S5) were synthesized accord-
ing to an already known procedure,10 except for the catalyst, which was
replaced with commercially available tetrakis(triphenylphosphine)-
palladium(0). Ruthenium complexes [RuHCl(CO)(PCy3)2] (2a) and
[RuHCl(CO)(PPh3)3] (2b) were also prepared according to the
literature procedure.11,12
polymer Mn [g·mol−1
]
Mw [g·mol−1
]
PDI
DPn time [days]
6a
6b
7a
7b
8a
8b
2275
2863
2343
2875
2681
3128
4027
5679
4461
5150
4160
5431
1.77
1.99
1.90
1.90
1.55
1.70
6
7
3
4
4
5
3
5
3
5
3
5
a
PDI = Mw/Mn; DPn = number-average degree of polymerization;
polystyrene Shodex standards calibration curve in a range from 1.31 ×
103 to 3.64 × 106 Da; THF.
Table 3. Thermal Properties of Oligomers after 3- and 5-Day
Synthesis (Heating Rate of 10°C·min−1)
temperature loss [°C]
oligomer
1%
5%
10%
residue at 800 °C [%]
6a
6b
7a
7b
8a
8b
201
232
189
228
242
232
264
290
313
334
297
292
295
339
373
387
333
338
39
37
35
38
32
37
2. General Methods. 1H NMR (300 MHz), 13C NMR (75 MHz),
and 29Si NMR (60 MHz) spectra were recorded on a Varian XL 300
MHz spectrometer in CDCl3 solution. Chemical shifts are reported in
1
δ (ppm) with reference to the residue solvent (CDCl3) peak for H
and 13C and to TMS for 29Si. Gas chromatographic (GC) analyses
were performed on a Varian Star 3400CX with a DB-5 fused silica
capillary column (30 m × 0.15 nm) and TCD. Mass spectra of the
organic and organometallic molecular products were obtained by GC-
MS analysis (Varian Saturn 2100T, equipped with a BD-5 capillary
column (30 m) and an ion trap detector). Gel permeation
chromatography (GPC) analyses were performed using a Waters
2414 RI detector and a set of three serially connected 7.8 × 300 mm
columns (Waters Styragel HR1, HR2, and HR4; THF; flow rate 0.80
mL/min; temperature 20 °C; injection volume 10 μL). The number-
average molecular weight (Mn), weight-average molecular weight
(Mw), and PDI were determined by polystyrene standard calibration
curves. Thin-layer chromatography (TLC) was performed on plates
coated with 250 mm thick silica gel (Aldrich and Merck), and column
chromatography was conducted with silica gel 60 (70e 230 mesh,
Fluka). A TA Instruments TGA Q50 analyzer was used to investigate
the thermal stability of the samples. The measurements were
conducted in a nitrogen flow of 60 mL·min−1 from ambient
temperature to 800 °C at a heating rate of 10 °C·min−1. Measurement
of the elemental composition of the samples was performed on a Flash
Figure 3. Thermal properties of copolymers 6−8.
emissions of S8 and 8 were structureless. The lack of vibronic
structure in the fluorinated compounds results from their
different sequence congestion compared to S7. All of the
compounds displyed large emission efficiencies and rather short
fluorescence lifetimes (below 1 ns). The fluorescence quantum
D
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Table 4. Absorption and Emission Properties of Compounds 3−8 (in CH2Cl2 as Solvent)
a
b
c
d
λexc = 260 nm. λexc = 360 nm. λexc = 280 nm. λexc = 300 nm.
2000 elemental analyzer. Absorption spectra were recorded using a
Cary 100 UV−vis spectrophotometer (at room temperature, RT).
Fluorescence spectra were measured on a PerkinElmer LS-50B
spectrofluorimeter (RT) and were corrected for nonlinear PMT
response. Both absorption and emission spectra were recorded for
argon-saturated solutions using 1 cm × 1 cm rectangular cells.
