Preparation and Reactions of Dichlorodithienogermoles

Article abstract of DOI:10.1021/acs.organomet.5b00832

The reaction of 3,3′-dilithiobithiophenes with tetrachlorogermane afforded 4,4-dichlorodithienogermoles, which readily underwent substitution on the central germanium atom. Reactions of a dichlorodithienogermole with LiAlH₄, MeLi, Me₂NC₆H₄Li, and C₆F₅MgBr gave the corresponding Ge-substituted products. Dihydrodithienogermole obtained from the reaction with LiAlH₄ was further treated with LDA to give a dimer whose structure was verified by a single-crystal X-ray diffraction (XRD) study. Hydrolysis of dichlorodithienogermoles provided cyclotetragermoxanes. Their optical properties were examined with respect to the UV absorption and fluorescence spectra. It was found that one of the cyclotetragermoxanes responded to a nitorobenzene vapor in the solid state, decreasing the PL intensity.

Full text of DOI:10.1021/acs.organomet.5b00832

Article
pubs.acs.org/Organometallics
Preparation and Reactions of Dichlorodithienogermoles
Joji Ohshita,* Masashi Nakamura, and Yousuke Ooyama
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
S
* Supporting Information
ABSTRACT: The reaction of 3,3′-dilithiobithiophenes with
tetrachlorogermane afforded 4,4-dichlorodithienogermoles,
which readily underwent substitution on the central germanium
atom. Reactions of a dichlorodithienogermole with LiAlH4,
MeLi, Me2NC6H4Li, and C6F5MgBr gave the corresponding
Ge-substituted products. Dihydrodithienogermole obtained
from the reaction with LiAlH4 was further treated with LDA
to give a dimer whose structure was verified by a single-crystal
X-ray diffraction (XRD) study. Hydrolysis of dichlorodithieno-
germoles provided cyclotetragermoxanes. Their optical proper-
ties were examined with respect to the UV absorption and fluorescence spectra. It was found that one of the cyclotetragermoxanes
responded to a nitorobenzene vapor in the solid state, decreasing the PL intensity.
bithiophene, namely dithienogermole (DTG in Chart 1), has
been extensively studied as an optoelectronic material.15,16 In
comparison to DTS derivatives, DTG-containing π-conjugated
oligomers and polymers exhibit enhanced interchain interac-
tion in the solid state, likely due to the higher flexibility of
germanium substituents arising from longer G−C bonds and to
the larger van der Waals interaction of heavier germanium, and
are thus expected to be better carrier-transporting materials
for OTFTs and PSCs.15 Emissive DTG derivatives have been
also reported.16 However, the synthetic procedure for DTG is
rather limited and no direct derivatization on the bridging
germanium atom of DTG has been demonstrated so far,
although olefin metathesis of 4,4-dialkenyl-substituted DTGs
was recently reported.17 Usually, DTGs are prepared by the
reactions of 2 equiv of RLi or RMgX with GeCl4 leading
to R2GeCl2, followed by cyclization with dilithiobithiophenes
(Scheme 1). However, this conventional methodology is difficult
INTRODUCTION
■
There has been considerable interest in silole-containing com-
pounds,1 since interesting properties of silole derivatives based
on the orbital interaction between the silicon σ* and the
butadiene π* orbital (σ*−π* conjugation) were demonstrated
by Tamao, Yamaguchi, and co-workers.1a−d The low-lying
LUMO arising from the σ*−π* interaction leads to sufficiently
high electron affinity of siloles, making it possible to utilize them
as efficient electron-transporting-layer (ETL) materials for multi-
layered organic light-emitting diodes (OLEDs).1 Highly lumi-
nescent2 and carrier transporting properties3 have been also
reported for silole-based compounds and polymers. In the course
of our studies concerning silole systems, we have developed new
element blocks4 in which biheteroaryls such as bithiophene,5
bipyridyl,6 and biindole7 are bridged by a silicon unit at the
β,β′-positions to form a silole ring, in the hope that the orbital
interaction between the silicon σ* and the heteroaromatic π* orbital
provides opportunities to tune the electronic states, leading to
improved functionalities. Of those, dithienosilole (DTS in Chart 1)
Scheme 1. Conventional Preparation of DTGs
Chart 1. General Structures of DTS and DTG
to be applied for the synthesis of DTGs with small and large
