High charge mobility in a tetrathiafulvalene-based microporous metal-organic framework

Article abstract of DOI:10.1021/ja3059827

The tetratopic ligand tetrathiafulvalene-tetrabenzoate (H₄TTFTB) is used to synthesize Zn₂(TTFTB), a new metal-organic framework that contains columnar stacks of tetrathiafulvalene and benzoate-lined infinite one-dimensional channels. The new MOF remains porous upon desolvation and exhibits charge mobility commensurate with some of the best organic semiconductors, confirmed by flash-photolysis-time-resolved microwave conductivity measurements. Zn₂(TTFTB) represents the first example of a permanently porous MOF with high charge mobility and may inspire further exploration of the electronic properties of these materials.

Full text of DOI:10.1021/ja3059827

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Communication
High Charge Mobility in a Tetrathiafulvalene-
Based Microporous Metal-Organic Framework
Tarun Chandru Narayan, Tomoyo Miyakai, Shu Seki, and Mircea Dinca
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja3059827 • Publication Date (Web): 24 Jul 2012
Downloaded from http://pubs.acs.org on July 25, 2012
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High Charge Mobility in a Tetrathiafulvalene-Based Mi-
croporous Metal-Organic Framework
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Tarun C. Narayan,† Tomoyo Miyakai,‡ Shu Seki,‡ and Mircea Dincă†*
†Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA
‡Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565ꢀ0871, Japan
Supporting Information Placeholder
cyanines, or triphenylenes define microporous structures with
The
tetratopic
ligand
tetrathiafulvaleneꢀtetrabenzoate
high photoconductivity and/or charge mobility.23 28 We sought
–
(H4TTFTB) is used to synthesize Zn2(TTFTB), a new metalꢀ
organic framework that contains columnar stacks of tetrathiaꢀ
fulvalene and benzoateꢀlined infinite oneꢀdimensional chanꢀ
nels. The new MOF remains porous upon desolvation and
exhibits charge mobility commensurate with some of the best
organic semiconductors, confirmed by flashꢀphotolysisꢀtimeꢀ
resolved microwave conductivity measurements. Zn2(TTFTB)
represents the first example of a permanently porous MOF
with high charge mobility and may inspire further exploration
of the electronic properties of these materials.
to apply a similar strategy to design MOFs with high charge
mobility. In doing so, we focused on TTF as a building block,
hoping that its high propensity to πꢀstack would balance well
with the stronger driving force of the metalꢀligand bond forꢀ
mation, thereby enforcing the construction of a material that
exhibits both porosity and a pathway for efficient charge
transport. Although there have been attempts to control the
supramolecular structure of TTFꢀbased materials while retainꢀ
ing conductivity, such as through NꢁꢁꢁI n→σ* interactions,29
coordination to metal ions through thioalkyl groups,30 and
carboxylates directly appended onto the TTF core,31 33 none
–
High surface area conductive materials are poised to transꢀ
form the energy landscape in the near future. Microporous
conductive ceramics and activated carbons have become the
have resulted in permanently porous materials. Herein we
show that a TTFꢀbased ligand containing benzoate spacers
generates a zincꢀbased MOF that exhibits both columnar
stacks of TTF and permanent pores lined by benzoate linkers.
The material displays charge mobility of a magnitude that
matches some of the best conductive organic polymers, as
determined by flash photolysisꢀtime resolved microwave conꢀ
ductivity (FPꢀTRMC). To our knowledge, this is the first
measurement of the intrinsic charge mobility in a permanently
porous MOF, and sets a standard that should encourage a susꢀ
tained research effort in this area.
3
norm in high temperature fuel cells and supercapacitors,1
–
while porous chalcogenide semiconductors and conductive
polymers are attractive targets for applications in electrocatalꢀ
ysis, separation, and sensing technologies.4 6 One class of maꢀ
–
terials with a great impact potential in this area is metalꢀ
organic frameworks (MOFs). These have high intrinsic porosiꢀ
ty that has led to applications in gas separation and storage
among others,7 9 but typically exhibit very low electronic conꢀ
–
The ligand tetrathiafulvaleneꢀtetrabenzoate (H4TTFTB) was
ductivity, which drastically impairs their utility as high surface
area conductors. The low conductivity of porous MOFs is not
surprising: they are usually made from hard metal ions conꢀ
nected by redoxꢀinactive organic ligands; this combination
does not provide a good conjugation pathway for charge
transport. As such, one of the most challenging and potentially
rewarding endeavors in this rapidly expanding field is to synꢀ
thesize porous frameworks that show good charge mobility
and conductivity.10
Scheme 1. Synthesis of H4TTFTB.