E
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(cyclohexanecarbonitrile) (1.76 g, 7.2 mmol). The mixture was frozen
in a liquid nitrogen bath and subjected to freeze−pump−thaw cycling.
After the mixture was warmed to RT, it was heated in an oil bath for 2
weeks at 150 °C. After the reaction was complete, the mixture was
cooled to RT and transferred to a 50 mL round-bottom flask. Careful
trap-to-trap distillation gave 3.6 g (75% yield) of chlorodimethylvi-
nylgermane.
1H NMR (CDCl3, δ, ppm): 0.48 (s, 3H, CH3), 5.98 (m, 3H,
−CHCH2). 13C NMR (CDCl3, δ, ppm): 3.00 (CH3), 132.50 (
CH−Ge), 137.00 (CH2). MS: m/z (rel intensity) 166 (1), 151
(100), 131 (20), 139 (22). Anal. Calcd (%) for C4H9ClGe: C, 29.08,
H, 5.49. Found: C, 29.12, H, 5.56.
3.2. 1,4-Bis(dimethylvinylgermyl)benzene (1). A solution of 1,4-
dibromobenzene (0.300 g, 1.7 mmol) in 10 mL of THF was added to
a suspension of Mg (0.09 g, 3.3 mmol, magnesium surface was
activated by the use of 1,2-dibromoethane, 0.1 mL) and
chlorodimethylvinylgermane (0.495 g, 3 mmol) in 10 mL of THF
(the mixture was warmed). After the addition was completed, the
reaction mixture was refluxed and the reaction progress was controlled
by GC analysis. After the full conversion of 1,4-dibromobenzene, the
mixture was cooled to RT and the solvent was evaporated. The crude
product was extracted with hexane/water solvents. The organic layer
was dried under magnesium sulfate and filtered off. The solvent was
evaporated, and the residue was separated on a silica gel column
(hexane, Rf = 0.45). The product was obtained as a colorless liquid
1
(yield 75%). H NMR (CDCl3, δ, ppm): 0.46 (s, 12H, −CH3), 5.69
(dd, 2H, JHH = 20.1, 3.0 Hz, −CHCH2), 6.05 (d, 2H, JHH = 13.5, 3.1
Hz, −CHCH2), 6.77 (dd, 2H, JHH = 13.4, 20.1 Hz, −CHCH2),
7.47 (s, 4H, −C6H4−). 13C NMR (CDCl3, δ, ppm): −3.5 (−CH3),
130.9 (−CHCH2), 133 (−C6H4−), 138.6 (Ci), 140.79 (−CH
CH2). MS (EI): m/z (rel intensity, %) (M+•) 335 (1), 321 (68), 295
(13), 279 (7), 265 (4), 251 (5), 235 (4), 219 (14), 207 (100), 191
(13), 177 (15), 165 (18), 151 (27), 127 (17), 105 (15), 89 (21), 74
(6), 51 (5). Anal. Calcd (%) for C14H22Ge2: C, 50.10; H, 6.61. Found:
C, 50.18 ; H, 6.64.
4. General Procedure for Catalytic Examination. In a typical
test, the syntheses were carried out in dried and evacuated (vacuum/
argon) 5 mL glass ampules equipped with a magnetic stirring bar,
under an argon atmosphere. Ruthenium catalyst and olefins were
dissolved in dried and degassed toluene. Then, 1,4-bis-
(dimethylvinylgermyl)benzene was added. The ampule was heated
for 24 h at 80, 100, 120, and 140 °C. Concentrations of solutions
ranged from 0.125 to 1 mol·dm−3, 1,4-bis(dimethylvinylgermyl)-
benzene and olefin were added in the molar ratio [ViGe]:[olefin] =
1:2, the catalyst content was 1−2% mol (per germane). The progress
of germylative coupling was monitored by GC-MS or 1H NMR
analyses (oligomers).
