An air-stable anionic two-dimensional semiconducting metal-Thiolate network and its exfoliation into ultrathin few-layer nanosheets

Article abstract of DOI:10.1039/c9cc09349d

The black, small-bandgap semiconducting framework Eu-dfdmat features extensive Eu³⁺-sulfur bridges from the linear linker 2,5-difluoro-3,6-dimercaptoterephthalate (dfdmt). Each Eu center is chelated to four dfdmt linkers to form an anionic coor

Full text of DOI:10.1039/c9cc09349d

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An air-stable anionic two-dimensional semiconducting metal-
thiolate network and its exfoliation into ultrathin few-layer
nanosheets †
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
a
Qi Zeng,‡ Lei Wang,‡ Yitao Huang, , Sai-Li Zheng, Yonghe He, Jun He,* Wei-Ming Liao,* Gang
DOI: 10.1039/x0xx00000x
b
c
d
Xu,* Matthias Zeller, and Zhengtao Xu*
www.rsc.org/
7
The black, small-bandgap semiconducting framework Eu-dfdmat from the metal-dithiolene systems ), metal-linker electronic
3
+
features extensive Eu -sulfur bridges from the linear linker 2,5- coupling in MOF solids has now proven a fruitful topic to pursue.
difluoro-3,6-dimercaptoterephthalate (dfdmt). Each Eu center is To investigate structure-property relations, well-defined
chelated to four dfdmt linkers to form an anionic coordination structures such as single crystals are crucial. As electronic
sphere involving four carboxyl O and four mercapto S centers coupling often involves strong links with significant covalent
(
4 4
EuO S ), wherein the charge buildup can be alleviated by the character (e.g., the less reversible metal-thiolate links) to
electron-withdrawing fluoro groups. The extensive metal-linker promote orbital overlap, many electronic MOF materials are
2
+
bonding, together with a trace of Eu species, appears to boost obtained as powder samples, and single crystals of 2D or 3D π-
electronic interaction in the 2D net, generating a small band gap of conjugated metal-thiolate networks remain rare, while related
-
6
-1
1
.31 eV (946 nm), albeit a modest conductivity (e.g., 10 S m ). The cases often involving metal-thiolate blocks linked via more
8
9
crystals also exhibit persistent EPR signals indicative of organic labile (e.g., pyridinyl and oxo ) donors.
radicals (g=2.002). The Eu-dfdmt solid are stable in air and can be
exfoliated into utrathin nanosheets (ca. 5 nm; 6-8 layers).
In this context, lanthanide (Ln)-sulfur complexes are
interesting. First, EuS and other RE chalcogenides are known for
1
0
intriguing optical and electronic properties ; RE complexes
with organic sulfur ligands including thiolates and
The structure-property relation remains a challenging topic in
1
the study of metal-organic frameworks as electronic materials.
11
thiocarboxylates have also been widely studied , with some
Because of the poor electronic coupling across metal-
carboxylate and other popular linkages, MOFs as solid state
materials had long been perceived as electronically inert; even
though systematic efforts had been earlier made to unveil the
feasibility of electronically integrating the metal centers and
12
exhibiting dark colors indicative of Ln-ligand electronic
coupling (e.g., involving the Eu 4f and S 3p orbitals). Second,
with RE(III) ions being hard acids and S donor soft bases, the RE-
S links offer lability and reversibility for crystallizing the
networks.
organic π-linkers, in order to clear the conceptual barrier to
However, Ln-S links for MOF construction remain under-
2
electronic MOF solids.
With the discovery of
explored: most reported RE-S complexes are discrete, with only
4
conductive/metallic
transport,3
ferromagnetic,
11a, 11c, 11d, 13
a few
being 1D polymeric structures. The underuse
5
6
superconductive and topological insulator properties (mostly
is perhaps (this is our speculation) due to the perceived ionicity
and lability of the RE-S bond, which had swayed our vision, and
made us think it unsuited for electronically bridging the organic
moieties. For example, a 3D Nd-dithiocarbamate MOF crystal
was recently made, but it is not π-conjugated, features light
a. School of Chemical Engineering and Light Industry, Guangdong University of
Technology, Guangzhou 510006, Guangdong, China junhe@gdut.edu.cn,
wmliao@gdut.edu.cn
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
1
4
b.
color and readily hydrolyses in air.
Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian,
China gxu@fjirsm.ac.cn.
Department of Chemistry, 560 Oval Drives, Purdue University, West Lafayette,
c.
Indiana, 47907 United States.
Department of Biology and Chemistry, City University of Hong Kong, 83 Tat
d.
Chee Avenue, Kowloon, Hong Kong, China zhengtao@cityu.edu.hk.