One means to address this challenge is to use softer, sulfurꢀ
based bridging ligands that form more covalent interactions
with the metal ions. For instance, diꢀ and tetraꢀthiobenzenes
were known to form conductive nonꢀporous coordination polꢀ
synthesized in two steps through a palladiumꢀcatalyzed cross
coupling between TTF and ethylꢀ4ꢀbromobenzoate34 followed
by saponification35 (see Scheme 1). Treatment of a solution of
ymers11 14 and served as inspiration for the only two examples
–
H4TTFTB in 3:1 DMF/EtOH with
a
solution of
Zn(NO3)2ꢁxH2O in 1:1 EtOH/H2O followed by heating at 75°C
for two days afforded the [Zn2TTFTB(H2O)2]⋅H2O⋅2DMF (1)
as dark red needles.
of permanently porous and electronically conductive
MOFs.15,16 An alternative to engineering throughꢀbond charge
delocalization17,18 is to employ πꢀstacks of electroactive moleꢀ
cules as the charge transport pathways. Most famously exemꢀ
plified by charge transfer salts such as tetrathiafulvaleneꢀ
tetracyanoquinodimethane (TTFꢀTCNQ),19,20 πꢀstacked moꢀ
lecular crystals can exhibit metallic conductivity and even
superconductivity.21,22 They inspired the development of elecꢀ
troactive covalentꢀorganic frameworks (COFs), wherein
stacked layers of flat π molecules such as porphyrins, phthaloꢀ
Xꢀray diffraction analysis of a single crystal of 1 revealed a
structure comprised of infinite helical chains of cornerꢀsharing
pseudoꢀoctahedra joined together by helical stacks of TTFTB4‾
linkers (see Figure 1). Compound 1 crystallizes in the space
group P65 with a racemic twinning domain. The 65 screw axis
bisects the central ethylene unit of the TTF core of TTFTB4‾,
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Figure 2. Isotherm for the adsorption of N2 in 1 at 77 K. The inset
shows the powder Xꢀray diffraction patterns of asꢀsynthesized 1
(black), simulated 1 (red), and desolvated 1 (blue).
one relatively close intermolecular SꢁꢁꢁS contact of 3.803(2) Å
is found between neighboring TTF moieties in 1. This value is
similar to the range of intermolecular SꢁꢁꢁS distances found in
39
TTFꢀTCNQ and other conductive chargeꢀtransfer salts,36
–
and it encouraged us to further investigate the potential for
charge mobility in 1.
Thermogravimetric analysis (TGA) of 1, shown in Figure
S1, exhibits a sharp mass loss of 28.3 % between 100 °C and
140 °C, which agrees well with the 28.2 % mass loss expected
for the elimination of 3.5 guest DMF molecules and coordiꢀ
nated water. Importantly, TGA suggested that 1 exhibits a
large plateau of thermal stability above 180 °C until the final
decomposition upwards of 400 °C. Evacuation of 1 was acꢀ
cordingly performed by heating asꢀsynthesized material at
200°C and 4 mtorr for 12 hours. Its crystallinity and identity
were confirmed by powder Xꢀray diffraction (Figure 2, inset)
and elemental analysis, respectively, which indicated that the
structure is maintained upon evacuation and exposure to air
and that indeed all solvent molecules are removed. Upon
desolvation, 1 absorbs ~170 cm3/g of N2 at 77 K and displays
a Type I isotherm, confirming its microporous nature (see
Figure 2). A BET analysis of the isotherm data revealed a
permanently porous structure with an apparent surface area of
662 m2/g and confirmed 1 as the first crystalline TTFꢀbased
material with intrinsic microporosity. Analysis of the N2 isoꢀ
therm data using the Tarazona nonꢀlocal density functional
theory40 also revealed a narrow pore size distribution centered
around 6 Å, in agreement with the pore size expected from a
space filling model of 1.
