Communication

Cite This: J. Am. Chem. Soc. 2019, 141, 6802−6806 pubs.acs.org/JACS

Porous Molecular Conductor: Electrochemical Fabrication of

Through-Space Conduction Pathways among Linear Coordination
Polymers
Liyuan Qu,† Hiroaki Iguchi,*,† Shinya Takaishi,† Faiza Habib,† Chanel F. Leong,‡
Deanna M. D’Alessandro,‡ Takefumi Yoshida,§ Hitoshi Abe,∥,⊥ Eiji Nishibori,#
and Masahiro Yamashita*,†,¶,⊗
†
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Sendai 980-8578, Japan
‡
School of Chemistry, The University of Sydney, Sydney, New South Wales 2006, Australia
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§
Electronic Functional Macromolecules Group, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki
305-0044, Japan
∥
Institute of Materials Structure Science High Energy Accelerator Research Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki
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305-0801, Japan
⊥
Department of Materials Structure Science, School of High Energy Accelerator Science, SOKENDAI (the Graduate University for
Advanced Studies), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan
#
Division of Physics, Faculty of Pure and Applied Sciences & Tsukuba Research Center for Energy Materials Science (TREMS),
University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
¶
Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
⊗
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
*
S Supporting Information

or ligands has been key to obtaining high σ,12−17 and

ABSTRACT: The first porous molecular conductor
(PMC), which exhibits porosity, a through-space
conduction pathway and rich charge carriers (electrons),
was prepared through electrocrystallization from Cd2+ and
N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxdiimide
(NDI-py). [Cd(NDI-py)(OH 2 ) 4](NO 3 ) 1.3±0.1·nDMA
(PMC-1) was assembled by π−π stacking among one-
dimensional (1D) linear coordination polymers. The NDI
cores were partially reduced into radical anions to form
conductive π-stacked columns, yielding (1.0−3.3) × 10−3
S cm−1 at room temperature. Moreover, the electrical
conductivity was significantly enhanced by removing the
solvent molecules from PMC-1, indicating that PMCs are
promising as molecule-responsive conductive materials.
particularly two-dimensional (2D) π-conjugated frame-
works6,18−20 show relatively high σ (>10 S cm−1). However,
the high covalent bonding character in the through-bond
approach makes it difficult to study their structures and
electronic states by single-crystal X-ray diffraction (SXRD)
analyses, especially in 2D π-conjugated frameworks. Moreover,
the design of the linkers providing the electron delocalization
has been confined to only a few systems such as dithiolate,12,18
semiquinonate,14 iminobenzene6,19,20 and azolate.16,17
Meanwhile, the through-space approach requires a relatively
rare π-stacked columnar structure of organic linkers suitable for
electron conduction.21,22 However, the σ of these MOFs is
generally moderate (up to the order of 10−3 S cm−1) despite
their high charge mobility.21a This indicates that developing
methodologies for increasing the carrier density is important in
order to increase σ. Recently, Kawano et al. reported the

M etal−organic frameworks (MOFs)1 or porous coordi-

nation polymers (PCPs)2 have recently been antici-
pated as a new group of electron-conductive porous materials3
that are promising materials as the basis for batteries4,5 and
supercapacitors5,6 among other energy storage and conversion
technologies.7 Essential to engendering electrical conductivity
(σ) in MOFs is to build charge transport pathways. To date,
the synthetic strategies used have been categorized as either
“through-bond” or “through-space”. The former approach is
common among charge transport in conductive coordination
polymers (CPs).8,9 Some of them exhibited a change of σ upon
desolvation.10,11 The field of electron-conductive MOFs has
more recently developed through the use of organic linkers. In
the through-bond approach, mixed valency in metal ions and/
formation of a conductive MOF with a π-stacked columnar
structure induced by a trace amount of radical species.23 The σ
was gradually enhanced from 10−6 to 10−1 S cm−1 over several
months by further oxidation in air. This result suggests that the
introduction of radical species can relatively quickly lead to π-
stacked columns with high carrier densities. Such rapid radical
generation and the formation of π-stacked conducting columns
is common in electrocrystallization of molecular conductors.24
Therefore, we propose a new electron-conductive porous
materials, named porous molecular conductors (PMCs),
created by the fusion of MOFs and molecular conductors.
Received: February 14, 2019
Published: April 17, 2019