†
Electronic Supplementary Information (ESI) available: Experimental details and
general procedures; XRD, IR, EPR, XPS, TGA, optical absorption spectrum and
temperature dependent I-V curves. CCDC 1941723 contains the supplementary
crystallographic data for Eu-dfdmt. See DOI: 10.1039/x0xx00000x
‡
These authors contributed equally to this work.
4
-
3-
Scheme 1 Linker dfdmt , its thiyl radical dfdmt· and two possible schemes for
coordination with Eu .
3
+
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That is why the black crystal of the conjugated Eu-thiolate 26.69, H 3.11, N 8.65, S 15.83%) is derived from X-ray
View Article Online
DOI: 10.1039/C9CC09349D
net Eu-dfdmt (Scheme 1) is instructive: it is a water- and air- photoelectron spectroscopy (XPS).
stable semiconductor, with a small band gap of 1.31 eV (946 nm)
to indicate strong electronic interaction throughout its two- 2p3/2 at 161.4 and 2p1/2 162.6 eV in one (major) set, and 163.7
dimensional (2D) grid. It is also highly anionic, and can be and 164.9 eV (respectively) in the other (minor) set (Fig. S7c).
XPS reveals two types of sulfur centers, with the signals of S
2
1
exfoliated into 2D MOF nanosheets amidst the thriving class of The major type can be ascribed to the anionic thiolate S centers
D materials.15
(RS , lower binding energies), and the minor type, thiyl radicals
-
2
-
The 2D MOF Eu-dfdmt was crystallized by solvothermally (RS·). Deconvolution of the peaks indicate the RS /RS· molar
reacting H dfdmt (Scheme 1; see ESI for synthesis) and ratio to be 7:5. The RS /RS· and NH /NH ratios, however, are
4 4 3
-
+
3 2
EuCl ·6H O in N,N-dimethylformamide (DMF), water and variable in this system; as XPS is surface sensitive, its results may
acetonitrile (1:1:1, v/v/v). Single-crystal X-ray diffraction (SCXRD) not reflect the bulk composition. The occupancy of the
revealed the connectivity and composition Eu(dfdmt)
anionic net (Fig. 1a and 1b). The structure is tetragonal (P4/n; refined using the XPS NH
2
for the associated H atoms was therefore not crystallographically
+
4
/NH
3
ratio.
Table S1, ESI), with ½ dfdmt and ¼ Eu in the asymmetric unit.
XPS also indicates Eu to be mostly trivalent, accompanied by
3
+
2+
4 4 4
The Eu is 8-coordinated (EuO S ), with the C -related carboxyl a trace of Eu : i.e., the prominent Eu(III) 3d3/2 (1165.9ꢀeV) and
1
7
O (2.384 Å) and thiolate S (2.988 Å) donors forming a square 3d5/2 (1136.4ꢀeV) peaks (Fig. S7b) , and the weak Eu(II) peaks at
antiprism (Fig. 1a): the multiple S atoms bonded to Eu(III) here lower binding energies of 1158.2 and 1126.9 eV. Lanthanides
1
8
2
+
therefore contrast with the known EuDMBD framework (DMBD, commonly being trivalent, the Eu is stabilized by its half-filled,
1
6
7
2
,5-dimercapto-1,4-benzenedicarboxylic acid), wherein the - 4f configuration. The Eu(II) fraction is however small (below 5%
SH groups remain unbonded to the metal center. The Eu(III) is as per XPS), and its impact on the overall charge of the
2
+
3+
thus chelated to four dfdmt bridges in the resulted puckered Eu(dfdmt)
2
net is insignificant. The Eu likely arises from Eu
4
-
square net (Fig. 1b), featuring neighboring Eu square antiprisms reduction by the electron-rich dfdmt linkers, which also forms
in opposing orientations. The Eu-S links afford a rare example of the radical anion dfdmt· mentioned above.
single crystalline 2D π-conjugated metal-thiolate net (Fig. S10; The paramagnetic organic radical and Eu(II) species are also
3
-
1
4
cf an unconjugated Eu-sulfur sheet ).
detected by EPR measurement (at 100 K) on the powder sample
, however, is of Eu-dfdmt. The asymmetric signal at g=2.002 is typical of
organic radicals (Fig. S8). The EPR signal was persistent even in
The precise charge on the 2D net of Eu(dfdmt)
2
air, which is consistent with the general stability of thiyl
1
9
2+
3+
6
3+
radicals. EPR also discriminates Eu from Eu : the 4f Eu ion
7
is diamagnetic with the F
silent, while the 4f , paramagnetic Eu is EPR-active (e.g., with
g ≈ 2.0, 2.8, 3.4, 4.5 and 6.0 observed of Eu in glassy systems ).
In our case, the EPR features of g ≈ 2.03, 2.8 and 4.3 can be
ascribed to Eu , with the split peak around g = 2.0 also
indicating the contribution from the organic radicals.