substituents on the germanium atom. Introduction of two small
organic substituents to GeCl4 is usually a nonselective process
and gives mixtures of RnGeCl4−n (n = 0−4), from which sepa-
ration of the desired R2GeCl2 is difficult. For heavy R2GeCl2, the
is widely used as a building unit of π-conjugated oligomers and
polymers that are applicable to ETL and emissive materials of
OLEDs, semiconducting materials for organic thin film transistors
(OTFTs) and polymer solar cells (PSCs), and sensing materials.8
In regard to this, we have prepared germanium-,9 tin-,10
bismuth-,11 and antimony-bridged bithiophenes12 and explored
their functionalities. Dithienophosphole13 and -borole14 have
been also extensively studied. Like DTS, germanium-bridged
Received: October 1, 2015
© XXXX American Chemical Society
A
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substitution reactions may proceed more selectively. However,
purification of them by distillation is difficult, because of the high
boiling points. Moreover, the high tendency of chlorogermanes
to undergo hydrolysis does not generally allow treatment of them
with column chromatography.
In this paper, we report the preparation of 4,4-dichloro-
dithienogermoles (DTGCl) by the reactions of dilithiobithio-
phenes with GeCl4 (see Scheme 2), which are useful as precursors
for DTGs with variously substituted bridging germanium atoms.
In fact, some reactions of DTGCl were examined, which led to
new DTG derivatives, including unsubstituted DTG and DTG-
containing cyclotetragermoxanes. The presently prepared DTG
derivatives were examined with respect to the optical and electro-
chemical measurements to understand how the substituents affect
the properties. Single-crystal structures of two new DTG deriv-
atives are also described.
No other impurities were detected in the mixtures by either
NMR or EI-MS analysis. Since these byproducts were inert under
ordinary reaction conditions, the dichlorides could be used for the
following reactions as the mixtures without sublimation. Using
the mixtures as the reactants did not change the product yields.
We next examined chemical reactivities of the DTG dichlorides.
Reduction of DTGCl with LiAlH4 provided 4,4-dihydrodithieno-
germole (DTGH) in 38% yield, as the first synthesis of
unsubstituted DTG (Scheme 2). In this reaction, approximately a
10% yield of bithiophene and a trace of 3-germylbithiophene were
also found to be formed, which were readily removed by silica
gel column chromatography. With methylmagnesium bromide,
pentafluorophenylmagnesium bromide, and 4-dimethylamino-
phenyllithium, the substitution products DTGMe, DTGPhF,
and DTGAPh were obtained in 22%, 51%, and 24% yields,
respectively. As described above, DTGs that have been prepared so
far always contain ordinal alkyl or aryl substituents on the bridging
germanium atom, and the effects of substituents have not yet been
well elucidated. We therefore examined these products with respect
to the optical and electrochemical properties. The UV absorption
and photoluminescence (PL) spectra of the substituted compounds
are presented in Figure 1, together with those of DTGPh that was
RESULTS AND DISCUSSION
The reaction of GeCl4 with 3,3′-dilithiobithiophene in ether gave
DTGCl, as shown in Scheme 2. After filtration of the reaction
■
Scheme 2. Preparation and Reactions of DTG Dichlorides
mixture and evaporation of the solvent, the dichloride was sep-
arated from the residue by sublimation in 62% yield. In this reac-
tion, the use of an excess amount of GeCl4 was essential to
obtain DTGCl in good yield. Using an equimolar amount of
GeCl4 provided spirobi(dithienogermole) as a major byproduct
(ca. 10%), as detected by the 1H NMR spectrum. The attempted
preparation of the silicon analogue dichlorodithienosilole by the
reactions of SiCl4 and 3,3′-dilithiobithiophene under similar con-
ditions was unsuccessful, and we always obtained complex mix-
tures containing bithiophene as viscous oils. Similar treatment
of GeCl4 with diethyldilithiobithiophene afforded DTGCl-Et in
71% yield after sublimation. Trimethylsilyl-substituted DTG
dichloride (DTSCl-Si) was also obtained in 50% yield. The lower
yield of DTGCl-Si was due to its high sublimation temperature.