© 2019 American Chemical Society 6802 DOI: 10.1021/jacs.9b01717

J. Am. Chem. Soc. 2019, 141, 6802−6806
Journal of the American Chemical Society Communication

The application of electrochemical reactions to the syntheses

of MOFs can provide not only high conductivity but also
various physical properties derived from molecular conductors.
Considering the opposite perspective, porosity can provide an
interface to control the electronic states and physical properties
of molecular conductors by chemical stimuli. These concepts
of PMCs open a new avenue for research in both electron-
conducive MOFs and molecular conductors. Herein, we report
the first PMC synthesized by the in situ electrochemical
reaction of an organic linker.
We focused on N,N′-di(4-pyridyl)-1,4,5,8-naphthalenetetra-
carboxdiimide (NDI-py) as an organic linker which is capable
of forming infinite π-stacked columnar architectures. The NDI
core is a well-known electron acceptor used in various fields in
chemistry.25 Its large π-conjugated plane and the ease of
modification at the core and imide-N sites are suitable for
preparing various molecular conductors. A few NDI-based
molecular conductors have already been reported,26 encourag-
ing us to use NDI-py in this study. To date, several MOFs with
mixed π-stacking between NDI-based ligands and donor
molecules have been reported.27,28 However, to the best of
our knowledge, a conductive MOF with π-stacked columns
consisting solely of NDI-based ligands has not reported.
In the present work, the electrocrystallization was carried out
by applying a constant direct current of 30 μA to a solution of
NDI-py and Cd(NO3)2·4H2O in N,N-dimethylacetamide
(DMA) at room temperature (RT). Rod-like dark brown
single crystals of [Cd(NDI-py)(OH2)4](NO3)x·nDMA (PMC-
1) were obtained from the cathode (PtIr alloy wire) after 2 Figure 1. Crystal structure of PMC-1 (space group P6222). (a)
days. The SXRD analysis revealed that PMC-1 crystallized as Thermal ellipsoid plot of the linear CP in PMC-1. The four water
molecules coordinating to the Cd2+ ion are disordered in eight
conglomerates with the hexagonal space groups P6222 and
positions. (b) The π-stacked NDI-py column projected along the c
P6422. [Cd(OH2)4]2+ ions are bridged by NDI-py ligands to axis. The pyridyl groups are oriented in 60° increments. (c) The
form linear CPs (Figure 1a). The NDI-py ligands form infinite columnar structure of NDI-py showing the interplanar distances. (d)
helical π-stacked columns along the crystallographic c axis Perspective view of PMC-1 along c axis. Yellow, Cd; blue, N; gray, C;
(Figure 1b,c), thus the linear CPs align along the a, b and a + b red, O.
axes (Figure 1d). The interplanar distance between the NDI-
py ligands is 3.18 Å, which is considerably shorter than those
(>3.3 Å) observed in typical NDI analogues,29 suggesting the discussed in the Supporting Information (Table S2). There-
presence of radical anion (NDI•−) species. However, the fore, the mean charge of NDI was calculated as −0.7 ± 0.1,
formula for PMC-1 found for the framework is [Cd(NDI- indicating that a part of the NDI-py ligand in PMC-1 was
py)(OH2)4], suggesting that the charge of NDI-py is −2 (i.e., reduced to its NDI•− state.
no NDI•− species). The above formula also conflicts with the The solid-state absorption spectra of PMC-1 and NDI-py
fact that a dianionic NDI2− state is very unstable under aerobic (Figure 2) indicate that the absorption bands above 3.0 eV
conditions. Therefore, some residual electron density in the correspond to the π−π* transition for the neutral NDI core.
pores, which is too dispersed to establish a meaningful The broad bands around 2.7 and 2.0 eV observed only in
molecular structure, should be assigned to the NO3− ions (and
some solvent molecules). Indeed, the infrared (IR) absorption
peak at 1383 cm−1 observed in PMC-1 (Figure S1) proves the
presence of NO3− ions.30 Therefore, a chemical formula for
PMC-1 of [Cd(NDI-py)(OH2)4](NO3)x·nDMA was tenta-
tively assigned.
To investigate the thermal stability of PMC-1, we performed
thermogravimetry (TG). As shown in Figure S2, gradual
weight loss started at RT due to the liberation of DMA and a
plateau was observed around 210 °C. To remove all DMA and
coordinated water molecules, PMC-1 was heated at 210 °C
under an N2 atmosphere for 30 min and then cooled to RT.
This solid readsorbed a small amount of water from the air to
afford the heated compound, [Cd(NDI-py)](NO3)x·mH2O
(PMC-1h). The absence of DMA was confirmed by the
disappearance of its signals from the NMR spectrum (Figure
S3). Finally, the number of NO3− ions was calculated as x = 1.3 Figure 2. Solid-state absorption spectra of NDI-py (orange) and
± 0.1 from the results of elemental analyses for PMC-1h, as PMC-1 (black) dispersed in KBr pellet.