0
a ground state, and is therefore EPR
2
0
7
2+
2
+
21
2
+ 22
The molar magnetic susceptibility (χ
field of 1000 Oe and in the 2-300 K range; with χ
plotted against temperature in Fig. S9) features χ
M
) data (at an applied
―1
T and 휒
T = 2.1 cm
M
푀
3
M
-1
3
-1
mol K at 300 K, slightly greater than the value of 1.5 cm mol
K for a Eu(III) ion calculated from the Van Vleck equation
2
3
allowing for population of the excited state. The higher
observed χ T at 300 K can be ascribed to the contribution from
organic radicals. The χ T value decreases continuously at
M
M
Fig. 1 Single crystal structure of Eu-dfdmt: a) Coordination environment of Eu; b) a 2D
lowering temperature, and approaches zero at 2K. The
observed graphs (Fig. S9) can be modelled by the depopulation
+
layer and the imbedded [(CH
the layered structure (along the a axis), showing also the intercalated NH
3
)
2
NH
2
] guests viewed along the c axis; c) a side view of
+
4
and water
of Stark levels for a single Eu(III) ion, which takes a J = 0 ground
molecules (H atoms were omitted for clarity.)
7
state ( F
0 M
) at 2 K to render χ T close to zero. With thermally
less defined, mainly because dfdmt is partially oxidized into
populated excited states, the magnetic susceptibility follows
the Curie-Weiss law in the temperature range of 180-300 K.
3
-
radicals (e.g., as the thiyl dfdmt· ; Scheme 1) as revealed in
electron paramagnetic resonance (EPR) and other studies. The
degree of linker oxidation is hard to quantify by SCXRD, e.g., by
3+
Alternatively, the graphs are also in accord with a single Eu
center in strong antiferromagnetic coupling with two free
+
+
charge balancing from the NH
4
/NH
3
and (CH
) NH
3 2 2
cations
3+
radicals (S = ½), i.e., (RS·)Eu (·SR), with the spin-orbit coupling
constant modeled to be 370(6) cm , and θ = -104 (2) K in the
Curie-Weiss expression. Structurally, the isolated Eu center
(
formed from acetonitrile and DMF hydrolysis), as the data
-1
generally do not locate the light H atoms. Elemental analysis
results (i.e., C 26.49, H 3.09, N 8.55, S 15.52%) also lacks the
precision to pinpoint the degree of protonation. The fitting
3+
-
3+
corresponds to a (RS )
4
Eu coordination node (Scheme 1) with
four thiolate ligands, while the second magnetic model of
7
·
5
·
2
formula Eu(dfdmt) ·(CH
) NH
3 2 2
3
NH
4
3
3
NH ·H
2
O (calculated C
3+
-
3+
(
2 2
RS·)Eu (·SR) corresponds to a (RS ) (RS·) Eu node containing
2
| J. Name., 2012, 00, 1-3
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Fig. 3 A diffuse reflectance spectrum (a), an I-V voltammetric curve based on left-
right surfaces at room temperature (b, inset: photograph of a single crystal, scale bar:
Fig. 2 Powder X-ray diffraction patterns (Cu Kα, λ = 1.5418 Å) of Eu-dfdmt: a)
calculated from the single crystal structure; b) measured from a fresh powder sample
at room temperature; c) from a powder exposed in air for one month.
1
mm), and at different temperatures (c), and the Arrhenius plot with linear fitting
(d) for Eu-dfdmt (with a formally fitted activation energy of 0.25 eV).
two neutral thiyl RS· radicals and two thiolate anions (Scheme
-
1
). The 7:5 RS /RS· ratio (e.g., as found above by XPS) in the Eu-
-
3+
-
3+
dfdmt solid suggests that the (RS )
nodes exist in 1:5 ratio to fit the magnetic data.
Together with the carboxylate donors, the two
anionic nodes can be
4 2 2
Eu and (RS ) (RS·) Eu
O
5
-
3-
corresponding EuO
S
4 4
4 4
and EuO S
formally deduced [even though at room temperature (rt) the
charges are likely averaged out in the 2D net], to match the
7
·
5
·
charge-balanced formula Eu(dfdmt)
2
·(CH
) NH
3 2 2
3
NH
4
3
NH
3
·H
2
O determined above. As shown Figs. 1b and 1c, the
+
organic cations (CH
) NH
3 2 2
are located in the cavities of the
coordination layer, while the interlayer space is filled by the
+
NH
4
/NH
3
and H
2
O species, further stabilizing the anionic host
sorption test (77 K)
via electrostatics/H-bonds (Table S2). A N
2
on a sample activated at 100 °C indicated no porosity (Fig. S11),
consistent with the compact X-ray crystal structure.