Figure 4. Absorption and emission spectra of 6−8 in comparison to
standards (in CH2Cl2).
5. General Procedure for Germylative Coupling Condensa-
tion. All the reagents and solvents were dried and deoxygenated. The
syntheses were carried out under argon using standard Schlenk
techniques. [RuHClCO(PCy3)2] was used as a catalyst. A mixture of
reagents was placed in a 25 mL glass reactor equipped with a magnetic
stirring bar and heated for 24 h (molecular products) or 72 h
(oligomers) at 140 °C. The concentration of the solutions was 0.125
mol·dm−3; monomers and olefins were added in the molar ratio
[monomer]:[olefin] = 1:2.5 (for molecular products) and 1:1 (for
macromolecular products); the catalyst loading was 2% mol (per
monomer). After the reaction was complete, the solvent was
evaporated under a vacuum. The molecular products were purified
on a silica gel column (hexane/CH2Cl2 = 1:1). The oligomers were
dissolved in THF and purified by repeated precipitation from
methanol, filtered, and dried. Yields ranged from 83% to 95% for
molecular derivatives and 65−77% for macromolecular compounds.
6. Analytical Data of Isolated Products. 6.1. 1,4-Bis{((E)-2-
phenylethenyl)dimethylgermyl}benzene (3). 1H NMR (CDCl3, δ,
Fluorescence lifetimes were measured on a time-resolved spectro-
fluorimeter operating on a nanosecond scale with the detection system
based on the single photon counting technique (fluorescence lifetime
spectrofluorimeter FluoTime 300 from PicoQuant, equipped with 255,
300, and 375 nm diodes as its excitation sources).
3. Syntheses of Organogermanium Compounds. 3.1. Chlor-
odimethylvinylgermane. Chlorodimethylvinylgermane was synthe-
sized according to the literature.8 A 100 mL high-pressure Schlenk
vessel connected to a gas and vacuum line was charged under argon
with tributylvinylstannane (15 mL, 51.32 mmol), dichlorodimethyl-
germane (3.36 mL, 28.8 mmol), and 1,1′-azobis-
F
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ppm): 0.55 (s, 12H, −CH3), 5.25 (d, traces, C−CHCH2), 5.76 (d,
traces, C−CHCH2), 6.74 (d, traces, C−CHCH2), 6.74 (d, 2H,
JHH = 18.8, Ge−CHCH−C<), 6.88 (d, 2H, JHH = 18.8, Ge−CH
CH−C<), 7.39 (s, 4H, −C6H4−), 7.54 (s, 4H, Ge−C6H4−Ge). 13C
NMR (CDCl3, δ, ppm): −3.08 (CH3), 126.42 (Ge−CHCH−C<),
126.55 (CH from C−C6H4−C), 128.65 (traces, −CHCH2), 132.94
(traces, −CHCH2), 133.14 (CH from Ge−C6H4−Ge), 137.59 (Ci),
4027 [g·mol−1], Mn = 2275 [g·mol−1], PDI (Mw/Mn) = 1.77, n = 6.
GPC analysis (6b): Mw = 5679 [g·mol−1], Mn = 2863 [g·mol−1],
PDI(Mw/Mn) = 1.99, n = 7.