6803 DOI: 10.1021/jacs.9b01717

J. Am. Chem. Soc. 2019, 141, 6802−6806
Journal of the American Chemical Society
PMC-1 can be assigned to the intramolecular transitions of the
NDI•− core according to previous reports.27a,31 Moreover,
PMC-1 shows other broad bands in the near-IR to IR region.
Disregarding the O−H stretching mode from water molecules
around 0.4 eV (3200 cm−1), a broad absorption band was
observed with a maximum at approximately 0.3 eV. This
transition can be assigned to charge transfer (CT) between
NDI•− and NDI0 cores in PMC-1. A very weak broad band
around 1 eV can also be regarded as CT between two NDI•−
cores. These bands in the near-IR to IR region only appear in
the presence of intermolecular interactions.32−34 In addition, a
sharp signal (g = 2.003) observed in the ESR spectrum
confirms the existence of NDI•− species (Figure S6).
The solid-state cyclic voltammogram of PMC-1 (Figure 3a)
showed the dependency of the redox states on the electrolyte.
Figure 3. (a) Cyclic voltammograms obtained at a scan rate of 100
mV/s for reduction of PMC-1-modified glassy carbon electrode in
contact with 0.1 M LiClO4 (black) and n-Bu4NPF6 (red) in CH3CN.
(b) Solid-state spectroelectrochemistry (SEC) in diffuse reflectance
mode, F(R), of PMC-1 in contact with 0.1 M LiBF4 in CH3CN. The
applied potential was scanned from 0 V (black) to −0.9 V (red). Gray
lines show the spectral transition.
The reduction of PMC-1 in 0.1 M LiClO4/CH3CN was
1/2 = −0.77
chemically reversible and its reduction potential (Ered
V vs Fc/Fc+) was comparable to the typical value for NDI/
NDI•− reduction,35 indicating that the remaining neutral NDI
cores are reduced. In contrast, the reduction in 0.1 M n-
Bu4NPF6/CH3CN was irreversible (Figure S7) and the current
was small. The reduction peak potential (Eredp ) in n-Bu4NPF6/
CH3CN (−1.12 V vs Fc/Fc+) is more negative than that in
LiClO4/CH3CN (−0.88 V vs Fc/Fc+). These results indicate
that the Li+ ions can readily enter the void space of PMC-1
under reduction, although the relatively bulky n-Bu4N+ ions are
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Communication
impeded from diffusion into the structure. This selectivity
supports the porosity of PMC-1. It is also suggested that the
NO3− ions remain in the void spaces probably close to the
framework during the reduction process. The areas of the
reduction and oxidation waves are approximately equal,
indicating that the companion oxidation process ceases at
the initial reduction state (−0.7 ± 0.1 e−).
To gain further insight into the redox processes, a solid state
spectroelectrochemical (SEC) measurement of PMC-1 was
performed under similar conditions to the cyclic voltammetry
(Figure 3b).32 Both bands for the radical species (2.7 and 2.0
eV) and for the CT between two NDI•− cores (1 eV) were
detected in the spectrum for the initial state (E = 0 V) owing
to the partially reduced NDI cores, in agreement with Figure 2.
Upon reduction, the intensity of these absorption bands
gradually increased and finally saturated at −0.9 V,
corresponding to the increase of NDI•− species. In the reverse
oxidation process, the intensity of these absorption bands
decreased and returned to their initial intensities at 0 V (Figure
S8), supporting the fact that oxidation does not proceed past
the initial reduction state of the NDI core. These results for the
SEC measurement are in good agreement with the electro-
chemical data (Figure 3a). The inactivity of the material
toward oxidation suggests that the initial amount of radical
species is necessary to maintain the well-packed columnar
structure of PMC-1.
A single crystal direct-current (DC) conductivity measure-
ment was conducted along the π-stacked columnar axis (c axis)
by using a two probe method (Figure S9). The σ measured at
300 K (σ300 K) of five crystals ranged from 1.0 × 10−3 to 3.3 ×
10−3 S cm−1 (Table S3). These values for σ300 K are
comparable to the most conductive NDI-based molecular
conductors.26a The σ increased with rising temperature,
revealing semiconducting behavior (Figure 4), whereas the
Figure 4. Temperature dependence of electrical conductivity (σ) of
