Efficient Synthesis of One- and Two-Dimensional Multimetallic Gold–Bis(dithiolene) Complexes

Article abstract of DOI:10.1002/ejic.201600595

Multimetallic complexes having π-conjugated dithiolate ligands have recently received attention because of their unique solid-state properties. Reported herein are efficient and versatile routes for the synthesis of structurally well-defined multimetallic gold–bis(dithiolene) complexes. A dichlorogold(III) complex having a benzene-1,2-dithiolate ligand was prepared as a key terminal unit. A one-dimensional dimetallic gold complex was synthesized in good yield by using benzene-1,2,4,5-tetrathiolate as a bridging ligand. Furthermore, by using benzenehexathiolate as a bridging ligand, this strategy was applied to the synthesis of a two-dimensional trimetallic complex with a starburst structure. The solid-state structures of the anionic complexes were unambiguously confirmed by X-ray diffraction analyses.

Full text of DOI:10.1002/ejic.201600595

DOI: 10.1002/ejic.201600595
Communication
Heterometallic Complexes
Efficient Synthesis of One- and Two-Dimensional Multimetallic
Gold–Bis(dithiolene) Complexes
[
a]
[a]
[a]
[a]
Michihisa Murata* Shoji Kaji, Hidetaka Nishimura, Atsushi Wakamiya, and
Yasujiro Murata*[
a]
Abstract: Multimetallic complexes having π-conjugated dithio- plex was synthesized in good yield by using benzene-1,2,4,5-
late ligands have recently received attention because of their tetrathiolate as a bridging ligand. Furthermore, by using benz-
unique solid-state properties. Reported herein are efficient and enehexathiolate as a bridging ligand, this strategy was applied
versatile routes for the synthesis of structurally well-defined to the synthesis of a two-dimensional trimetallic complex with
multimetallic gold–bis(dithiolene) complexes. A dichlorogold(III) a starburst structure. The solid-state structures of the anionic
complex having a benzene-1,2-dithiolate ligand was prepared complexes were unambiguously confirmed by X-ray diffraction
as a key terminal unit. A one-dimensional dimetallic gold com- analyses.
Introduction
(tto) ligand(s) as the linking bridge,[5] albeit in suppressed
yields. For example, Kitagawa and co-workers recently reported
the preparation of the dianion of the dimetallic nickel–bis(di-
[
1]
One-dimensional (1D) polymers and two-dimensional (2D)
[
2]
nanosheets consisting of π-conjugated metal–bis(dithiolene)
units have received significant attention because of their
unique properties, which include high conductivity and mag-
netism, as well as their potential use in organic thermoelectric
[
5f]
thiolene) complex with the tto ligand in 3.4 % yield.
Kato
and co-workers reported the synthesis of a trimetallic nickel–
bis(dithiolene) complex by using the tto ligands in ca. 5 %
[
5e]
[
1h,1j,3]
yield.
Therefore, it is of great importance to establish a syn-
materials.
Whereas the relationship between the solid-
thetic strategy from which a wide variety of π-conjugated mul-
timetallic complexes can be realized. Herein, we report the de-
velopment of a rational route for the synthesis of di- and trime-
tallic complexes that leads to the creation of not only 1D rod-
shaped structure 2 but also 2D starburst structure 3 as potential
precursors for molecular conductors. Whereas the structure of
state structure and the electronic properties of the monometal-
lic bis(dithiolene) complexes with identical π-conjugated units
(
denoted as A for 1 in Figure 1) have been deeply studied from
[
4]
experimental and theoretical standpoints, research on multi-
metallic complexes has remained largely unexplored thus far,
owing in large part to the lack of an efficient and versatile route
for their synthesis.
[
2]
3
is a segment of a multimetallic nanosheet, this is the first
example of the selective synthesis of the structurally well-de-
fined 2D trimetallic complex. Gold complexes were selected not
[
4]
only because of their potential for molecular conductors by
oxidation but also because of the moderate stability against air
oxidation, which permits characterization of the anionic com-
plexes by NMR spectroscopy.