Figure 1. Portions of the crystal structure of 1: (a) the infiꢀ
nite helical Znꢀcarboxylate chains, (b) a side view of a helical
TTF stack with a depiction of the shortest intermolecular
S⋅⋅⋅S contact, and (c) a view of the benzoateꢀlined infinite
pores down the c axis. Orange, yellow, red, and grey spheres
represent Zn, S, O, and C atoms, respectively. H atoms and
water molecules in (b) were omitted for clarity.
such that adjacent TTF units are rotated by 60° relative to one
another and translated by 3.47 Å in the c direction. The two
dithiole rings in each TTF core are slightly twisted around the
central ethylene bond to give a dihedral angle of 2.32°. The
phenyl rings also exhibit a significant torsion with respect to
the TTF core, defining dihedral angles ranging from 40° to 52°
with the latter. Together with the helical metalꢀcarboxylate
chains that run roughly perpendicular to the TTF cores, the
benzoate groups delineate cylindrical pores with a van der
Waals diameter of ~5 Å. Finally, the infinite metalꢀ
carboxylate chains are built from two crystallographically
independent Zn atoms, each of which exhibits a pseudoꢀ
octahedral coordination sphere of six oxygen atoms pertaining
to carboxylates in one case and four carboxylates and two cisꢀ
oriented water molecules in the other case. Importantly, altꢀ
hough the TTF cores are not perpendicular to the screw axis,
Interestingly, an EPR spectrum of asꢀsynthesized 1, shown
in Figure S2, displayed a sharp signal at g = 2.006 characterisꢀ
tic of organicꢀbased radicals, and suggested that TTF cores in
1 are at least partially oxidized during the MOF synthesis and
that 1 is already partially doped in its asꢀsynthesized form. To
confirm that the radical character of 1 is centered on the TTF
moieties, the free ligand H4TTFTB was oxidized with I2 in
ethanol and the product displayed an EPR signal centered at g
= 2.006 as well. Encouraged by the inherent partial doping of
1 and by the relatively short SꢁꢁꢁS distances between neighborꢀ
ing TTF cores, we sought to investigate the conductive properꢀ
ties of this MOF. Because of the anisotropic structure of 1, we
expected that its bulk conductivity would be greatly affected
not just by grain boundary resistances, but also by the highly
randomized orientation of individual grains within a pellet or a
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film. Low bulk conductivity values defined by an average of
1
2
the conductivity in all three directions are well documented in
chargeꢀtransfer salts and other oneꢀdimensional conductors.41
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9
To eliminate anisotropy effects in our electrical measureꢀ
ments, we explored the conductivity of asꢀsynthesized 1 using
FPꢀTRMC. This technique allows the measurement of charge
mobility on the multiꢀnanometer length scale, much smaller
than the size of an individual grain or crystallite, and is thereꢀ
fore indicative of the intrinsic charge mobility of a given mateꢀ
rial.42,43 The technique effectively eliminates almost all of the
perturbations resulting from impurities, grain boundaries, elecꢀ
trode contacts and, most importantly, the directionality of
charge transport, whose influences are unavoidable in other
configurations such as pressed pellets and fieldꢀeffect transisꢀ
tors (FETs). FPꢀTRMC measurements were carried out in
ambient conditions on films made from 1 and PMMA (40/60
wt%). Samples were pulsed with 355 nm light, and the charge
carrier generation efficiency was obtained by a timeꢀofꢀflight
(TOF) transient current integration. The FPꢀTRMC profiles for
1 and a similar film made from H4TTFTB, both shown in Figꢀ
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ure 3a, display maximum values of
φΣ
ꢀ
of 3 × 10ꢀ5 and 9 × 10ꢀ
is the photocarrier generation
is the sum of the generated charge carrier mobiliꢀ
ties for both electrons and holes. The TOF current transients,
shown in Figure 3b, give
values of 4 × 10ꢀ3 and 2 × 10ꢀ4 for
H4TTFTB and 1, respectively. Because of the higher value of
in H4TTFTB, its current transient response could be verified
6
cm2/V⋅s, respectively, where
φ
yield and Σ
ꢀ
φ
Figure 3. (a) Conductivity transients observed by FPꢀTRMC upon
excitation at 355 nm with 6.5
1015 cmꢀ2 photons per pulse for 1
×
φ
(black trace) and H4TTFTB (red trace); (b) photocurrent transiꢀ
ents observed for 20ꢀ26 ꢀm thick solid films of materials in
PMMA matrices sandwiched between Auꢀsemitransparent and Al
electrodes. The transients were observed with a terminate reꢀ
using transient absorption measurements, an entirely nonꢀ
contact technique. Transient absorption spectra of H4TTFTB
dispersed in PMMA matrices and the corresponding kinetic
trace observed at 650 nm (1.9 eV) are shown in Figure S10.