single crystalline PMC-1 measured along the π-stacked column (filled,
black), in addition to pressed pellets of PMC-1 (hollow, gray) and
PMC-1h (hollow, red).
noninteger charge on the NDI cores and the crystallo-
graphically equal interplanar distances promise to induce
metallic conduction in PMC-1. This is likely due to charge
localization that occurs randomly in the π-stacked columns,
owing to the electrostatic interaction with NO3− ions
accommodated in the random sites of the pores.
DOI: 10.1021/jacs.9b01717
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Journal of the American Chemical Society
The removal of DMA molecules from the pores induced a
structural change and the broadening of peaks in the powder
X-ray diffraction (PXRD) pattern in PMC-1h (Figure S10). As
shown in the absorption spectrum of PMC-1h (Figure S11);
however, the radical and CT bands still exist. Unexpectedly,
the pressed pellet of PMC-1h showed a σ300 K of (1.2−3.7) ×
10−2 S cm−1, which is a 104 times higher than the σ300 K of the
PMC-1 pellet ((1.5−7.6) × 10−6 S cm−1) and higher than that
of the single crystal. The structure of PMC-1h can be
estimated from the isomorphic and more crystalline complex,
PMC-1s, which was prepared by soaking PMC-1 in toluene for
a week. The results of extended X-ray absorption fine structure
(EXAFS) (Figure S15) and high resolution PXRD measure-
ment (Figure S16) suggest that linear CPs were retained in
PMC-1s and PMC-1h but π-stacked structures were changed
to 2D-like packing modes,36 which can provide high carrier
mobility and low grain boundary resistivity compared with 1D
columnar structure (see the Supporting Information). The
enhancement of σ is likely due to this structural change.
In conclusion, we have demonstrated the electrochemical
synthesis of PMC-1, which shares features of both MOFs and
molecular conductors. The linear CPs formed face-to-face
helical π-stacked columns of NDI cores, yielding a through-
space conduction pathways. The removal of lattice DMA
molecules induced a structural change and an enhancement in
the conductivity, demonstrating that PMCs are promising as
molecule-responsive conductive materials, i.e., conductive soft
crystals.37 The chemical reduction method using hydrazine
monohydrate gave PMC-1 with numerous unisolable by-
products. Thus, we conclude that the electrochemical method
is an effective technique for fabricating PMCs as new
electroactive frameworks. The concepts of PMCs will stimulate
new researches in further functionalization of MOFs and in
postsynthetic control of electronic states of molecular
conductors.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.9b01717.
X-ray crystallographic information (CIF)
Additional experimental details for the synthesis and
characterization (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*h-iguchi@m.tohoku.ac.jp (H.I.)
*yamasita@agnus.chem.tohoku.ac.jp (M.Y.)
ORCID
Hiroaki Iguchi: 0000-0001-5368-3157
Shinya Takaishi: 0000-0002-6739-8119
Hitoshi Abe: 0000-0001-6970-3642
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We acknowledge Prof. Akutagawa and Dr. Hoshino at Tohoku
University for acquiring the ESR spectra. This work was
performed under the approval of the Photon Factory Program
Advisory Committee (Proposal No. 2018G083, beamline
NW2A and No. 2017P016, beamline NW10A). The
6805
Communication
synchrotron radiation experiments for PXRD were performed
at BL02B2 of SPring-8 (Proposal No. 2018B0074). This work
was partly supported by JSPS KAKENHI Grant Numbers
JP18H04498 (H.I.), JP18H04499 (E.N.) and JP18K14233
(H.I.), by the CASIO Science Promotion Foundation (H.I.),
by the Ogasawara Foundation for the Promotion of Science
and Engineering (H.I.), by the Australian Research Council
Grant FT170100283 (D.M.D.) and by the Program for
Interdisciplinary Research in Tohoku University Frontier
Research Institute for Interdisciplinary Sciences (H.I.). M.
Yamashita thanks the support by the 111 project (B18030)
from China.
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DOI: 10.1021/jacs.9b01717
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