ppm): 0.57 (s, 12H, −CH3), 6.76 (d, 2H, JHH = 18.8, Ge−CHCH-
C<), 6.92 (d, 2H, JHH = 18.8, Ge−CHCH−C<), 7.28 (t, 2H, p-
C6H5), 7.35 (t, 4H, m-C6H5), 7.46 (t, 4H, o-C6H5), 7.56 (s, 4H, Ge−
C6H4−Ge). 13C NMR (CDCl3, δ, ppm): −3.07 (CH3), 126.36 (Ge−
CHCH−C<), 127.95 (p-C from C6H5), 128.52 (m-C from C6H5),
128.55 (o-C from C6H5), 133.15 (CH from Ge−C6H4−Ge), 138.02
(Ci), 141.02 (Ci), 143.70 (Ge−CHCH−C<). MS (EI): m/z (rel
intensity, %) (M+•) 488 (6), 471 (31), 369 (44), 283 (49), 267 (21),
206 (69), 191 (100), 179 (48), 165 (33), 147 (46), 117 (34), 105
(93), 87 (77), 73 (39). Anal. Calcd (%) for C26H30Ge2: C, 64.02; H,
6.20. Found: C, 64.09 ; H, 6.26.
140.99 (Ci), 143.23 (Ge−CHCH−C<). GPC analysis (6a): Mw
=
6.5. Poly[dimethylgermylene-1,4-phenylenedimethylgermylene-
(E)-vinylene-9,10-bis(4-phenyl)anthracenylene, (E)-vinylene] (7).
6.2. 1,4-Bis(((E)-4-(anthracen-9-yl)styryl)dimethylgermyl)benzene
(4). 1H NMR (CDCl3, δ, ppm): 0.63 (s, 12H, −CH3), 6.93 (d, 2H, JHH
1H NMR (CDCl3, δ, ppm): 0.65 (s, 12H, −CH3), 5.39 (d, traces,
C−CHCH2), 5.94 (d, traces, C−CHCH2), 6.91 (d, traces, C−
CHCH2), 6.95 (d, 2H, JHH = 18.8, Ge−CHCH−C<), 7.11 (d,
2H, JHH = 18.8, Ge−CHCH−C<), 7.29−7.51 (m, 8H, H3 from
−C6H4− and H2 from −C14H8), 7.65 (s, 4H, Ge−C6H5−Ge), 7.59−
7.71 (m, 8H, H2 from −C6H4− and H1 from −C14H8) 13C NMR
(CDCl3, δ, ppm): −3.06 (CH3), 125.02, 126.37 (Ge−CHCH−C<),
126.90, 129.78 (CH from C−C6H4−C), 131.55 (CH from C−C6H4−
C), 133.11, 133.20 (CH from Ge−C6H4−Ge), 136.80, 137.17 (Ci),
= 18.9, Ge−CHCH-C<), 7.09 (d, 2H, JHH = 18.9, Ge−CHCH−
C<), 7.32−7.48 (m, 12H, H3 from −C6H4−, H2 and H3 from
−C14H9), 7.63 (s, 4H, Ge−C6H5−Ge), 7.66−7.70 (m, 8H, H2 from
−C6H4− and H1 from −C14H9), 8.05 (d, 4H, JHH = 8.4, H4 from
−C14H9), 8.50 (s, 2H, H10 from −C14H9). 13C NMR (CDCl3, δ, ppm):
−3.02 (CH3), 125.10, 125.35, 126.34 (Ge−CHCH−C<), 126.76,
128.33, 128.41, 130.13 (CH from −C6H4−), 130.17, 131.32, 131.53,
133.21 (CH from Ge−C6H4−Ge), 136.67, 136.71, 137.19 (Ci), 138.49
(Ci), 143.40 (Ge−CHCH−C<). MS (EI): m/z (rel intensity, %)
(M+•) 840 (5), 739 (2), 723 (2), 634 (24), 459 (13), 367 (37), 352
(23), 280 (100), 251 (38), 209 (10), 181 (38), 165 (19), 151 (20),
126 (13), 105 (44), 89 (22). Anal. Calcd (%) for C54H46Ge2: C, 77.19;
H, 5.52. Found: C, 77.15; H, 5.57.
138.74 (Ci), 143.38 (Ge−CHCH−C<). GPC analysis (7a): Mw
=
4461 [g·mol−1], Mn = 2343 [g·mol−1], PDI (Mw/Mn) = 1.90, n = 3.
GPC analysis (7b): Mw = 5150 [g·mol−1], Mn = 25875 [g·mol−1],
PDI(Mw/Mn) = 1.90, n = 4.