Results and Discussion
For the preparation of multimetallic gold complexes 2 and 3,
which include two different π-conjugated ligands denoted as
A and B for the terminal and bridging units (Figure 1), respec-
tively, we anticipated that a dichlorogold(III) complex having a
π-conjugated dithiolate ligand could be used as a key terminal
unit. Thus, dichlorogold complex 5 with a benzene-1,2-di-
thiolate ligand was prepared as an air-stable green powder
from dimethyltin complex 4 (Scheme 1). The structure of di-
chlorogold complex 5 was unambiguously confirmed by single-
crystal X-ray diffraction analysis (see the Supporting Informa-
tion). Then, we studied the synthesis of the bridging ligands.
Because unprotected 1,2,4,5-benzenetetrathiol was reported to
Figure 1. The structures of mono-, di-, and trimetallic bis(dithiolene) com-
plexes 1–3.
Over the past decades, di- and trimetallic bis(dithiolene)
complexes have been mostly prepared with tetrathiooxalate
[
a] Institute for Chemical Research, Kyoto University,
Uji, Kyoto 611-0011, Japan
[
6]
E-mail: mmurata@scl.kyoto-u.ac.jp
yasujiro@scl.kyoto-u.ac.jp
http://www.scl.kyoto-u.ac.jp/~kouzou/index.html
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/ejic.201600595.
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Communication
be air sensitive,[7] we developed routes for the synthesis of pre-
cursors 9 and 11, in which the thiol groups were fully protected
[
8]
with cyanoethyl groups, by Stille coupling (Scheme 2). Nota-
bly, we developed a useful method for the one-pot synthesis
of tributylstannyl reagent 7. This allowed us to isolate 7 in 89 %
yield readily by extractions, whereas the conventional two-step
synthesis includes isolation of 2-cyanoethanethiol with extreme
stench by distillation and subsequent stannylation to give 7
[
9]
only in 25 % overall yield.
Scheme 1. Synthesis of dichlorogold(III) complex 5 as a terminal unit.
Scheme 3. Synthesis of mono-, di-, and trimetallic complexes 12–14.
the terminal and central benzene rings is 6.1° for 13 and 4.0–
.6° for 14 (see the Supporting Information). The data for trime-
tallic complex 14 show that the Au–S bonds between Au and
6
[
11]
the central benzenehexathiolate ligand [2.305(1) Å as an av-
erage for the inner six bonds] is slightly shorter than those be-
tween Au and the terminal benzene-1,2-dithiolate ligand
[
11]
[2.315(1) Å
as an average for the outer six bonds], whereas
such a trend is not clearly seen in the structure of 13. According
[
12]
to the results of the DFT calculations
[CAM-B3LYP/6-31G*,
Scheme 2. Synthesis of 9 and 11 as the precursors for the bridging units;
dba = dibenzylideneacetone.
SDD (Au)], 13 and 14 optimized without countercations should
have a planar structure. Thus, the twisted geometries in the
We first performed the synthesis of simple monometallic solid state can be ascribed to the effect of the countercations
[
10]
complex 12
by using triethylamine as the base and isolated and the crystal-packing forces, and this is indicative of the con-
1
2 in 84 % yield as a green solid (Scheme 3). Then, the synthesis formational flexibility of these complexes. In addition, the bond
of the 1D dimetallic complex was examined with complex 5 lengths of the inner Au–S bonds (2.34 Å) were calculated to be
and precursor 9 as the terminal and bridging units, respectively. shorter than the outer Au–S bonds (2.38 Å), probably owing to
Although the reaction did not proceed if triethylamine was em- the electron-rich character of the central ligand.
ployed, dimetallic complex 13 was synthesized efficiently in the
To clarify the electronic properties, we conducted cyclic vol-
presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). By simply tammetry (CV) experiments for di- and trimetallic complexes 13
washing the resulting precipitate with chloroform, 13 was ob- and 14 together with monometallic complex 12 for comparison
tained in 53 % yield as an air-stable yellowish green solid. Fur- (Table 1). Complexes 13 and 14 exhibit irreversible oxidation
thermore, this method could be applied to the synthesis of a waves presumably as a result of adsorption phenomena on the
[
4h,5a,5b]
2D trimetallic complex with a starburst structure. Thus, reaction electrode, as reported for monometallic complexes.