They were obtained as mixtures with 4,4′-diethylbithiophene and
4,4′-bis(trimethylsilyl)bithiophene, respectively, in molar ratios
of approximately 9:1, after filtration followed by evaporation.
Figure 1. (a) UV absorption and (b) PL spectra of DTGs in THF.
prepared by a conventional method (Scheme 1) for comparison.9
Their optical and electrochemical data are summarized in Table 1.
The absorption and PL bands shifted to lower energies in the
order DTGH ≈ DTGMe ≈ DTGAPh < DTGPh < DTGPhF,
due to the lowered LUMO in that order, as estimated on the basis
of the anodic onsets of the cyclic voltammograms (CVs) and the
optical band gaps (Table 2). The CVs showed irreversible profiles;
thus, a detailed discussion on the basis of those data would be
difficult. However, similarity of the molecular structures of these
B
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Table 1. Optical Data of DTGs
Scheme 3. LDA-Derived Dimerization of Dithienogermole
PL
UV−vis abs λmax/nm
λem/nm in THF Φ/% in THF
compd
(ε/L (mol cm)−1
)
(solid)
(solid)
DTGH
333 (11100)
333 (12700)
337 (12000)
347 (8100)
393 (409)
391 (395)
400 (422)
423 (429)
406 (451)
69 (22)
70 (32)
79 (19)
32 (45)
6 (6)
DTGMe
DTGPh
DTGPhF
DTGAPh
268, 333 (50400)
Table 2. Experimentally and Theoretically Estimated
HOMO and LUMO Energy Levels of DTGs
experimental
theoretical
a
b
c
c
compd
HOMO
LUMO
HOMO
LUMO
DTGH
−5.4
−5.4
−5.5
−5.6
−5.2
−2.0
−2.0
−2.2
−2.4
−1.9
−5.5
−5.3
−5.3
−5.7
−5.0
−1.4
−1.2
−1.3
−1.8
−1.0
DTGMe
DTGPh
DTGPhF
DTGAPh
a
b
Based on the CV oxidation peak. Estimated from the HOMO
energy level and optical band gap. Calculated from DFT calculations
c
(B3LYP/6-31G(d)).
Figure 2. ORTEP drawing of dDTGH with thermal ellipsoids at the
50% probability level. Hydrogen atoms were omitted for clarity.
DTG derivatives seems to allow the approximate comparison of
the onset potentials. The absorption bands of DTGAPh at 268
and 305 nm is likely ascribed to the local absorption of dimethyl-
aminophenyl units (cf. λmax 255, 301 nm for dimethylaniline in
THF). To understand the effects of substituents on the electronic
states of DTGs, we carried out quantum chemical calculations
of the molecules. As can be seen in Figure S-31 in the Supporting
Information, the HOMOs of the present DTGs are not evidently
affected by the substituents, except for DTGAPh, while the
LUMOs clearly exhibit perturbation by the substituents to some
extent. The HOMO of DTGAPh shows the contribution of
dimethylaminophenyl substituents, being presumably responsible
for its lower oxidation potential in the CV. All of the present
DTGs showed PL spectral changes depending on the states: that
is, measuring the PL spectra as solids resulted in a red shift of
the maximum by approximately 10 nm. At the same time, the PL
quantum yield decreased likely due to the concentration quenching,
except for DTGPhF, whose efficiency increased from Φ = 32% to
45%. It is speculated that packing in the solids affects the solid-state
PL properties of DTGPhF, although we have not obtained any
direct information to support this.
In an attempt to introduce substituents on the thiophene
rings of DTGH, we obtained a dimer (dDTGH) in 30% yield
by the reaction with lithium diisopropylamide (LDA), as pre-
sented in Scheme 3. However, no evidence for the lthiation
of the α-position of DTGH was obtained. The dimerization
may be understood by the formation of 4-lithiodithienogermole
(DTGLi) as an intermediate. The formation of a silyl anion
by the reaction of phenylsilole containing a Si−H bond on the
ring silicon has been reported previously.18 The structure of
dDTGH was verified by an X-ray single-crystal diffraction study.
As presented in Figure 2, the molecule possesses two twisted
bithiophene units linked by two germylene units. All of the bond
distances and angles in this molecule are in the standard ranges,19
indicating that no significant strain is involved. Both the UV
absorption and PL bands of dDTGH in THF appeared at
energies higher (λmax 247, 277 nm, λem 411 nm) than those of
DTGH, reflecting the twisted bithiophene structure. In the
solid state, a slight red shift by approximately 5 nm and an
increase in quantum yield of the PL band were observed from
Φ = 15% to 26%, similar to the case for DTGPhF. On the basis
of these observations, we examined aggregation-induced emission
of dDTGH and DTGPhF by adding ethanol as a poor solvent to
the THF solutions. However, no obvious changes occurred.
Functionalization of the α-positions of DTGH was achieved
by treatment with NBS in chloroform, which gave dibromide
DTGH-Br in 88% yield (Scheme 4). In this reaction, Ge−H
Scheme 4. Bromination of DTGH
bonds were found to be inert under the reaction conditions and
remained unchanged in the product.
Recently, cyclic tetrasiloxanes with dibenzosilole units were
synthesized and their PL properties were investigated by West,
Tang, and co-workers.20 Cyclic compounds containing perpen-
dicularly arranged and accumulated π-conjugated systems are
of interest, because of their potential applications to emissive
materials. Hydrolysis of DTG dichlorides in the presence of
triethylamine as an HCl scavenger provided the corresponding
cyclotetragermoxanes DTGO, DTGO-Et, and DTGO-Si in 6%,
60%, and 40% yields, respectively, as shown in Scheme 5. The
lower yield of DTGO is presumably due to the formation of
insoluble polymeric substances, which were removed by filtra-
tion. DTGO-Et crystallized from toluene, giving single crystals
with quality sufficient for an X-ray diffraction study. The ORTEP
drawing is depicted in Figure 3, showing the inclusion of toluene
molecules in the crystal. The molecule possesses a chairlike
cyclotetragermoxane core with two germanium and four oxygen
C
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previously,20 which has a boatlike cyclotetrasiloxane core. The
DTG systems keep the high planarity and are arranged in a per-
pendicular fashion with respect to the cyclogermoxane pseudo
plane. All of the bond distances and angles are in the standard
ranges.19
Scheme 5. Hydrolysis/Condensation of DTG Dichlorides
UV absorption and PL spectra of the present cyclo-
tetragermoxanes are presented in Figure 4. The UV absorption
and PL bands moved to longer wavelengths on the introduction
of electron-donating ethyl and trimethylsilyl groups. Interestingly,
the PL quantum efficiencies increased as DTGO-Et < DTGO <
DTGO-Si in both the solution and solid states (Table 3). It is
Table 3. Optical Data of DTG-Containing
Cyclotetragermoxanes
PL
UV−vis abs λmax/nm (ε/L λem/nm in THF Φ/% in THF
compd
(mol cm)−1
)
(solid)
(solid)
DTGO
350 (42120)
367 (59200)
360 (49500)
431 (443)
451 (477)
434 (430)
45 (9)
33 (5)
DTGO-Et
DTGO-Si
80 (49)
known that silyl substitution often enhances the PL efficiencies of
π-conjugated compounds.21 In the present case, the PL quantum
yields of DTGO-Si reached 80% in THF and 49% in the solid
state. The high quantum yield of DTGO-Si is likely also due
to the fact that the sterically bulky silyl substitution prevents
aggregation-caused quenching.
Figure 3. ORTEP drawings of DTGO-Et with thermal ellipsoids at
the 50% probability level. Hydrogen atoms are omitted for clarity.
Recently, we reported that an octahedral silsesquioxane (T8)
with a DTG-containing substituent at each corner exhibited
sensing behavior toward nitrobenzene and the PL intensity
decreased upon addition of nitrobenzene to the solution.16a
DTGO-Si also responded to nitrobenzene in a fashion similar
to that above. Thus, when a solid of DTGO-Si was exposed to
a saturated nitrobenzene vapor in air at room temperature
(nitrobenzene vapor pressure at 20 °C is 20 Pa), the PL
intensity markedly decreased on increasing the exposure time
(Figure 5), indicating the potential applications of the present
Figure 5. PL spectral changes of DTGO-Si solid on exposure to
nitorobenzene vapor.
Figure 4. (a) UV absorption and (b) PL spectra of cyclotetragermoxanes
in THF.
cyclotetragermoxane system as the core structure of sensing
materials for nitroaromatic explosives. The quenching was revers-
ible, and removal of nitorobenzene under reduced pressure
reproduced the original intensity. As the spectral shape was not
changed during the experiment, it is most likely that the quenching
atoms nearly on one plane and two other germanium atoms
located above and below the plane. This is a situation different
from that of dibenzosilole-containing cyclotetrasiloxane, reported
D
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occurred by photoelectron transfer from the excited state of
relatively electron rich DTGO-Si to electron deficient nitoro-
benzene, as often proposed for the sensing of nitroaromatics.22 It
is noteworthy that the compound exhibited the sensitivity in the
solid state. Solid-state sensing toward the vapor is an important
issue for the convenient detection of nitroaromatics.23 However,
organic fluorophores usually show concentration quenching in the
solid state that decreases the fluorescence intensity and thus are
difficult to use for turn-off sensors in the solid state.
Optimized geometry of DTGMe (MOL)
Optimized geometry of DTGPh (MOL)
Optimized geometry of DTGPhF (MOL)
Optimized geometry of DTGAPh (MOL)
AUTHOR INFORMATION
Corresponding Author
*E-mail for J.O.: jo@hiroshima-u.ac.jp.
■
Notes
The sensitivity of DTGO-Si was examined in THF in com-
parison with that of DTGH. As shown in Figure 6, DTGO-Si
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by a Grant-in-Aid for Scientific
Research on Innovative Areas “New Polymeric Materials Based
on Element-Blocks (No. 2401)” from The Ministry of Education,
Culture, Sports, Science, and Technology of Japan.
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CONCLUSIONS
■
In summary, we prepared DTG dichlorides in moderate to good
yields and explored their usefulness as precursors of variously
Ge-substituted DTGs. They readily undergo reduction and
nucleophilic substitution to provide new DTG derivatives,
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acs.organomet.5b00832.
■
S
Experimental details and 1H and 13C NMR spectra of the
presently prepared DTG derivatives, CVs, and HOMO
and LUMO profiles of DTGH, DTGMe, DTGPh, and
DTGPhF, derived from quantum chemical simulation
(PDF)
X-ray crystallographic data for DTGH (CIF)
X-ray crystallographic studies for DTGO-Et (CIF)
Optimized geometry of DTGH (MOL)
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DOI: 10.1021/acs.organomet.5b00832
Organometallics XXXX, XXX, XXX−XXX