6.6. Poly[dimethylgermylene-1,4-phenylenedimethylgermylene-
(E)-vinylene-1,4-(2,3,5,6-tetrafluoro)bis(4′-phenyl)phenylene, (E)-vi-
6.3. 1,4-Bis(dimethyl((E)-2-(2′,3′,4′,5′,6′-pentafluoro-[1,1′-bi-
1
phenyl]-4-yl)vinyl)germyl)benzene (5). H NMR (CDCl3, δ, ppm):
nylene] (8). 1H NMR (CDCl3, δ, ppm): 0.59 (s, 12H, −CH3), 5.37 (d,
traces, C−CHCH2), 5.87 (d, traces, C−CHCH2), 6.77 (d, traces,
C−CHCH2), 6.87 (d, 2H, JHH = 18.8, Ge−CHCH−C<), 6.97 (d,
2H, JHH = 19.0, Ge−CHCH−C<), 7.47 (m, 8H, −C6H4−), 7.57 (s,
4H, Ge−C6H4−Ge). 13C NMR (CDCl3, without C6F4 δ, ppm): −3.11
(CH3), 126.41 (Ge−CHCH−C<), 126.50 (CH from C−C6H4−C),
130.42 (CH from C−C6H4−C), 133.19 (CH from Ge−C6H4−Ge),
134.56 (Ci), 138.71 (Ci), 140.89 (Ci), 142.85 (Ge−CHCH−C<).
GPC analysis (8a): Mw = 4160 [g·mol−1], Mn = 2681 [g·mol−1],
PDI(Mw/Mn) = 1.55, n = 4. GPC analysis (8b): Mw = 5431 [g·mol−1],
Mn = 3128 [g·mol−1], PDI(Mw/Mn) = 1.70, n = 5.
0.58 (s, 12H, −CH3), 6.89 (d, 2H, JHH = 18.8, Ge−CHCH−C<),
6.91 (d, 2H, JHH = 19.0, Ge−CHCH−C<), 7.40 (d, 4H, −C6H4−),
7.55 (m, 8H, −C6H4− and Ge−C6H4−Ge). 13C NMR (CDCl3,
without −C6F5, δ, ppm): −3.16 (CH3), 126.54 (Ge−CHCH−C<),
130.33 (CH from −C6H4−), 130.79 (Ci), 133.14 (CH from Ge−
C6H4−Ge), 138.83 (Ci), 140.80 (Ci), 142.64 (Ge−CHCH-C<). MS
(EI): m/z (rel intensity, %) (M+•) 820 (1), 805 (3), 703 (10), 614
(8), 537 (6), 474 (4), 449 (93), 431 (10), 419 (7), 396 (7), 373 (74),
357 (67), 345 (7). 317 (11), 270 (14), 204 (100), 181 (22), 151 (27),
127 (12), 115 (10), 105 (80), 87 (30), 73 (6). Anal. Calcd (%) for
C38H28F10Ge2: C, 55.67; H, 3.44. Found: C, 55.61; H, 3.48.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.6b00336.
■
S
6.4. Poly[dimethylgermylene-1,4-phenylenedimethylgermylene-
Synthesis procedures for S1 and S2; NMR spectra of
new compounds (PDF)
(E)-vinylene-1,4-phenylene-(E)-vinylene] (6). 1H NMR (CDCl3, δ,
AUTHOR INFORMATION
Corresponding Author
*E-mail: Bogdan.Marciniec@amu.edu.pl. Fax: +48 (61)
8291987.
■
G
DOI: 10.1021/acs.organomet.6b00336
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Science Center UMO-
2011/02/A/ST5/00472 (Maestro) is gratefully acknowledged.
The authors would like to thank Dr. Gordon L. Hug for his
interest in the photophysical part of this study.
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DOI: 10.1021/acs.organomet.6b00336
Organometallics XXXX, XXX, XXX−XXX