Notably, this band is redꢀshifted from that observed for an
isolated TTF radical cation (2.17 eV), but blueꢀshifted relative
to that expected for a mixedꢀvalent TTF radical cation dimer
(1.69 eV),44,45 suggesting increased delocalization over neighꢀ
sistance of 10 kꢁ under applied bias at 1.2 – 1.5
×
104 V/cm.
these values, the minimum charge mobility necessary for treatꢀ
ing a system with a band model is 0.3 cm2/Vꢁs.50 This is only
slightly larger than the mobility value found in 1, suggesting
that our system can indeed be described as partially delocalꢀ
ized. This analysis also suggests that if the molecular overlap
between neighboring TTF cores can be engineered to either
increase the number of SꢁꢁꢁS contacts or shorten the length of
the contacts, MOFs with even higher charge mobility may be
accessible.
boring TTF cores in H4TTFTB. Most importantly, the
φ value
for H4TTFTB obtained by transient absorption measurements,
2.5 × 10ꢀ3, agrees well with that obtained from the TOF measꢀ
urements and suggests that holes are the major carriers in
H4TTFTB and, by analogy, in 1.
Combined, the FPꢀTRMC and TOF current transient measꢀ
urements reveal an outstanding intrinsic charge mobility of 0.2
cm2/V⋅s for 1. This value is two orders of magnitude higher
than that found for H4TTFTB, and is in line with values found
for highlyꢀoriented porphyrin and phthalocyanineꢀbased
In summary, we have shown that the use of a benzoateꢀ
extended TTF core leads to a permanently porous MOF that
shows very high intrinsic charge mobility within the class of
organicꢀbased conductors. Many challenges must be overcome
before such materials will be implemented in functional elecꢀ
tronic devices, not least of which is their processing as orientꢀ
ed thin films for interfacing with electrodes.51,52 Nevertheless,
these results demonstrate that MOFs are amenable to designs
that promote good charge transfer among the individual buildꢀ
ing blocks. We hope that this study will inspire the exploration
of the electronic properties of MOFs, which have received
comparatively less attention than more traditional applications
such as gas storage and separation.
COFs.23,24,26 28 Most remarkably, the charge mobility in 1 is
–
higher than those found for common organic conductors such
as some polyphenylenevinylenes (
ꢀ
= 0.01 – 0.1 cm2/V⋅s)46
and polythiophenes (
ꢀ
= 0.015 – 0.075 cm2/V⋅s)47 measured
by the same technique. We note also that even polythiophenes
used in organic photovoltaic devices, such as poly(3ꢀ
hexylthiophene)
and
poly(2,5ꢀbis(3ꢀalkylthiophenꢀ2ꢀ
yl)thieno[3,2ꢀb]thiophene have fieldꢀeffect (bulk) mobilities of
approximately 0.1 and 0.2ꢀ0.6 cm2/Vꢁs, respectively.48,49
ASSOCIATED CONTENT
It is stimulating to discuss the nature of the charge delocaliꢀ
zation in 1, which displays high charge mobility despite its
unusual and lessꢀthanꢀideal TTF stacking sequence that allows
only one relevant intermolecular SꢁꢁꢁS contact. To test whether
a band model is an appropriate description of the electronic
structure of 1, one can apply the energyꢀtime uncertainty prinꢀ
Supporting Information. Experimental details, table of Xꢀray
refinement details, TGA trace, EPR spectra, additional graphs
from the isotherm data, NMR and transient absorption spectra of
H4TTFTB, and an ORTEP representation of a portion of the strucꢀ
ture of 1. This material is available free of charge via the Internet
at http://pubs.acs.org.
ciple by assuming a typical electronꢀlattice scattering time of
τ
= 10ꢀ14 s and a spacing of 3.81 Å between components. Using
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mdinca@mit.edu
ACKNOWLEDGMENT
This work was supported by the U.S. Department of Energy, Ofꢀ
fice of Science, Office of Basic Energy Sciences under Award
Number DEꢀSC0006937. Grants from the NSF provided instruꢀ
ment support to the DCIF at MIT (CHEꢀ9808061, DBIꢀ9729592).
This work made use of the MRSEC Shared Experimental Faciliꢀ
ties at MIT, supported in part by the NSF under award number
DMRꢀ0819762. We thank Dr. N. Shustova for assistance with the
Xꢀray data analysis.
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Figure 1. X-ray crystal structure of compound 1.
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Figure 2. N2 adsorption isotherm and powder X-ray diffraction pattern of Compound 1.
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Figure 3. Conductivity and photocurrent transients for compound 1 obtained by FP-TRMC measurements.
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