Powder X-ray diffraction (PXRD) indicates a pure crystalline
phase for the air-stable Eu-dfdmt solid (Fig. 2).
Thermogravimetric analysis (TGA) found a steep weight loss (ca
Fig. 4 An AFM image (a) and height profile (b) of a nanosheet of Eu-dfdmt, TEM and
HRTEM images under different resolutions (c and d), periodic lattice fringes found in
panel d (e), and electron diffraction spots of corresponding fast-Fourier-transform
(FFT) pattern (f) for nanosheets at 300 kV.
1
6%; between 235 and 270 °C) attributable to the departure of
MOF nanosheets offer advantages of high aspect ratio, large
surface area and numerous exposed active sites . Notably, Eu-
dfdmt can be exfoliated into ultrathin and few-layer nanosheets
1
5
one dimethylamine, four ammonia and one water molecules
from the formula Eu(dfdmt)
7
·
5
3
NH
3
3 2
· NH ·H O
2
·(CH
) NH
3 2 2
4
(
Fig. 4) by simple ball-milling. Atomic force microscopy (AFM)
(calcd. 16.1%; Fig. S12).
height profile diagrams of two randomly selected nanosheets
indicate the respective thicknesses to be 5.0 and 6.6 nm (Fig. 4b
and Fig. S14): i.e., those of 6-8 layers (a single layer being 0.84
nm thick; Fig. 1). The lateral dimensions feature 324 and 476 nm,
highlighting the ultrathin morphology and high aspect ratios.
TEM and HRTEM (high-resolution transmission electron
Diffuse reflection measurement reveals a small band gap of
2
4
1
.31ꢀeV (946 nm), as per the tangent method (Fig. 3a). The
electrical conductivity was measured by the two-probe method
on a single crystal (rectangular block: 1.31 × 0.75 × 0.32 mm). At
rt, the I-V curve (from -5 to 5 V) in the left-right direction (in
plane of the 2D net) indicates a conductivity [σ=L/(R·S)] of 4.56 microscopy) images reveal translucent, crystalline thin
-6
-1
×
10 S m (Fig. 3b), while lower conductivity was found along morphology (Figs. 4c and 4d), with distinct lattice fringes (Fig.
the top-down direction (through planes of the 2D net; Fig. S13): 4e) corresponding to d031 (0.380 nm), and the fast-Fourier-
transform (FFT) pattern indexed to the Eu-dfdmt lattice (e.g.,
31, 012 and 02-1, Fig. 4f). PXRD and FT-IR (Figs. S15 and S16)
also verifies sample stability in the exfoliation process. The
-6
-1
1
.78 × 10 S m . The limited conductivity can be due to the non-
0
coplanar arrangement of the dfdmt linkers, which may hinder
in-plane charge transport. The stable currents at rt point to
electronic conduction, which is consistent with the negligible rt
ionic conductivity (below 10
measurement). The conductivity increases at rising
conductivity of nanosheets (2.36 × 10- S m at room
temperature, see Fig. S17) was found to be slightly lower than
the in-plane value of the bulk crystal, which might be partly due
to the structural defects and traps caused by exfoliation.
In conclusion, by taking our early design of thiol-carboxyl
6
-1
-12
-1
S m as per impedance
-5
-1
temperature (Fig. 3c), reaching 1.02 × 10 S m at 120 °C,
although ionic conductivity remains to be further studied under combination into the fluorination domain, we have discovered
these heated conditions.
the highly anionic 2D Eu-dfdmt network as a rare example of
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conjugated lanthanide-sulfur framework. The Eu ions were
found to be mostly trivalent (3+), but the small amount of Eu(II)
ions may likely impact electronic properties, e.g., to reduce the
band gap to generate the black color. In spite of the substantial
thiyl radical species (accounting for 42% of the S atoms), the
solid sample of Eu-dfdmt are stable in air. The electrical
Sakamoto, S. Tsuneyuki, S. Sasaki and H. Nishihara, ChemV.ieSwciA.,rt2ic0le19O,n1li0ne,
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-6
conductivity, however, appears to be quite modest (e.g., 10 –
-5
-1
1
alloying with various other transition metal ions may be needed
to improve the electronic properties.
This work was funded by the National Natural Science
Foundation of China (21871061, 21901046), Local Innovative
and Research Teams Project of Guangdong Pearl River Talents
Nakanishi, Y. Kitagawa, K. Yamaguchi, A. Kobayashi and H. Kitagawa,
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Project of Guangdong Province (2017A050506051), Science and
Technology Program of Guangzhou (201807010026). ZX
acknowledges an SRG-Fd (CityU 11304717) grant.
Dobeli, M. A. Husanu, I. Keren, T. Prokscha, A. Suter, C. Z. Chang, J. S.
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Conflicts of interest
There are no conflicts to declare.
1
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