The
of 5 with precursor 11 under similar conditions gave trimetallic oxidation potentials [E
complex 14 in 86 % yield as an air-stable brown solid. Com- nium (Fc/Fc ) for 13 and –0.42 V for 14] are shifted to more
plexes 13 and 14 are well soluble in solvents such as dichloro- negative values by ΔEonset,ox = –0.58 and –0.70 V, respectively,
= –0.30 V vs. ferrocene/ferroce-
onset,ox
+
methane, acetonitrile, DMF, and PhCN to degrees similar to that with reference to the oxidation potential of 12 (E
=
onset,ox
[
13]
of monometallic complex 12.
+0.28 V). The data indicate that di- and trimetallic complexes
The structures of these complexes were characterized by 13 and 14 are markedly more electron rich than monometallic
H NMR and C NMR spectroscopy, mass spectrometry, as well complex 12. In the reduction process, 13 and 14 show irreversi-
1
13
as single-crystal X-ray diffraction analyses (Figures 2 and 3). Di- ble reduction waves (Eonset,red = –1.99 V for 13 and –2.04 V for
metallic and trimetallic complexes 13 and 14 were found to 14), and the potential is shifted to more negative values by
possess a slightly twisted structure; the twist angle between ΔEonset,red = –0.17 and –0.22 V, respectively, relative to that of
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Communication
Table 1. Electrochemical and optical data.
Oxidation Reduction
HOMO[b]
[eV]
λabs [nm]
[c]
potential[
a]
potential
[a]
(log ε)
Eonset,ox [V]
Eonset,red [V]
12
13
14
+0.28
–0.30
–0.42
–1.82
–1.99
–2.04
–5.38
–4.80
–4.68
637 (1.75)
685 (2.39)
695 (2.58)
[
a] Onset potentials of the first oxidation peak measured by cyclic voltamme-
+
–
4 6
try in PhCN with [Bu N ][PF ] (0.1 M) as a supporting electrolyte at a scan
rate of 100 mV s by using Fc/Fc+ as an internal standard. [b] HOMO levels
estimated from the oxidation potentials by using the following equation:
HOMO [eV] = –(Eonset,ox + 5.1).[ [c] Absorption maxima measured in DMF
–1
14]
–
5
(
10
M), ε = absorption coefficient.
Figure 2. ORTEP drawing (50 % probability for thermal ellipsoids) of dimetallic
complex 13. Selected bond lengths [Å] and angles [°]: Au1–S1 2.323(4), Au1–
S2 2.317(4), Au1–S3 2.323(4), Au1–S4 2.321(5), S1–Au1–S2 89.88(16), S1–Au1–
S3 91.07(17), S2–Au1–S4 89.57(16), S3–Au1–S4 89.67(18).
Figure 4. Pictorial representation of the frontier orbitals of trimetallic complex
4. Geometry optimization was performed at the CAM-B3LYP/6-31G* (SDD
1
for Au) level with no countercations.
Figure 3. ORTEP drawing (50 % probability for thermal ellipsoids) of trimetallic
complex 14. Selected bond lengths [Å] and angles [°]: Au1–S1 2.304(2), Au1–
S2 2.307(2), Au1–S7 2.314(2), Au1–S8 2.310(2), S1–Au1–S2 89.93(8), S1–Au1–
S7 89.63(8), S2–Au1–S8 90.39(8), S7–Au1–S8 90.08(8).
Di- and trimetallic complexes 13 and 14 exhibit similar absorp-
tion bands at λabs = 685 and 695 nm, respectively (Figure 5). It
is notable that an intense absorption band is observed at λabs
=
1
2. The electron-rich characters of 13 and 14 were also demon-
strated in bulk powder by means of photoelectron spectro-
scopy, which shows that the ionization potentials (IPs, HOMO
levels) of the multimetallic complexes (–5.02 and –5.09 eV for
1
3 and 14, respectively) are elevated relative to that of 1
(
–5.51 eV), in good agreement with the results of the CV meas-
urements. DFT calculations (see the Supporting Information) in-
dicate that di- and trimetallic complexes 13 and 14 have well-
delocalized π-orbitals (HOMO) and Au/ligand σ* orbitals
(LUMO), both of which are doubly degenerate in the case of
1
4, and this is indicative of the removal of an electron from the
π orbital upon oxidation (Figure 4).
Monometallic complex 12 exhibits a weak absorption band
with a maximum wavelength (λabs) at 637 nm in DMF. Accord-
[
10]
ing to previous reports,
this band can be attributed to a
Figure 5. UV/Vis absorption spectra of 12–14 in DMF with their absorption
maxima and logarithm of absorption coefficient. Inset shows the expanded
spectra.
symmetry-forbidden transition from the π orbital (HOMO) to
the Au/ligand σ* orbital (LUMO) with charge-transfer character.
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Communication
3
27 nm with a tail up to 460 nm for 14. Single-point time- rated under reduced pressure. The solid residue was dissolved in
CH Cl and then MeOH was added. The resultant precipitate was
dependent DFT calculations [TD-CAM-B3LYP/6-31G*, SDD (Au),
see the Supporting Information] for 13 and 14 indicate that
the absorption bands in the visible region maintain the π–σ*
character in a manner similar to that of 12. The intense absorp-
tion band (λabs = 327 nm) observed for 14 is attributed to a
transition having significant σ–σ* character (HOMO–8→LUMO,
see the Supporting Information). Judging from the systematic
comparison of the absorption spectra of the mono-, di-, and
trimetallic complexes, the redshift in the σ–σ* transition band
is remarkable, and a further redshift in this band can be ex-
pected upon increasing the number of gold–bis(dithiolene)
segments.
2
2
collected by filtration to give 14 (131 mg, 65.5 μmol) in 86 % yield
as a brown solid, m.p. 151–152 °C (dec.). H NMR (500 MHz, [D ]-
acetone): δ = 7.09 (dd, J = 6.0, 3.5 Hz, 6 H), 6.73 (dd, J = 6.0, 3.5 Hz,
H), 3.30 (m, 24 H), 1.71 (m, 24 H), 1.41 (m, 24 H), 0.94 (t, J = 7.5 Hz,
6 H) ppm. C NMR (126 MHz, [D ]acetone): δ = 140.59, 125.39,
24.40, 59.16, 24.09, 19.83, 13.51 ppm. HRMS (ESI-TOF–): calcd. for
C H N S Au [M – Bu N ] 1759.2285; found 1759.2218.
6
1
6
6
3
1
13
6
+ –
5
84
2
12
3
4
CCDC 1476788 (for 5), 1476786 (for 13), and 1476787 (for 14) con-
tain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre.
Acknowledgments
Conclusions
Financial support was in part provided by the Japan Society for
the Promotion of Science (JSPS), Grant-in-Aid for Challenging
Exploratory Research (grant number 16K13626. XRD measure-
ments were in part performed at the BL38B1 and BL40XU of
SPring-8 with the approval of the Japan Synchrotron Radiation
Research Institute (JASRI) (proposal no. 2014B1556 and
In summary, we demonstrated efficient and versatile methods
for the synthesis of 1D and 2D multimetallic gold–bis(dithiol-
ene) complexes with well-defined structures by using a di-
chlorogold(III) complex having a benzene-1,2-dithiolate ligand
as a terminal unit. By using benzene-1,2,4,5-tetrathiolate as a
bridging unit, a 1D rod-shaped dimetallic complex was synthe-
sized in good yield. Furthermore, on the basis of this synthetic
strategy, we prepared a 2D trimetallic complex with a starburst
structure by using a benzenehexathiolate bridging unit. The
solid-state structures of the anionic complexes were unambigu-
ously revealed by X-ray diffraction analyses. The multimetallic
complexes were shown to possess HOMO(s) that were elevated
relative to that of the monometallic complex. The new synthetic
methods can offer a way to prepare a wide variety of unprece-
dented 1D and 2D multimetallic gold–bis(dithiolene) com-
plexes. Further studies on the structures and properties of the
oxidized states as well as replacing gold with nickel or copper
are currently underway in our group.
2
015B1074).
Keywords: Gold · Multimetallic complexes · S ligands ·
Conjugation
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[
1
(
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4
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2
2
4
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Published Online: ■
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
Heterometallic Complexes
We establish efficient and versatile
methods for the synthesis of multime-
tallic gold–bis(dithiolene) complexes
with well-defined structures. A two-di-
mensional trimetallic complex with a
starburst structure is prepared and iso-
lated in high yield. The solid-state
structures of the complexes are unam-
biguously revealed by X-ray diffraction
analyses.
M. Murata,* S. Kaji, H. Nishimura,
A. Wakamiya, Y. Murata* ................. 1–6
Efficient Synthesis of One- and Two-
Dimensional Multimetallic Gold–
Bis(dithiolene) Complexes
DOI: 10.1002/ejic.201600595
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim