Ueda (2014)
Ueda (2014)
Ueda (2014)
pubs.acs.org/JACS
The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581, Japan
Department of Physics, Faculty of Science, Toho University, Funabashi, Chiba 274-8510, Japan
Comprehensive Research Organization for Science and Society (CROSS), Tokai, Ibaraki 319-1106, Japan
CMRC and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK),
Tsukuba, Ibaraki 305-0801, Japan
INTRODUCTION
A hydrogen bond (H-bond) is one of the most fundamental
thermal orderdisorder behavior of the H-bonded proton
(or hydrogen atom), increases with increasing OO distance
and important noncovalent interactions in materials and thus (dOO).911 In particular, the signicant increase of Tc is observed
has played an essential role in chemistry, biology, physics, and when the H-bonded hydrogen is deuterated, in which the
all other molecular sciences, because of its inherent ability to increase in dOO by deuteration, i.e., the so-called geometric
form a wide variety of structures, depending on the constituent isotope eect12,13 or the Ubbelohde eect,14 is believed to play
elements, geometry, charge, temperature, states of matter, and an important role.911 Furthermore, the deuteration sometimes
so on.17 From the geometric viewpoint, the H-bond distance induces a new phase transition which is absent in the parent
or the interatomic distance between the participating heavy atoms hydrogen system.15,16 The origin of this so-called deuteration-
(oxygen, nitrogen, sulfur, halogen, etc.) is a particularly important induced phase transition has been discussed from both the
parameter. This is because, depending on that distance, the shape experimental geometric aspect17 and the theoretical aspect1820
of the potential curve or the dynamics of the proton (or hydrogen which takes into account the dierence in zero-point energy.
atom) in the H-bond is sensitively changed.8 For example, in
several isostructural series of OHO-type H-bonded dielectrics, Received: July 15, 2014
their phase transition temperature (Tc), which corresponds to Published: August 15, 2014
2014 American Chemical Society 12184 dx.doi.org/10.1021/ja507132m | J. Am. Chem. Soc. 2014, 136, 1218412192
Journal of the American Chemical Society Article
Figure 1. (a) Synthetic scheme of -H35 and -D. (b) Top and (c) side view of the H-bonded molecular unit in the crystal of -H and its molecular
arrangement (d) along the molecular long axis and (e) within the -type two-dimensional conducting layer. In (b), values represent the bond lengths
or interatomic distances. In (b), (c), the thermal ellipsoids are scaled to the 50% probability level. In (e), b1, b2, p, and q represent intermolecular
transfer integrals within and between the -dimer(s), respectively (b1 = 213 meV, b2 = 78 meV, p = 41 meV, q = 16 meV at 293 K and
b1 = 230 meV, b2 = 85 meV, p = 46 meV, q = 12 meV at 50 K).
Importantly, all of the above-mentioned interesting dielectric pro- organic -electron components.23,24 However, high pressure
perties are fundamentally attributable to the proton (or hydrogen (25 kbar) is required for the realization of the proton
atom) dynamics in the H-bond, and thus, conversely, the electron transferred state, and thus a detailed investigation has
electrons are not relevant to these dynamic properties. not been achieved. In addition, several kinds of possible candidates
Cooperative behavior between a proton (or a hydrogen were prepared;2534 however, such dynamic coupling phenom-
atom) and an electron has frequently been observed in a wide ena between H-bond dynamics and electrons in the solid state
variety of biological and chemical processes.21 For example, in have scarcely been observed to date.26,31
the photosynthetic reaction center, the electron is transported Recently, our group originally prepared an H-bonded-
by a sequential protonelectron transfer reaction through a molecular-unit-based purely organic conductor crystal,
p-benzoquinone derivative, plastoquinone.22 Importantly, in -H3(Cat-EDT-TTF)2 (abbreviated as -H)35 (Figure 1a), in
this reaction, the proton- and electron-accepting abilities of which two crystallographically equivalent catechol-fused
the -electronic benzoquinone molecule play a vital role. ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a
Furthermore, such cooperation between an H-bonded +0.5 charge are linked by a symmetric anionic [OHO]1-type
proton (or a hydrogen atom) and an electron is also observed strong H-bond (dOO = 2.486(5) at 293 K, dOO = 2.453(5) at
in molecular materials. Quinhydrone, the p-benzoquinone 50 K) (Figure 1b,c). Notably, the conductor -H is composed
hydroquinone organic 1:1 cocrystal, exhibits a cooperative only of this H-bonded neutral open-shell molecular unit, which
protonelectron transfer, based on the coupling of the charge- enabled the construction of an unprecedented packing structure
transfer interaction and H-bond dynamics between the two where the two-dimensional (so-called -type) -electron
12185 dx.doi.org/10.1021/ja507132m | J. Am. Chem. Soc. 2014, 136, 1218412192
Journal of the American Chemical Society Article
conducting layers are connected by the H-bonds (Figure 1d,e). the H-bonded molecular unit of -D and -H35 were taken from the
Thus, a signicant interplay between the H-bond dynamics and X-ray analysis data.
-electron is expected in this system. Here we report Electrical Resistivity. Electrical resistivity measurements of a single
crystal of -D were performed on a Physical Properties Measurement
unprecedented H-bond-dynamics-based switching of electrical
System (PPMS, Quantum Design) by the conventional four-probe
conductivity and magnetism in a deuterated analogue of this method using carbon paste and annealed Au wires ( = 10 m).
H-bonded purely organic conductor system, -D3(Cat-EDT- Magnetic Susceptibility. The magnetic susceptibility of a poly-
TTF)2 (abbreviated as -D, Figure 1a). Although the deuterated crystalline sample of -D was measured on a Quantum Design SQUID
and parent hydrogen systems, -D and -H, are isostructural magnetometer MPMS-XL in the temperature range 2300 K at the
paramagnetic semiconductors with a dimer-Mott-type electronic static eld of 1 T. The magnetic responses were corrected with the
structure at room temperature, only -D undergoes a phase blank data of the sample holder obtained separately. The diamagnetic
transition at 185 K, to change to a nonmagnetic insulator with contribution of the sample itself was estimated to be 3.73 104
a charge-ordered (CO) electronic structure. The X-ray crystal emu/mol from Pascals constants.
Raman Spectroscopy. The Raman spectra of a single crystal of
structure analysis demonstrates that this dramatic switching of -D and -H were measured on a Renishaw inVia Reex Raman
the -electronic structure and physical properties originates from microscope (excitation wavelength = 633 or 532 nm) at the Institute
deuterium transfer or displacement within the [ODO]1 for Molecular Science, Japan.
H-bond accompanied by electron transfer between the
H-bonded Cat-EDT-TTF -systems, proving that the H-bonded RESULTS AND DISCUSSION
deuterium dynamics and the conducting TTF -electron are
cooperatively coupled. Furthermore, the reason why this unique High-quality single crystals of the deuterated analogue -D were
phase transition occurs only in -D is qualitatively discussed in readily prepared from H2Cat-EDT-TTF, Hdonor,36 in a one-step
terms of the H/D isotope eect on the H-bond geometry and one-pot synthesis (Figure 1a): Applying a constant current
potential energy curve. (0.3 A, about 1 week) to Hdonor in a mixed solvent of PhCl
Figure 3. (a) Temperature dependence of relative X-ray reection intensity for three pairs of peaks from the high-temperature (HT) C2/c phase
(red colored) and low-temperature (LT) P1 phase (blue colored) in a single crystal of -D; (squares, (13, 3, 3), (3, 3, 8)), (triangles, (14, 4,
5), (4, 5, 9)), (circles, (10, 2, 3), (2, 3, 6)). (b) Chemical structures, (c) X-ray crystal structures, (d) electrostatic potential surfaces, and
(e) SOMO distributions of the H-bonded molecular unit in -D at 270 K (left column) and 50 K (right column). At 270 K, the terminal ethylene
groups are thermally disordered. Values in (c) are the bond lengths or interatomic distances. In (c), the thermal ellipsoids are scaled to the 50%
probability level. Theoretical calculations for (d) and (e) were performed at the UB3LYP/6-31G(d) level of theory and the ROB3LYP/6-31G(d)
level of theory, respectively. The molecular geometries used for the calculations were taken from the X-ray analysis data.
by the bond length analysis of the catechol moiety (Figure S4 molecular orbital (SOMO) are found on the Cat-EDT-TTF+0.94
in Supporting Information). Furthermore, density functional skeleton (Figure 3e right). In addition, we successfully observe
theory (DFT) calculations based on the X-ray structures the charge disproportionation behavior between the TTF
(Figure 3d,e) also support the occurrence of the charge dis- skeletons by single-crystal Raman measurements of -D and
proportionation between the H-bonded TTF skeletons. The -H (Figures S5, S6 in the Supporting Information). The
electrostatic potential surface at 50 K (Figure 3d right) illustrates temperature dependence suggests that the charge disproportio-
the presence of a more positively charged TTF skeleton (aqua- nated state in -D (+0.94 vs +0.06) is directly formed from the
to-blue-colored) and a less positively charged one (green-to- initial +0.5 oxidized state without passing through other
yellow-colored), which correspond to the experimental charge- intermediate states (e.g., +0.7 vs +0.3, etc.).
rich (+0.94) and charge-poor (+0.06) skeletons, respectively. Due to the above-mentioned intraunit charge disproportio-
Concurrently, almost all of the coecients of the singly occupied nation through the H-bond, the overall electronic structure of
12188 dx.doi.org/10.1021/ja507132m | J. Am. Chem. Soc. 2014, 136, 1218412192
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Figure 4. Crystal packing structures of -D. (a) Molecular arrangement of the Cat-EDT-TTF skeletons between the conducting layers at 50 K and
(b) within the conducting layer (left: 270 K, right: 50 K). Blue- and orange-colored molecules correspond to the charge-rich (+0.94) and charge-
poor (+0.06) Cat-TTF-skeletons, respectively. The parameters b1 and b2 in (b) represent intermolecular transfer integrals within and between the -
dimer(s), respectively (b1 = 218 meV, b2 = 79 meV at 270 K (left) and b1 = 335 meV, b2 = 79 meV at 50 K (right)).
-D in the LT phase is intrinsically dierent from that in the X = monovalent anion],4648 derived from the Coulomb
HT phase. At 50 K, as shown in Figure 4a,b, the charge-rich interactions between the BEDT-TTF molecules, i.e., the charge
(blue-colored) and -poor (orange-colored) Cat-EDT-TTF degree of freedom of -electrons. Therefore, the present system
skeletons are separately -dimerized with their neighboring is a truly new type of organic CO crystal in which the proton
cofacial Cat-EDT-TTF skeletons having the same valence, to degree of freedom plays a vital role.
form two kinds of -dimeric pairs, composed of the charge-rich Finally, let us discuss why this phase transition occurs not
skeletons or the charge-poor ones. These -dimers are stacked in the parent system -H but in the deuterated system -D.
two-dimensionally while maintaining the -type molecular We therefore focused on the structural dierence in the
arrangement, which results in a charge-ordered (CO) electronic geometry of the [OH(D)O]1 H-bond part of both the
structure (Figure 4b right) from a dimer-Mott state in the HT systems and calculated the potential energy curves as a function
phase (Figure 4b left). In this CO state, since the charge-rich of the distance between the O1O2 center position and the
TTF+0.94 skeleton is expected to have nearly one electron spin H-bonded hydrogen or deuterium atom, which moves linearly
(S = 1/2), as shown in the SOMO distribution map (Figure 3e between O1O2 (Figure 5). We note here that the calculations
right), a spin singlet should be formed within each charge-rich were performed on the basis of the X-ray structural data of
-dimer, which rationalizes the paramagneticnonmagnetic -H (293 and 50 K) and -D (270 and 50 K), in which the
transition in magnetic susceptibility (Figure 2b) as well as the deuterium atoms in -D were replaced with hydrogen atoms
semiconductorinsulator-like transition in resistivity (Figure 2a). to simply estimate the eect due to the geometric dierence:
Due to the spin-singlet formation, the interplanar distance The H/D quantum isotope eect relevant to the dierence in
within the charge-rich -dimer at 50 K (d = 3.343.37 ) is vibrational frequency was not taken into consideration in the
signicantly shortened from that within the original -dimer at present calculations. At high temperatures, both -H (Figure 5a,
270 K (d = 3.443.47 ) (Figure 4b), and accordingly the at 293 K) and -D (Figure 5c, at 270 K) provide a symmetric
transfer integral within the charge-rich -dimer (b1) at 50 K double-well potential curve, in which the energy barrier for
(331 meV) is greatly enhanced from that within the original hydrogen transfer is calculated to be 0.09 eV for -H and
one at 270 K (218 meV). Importantly, this CO state is obviously 0.14 eV for -D, respectively. On cooling down to 50 K, -H
triggered by the H-bonded deuterium transfer, followed still maintains the symmetric potential curve, in which the
by the charge disproportionation, thus which intrinsically diers barrier is lowered to 0.07 eV (Figure 5b). On the other hand,
in its origin from the typical CO state in (BEDT-TTF)2X the potential curve of -D desymmetrizes at 50 K with a much
salts [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, higher barrier (0.26 eV) (Figure 5d), as expected from the
12189 dx.doi.org/10.1021/ja507132m | J. Am. Chem. Soc. 2014, 136, 1218412192
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Figure 5. Theoretical potential energy curves for the intraunit H-bond part in -H and -D. The total energy proles (E, in eV) of -H at (a)
293 K and (b) 50 K and of -D at (c) 270 K and (d) 50 K as a function of the distance between the O1O2 center position and the H-bonded
proton, which moves linearly between O1O2. The calculations were performed at the UB3LYP/6-31G(d) level of theory by using the X-ray
structural data with changing the H-bonded hydrogen atom position. In these calculations, the deuterium atoms in -D were replaced with hydrogen
atoms: The H/D quantum isotope eect relevant to the dierence in zero-point energy was not taken into consideration. In the inset, each
H-bonded molecular unit structure in the crystal is shown. The thermal ellipsoids are scaled to the 50% probability level.
asymmetric O0.06DO0.94 H-bond structure. On the basis of much higher than that in -H at 50 K. (4) In addition, due to its
these calculated results relevant to the geometric dierence, the lower zero-point energy resulting from the heavier atomic mass,
presence or absence of the phase transition in the -H and -D the deuterium at low temperatures would be no longer capable
systems can be qualitatively interpreted as follows: (1) At high of jumping over the energy barrier, to localize at one minimum
temperatures, due to the short O1O2 distance (dO1O2) site such as O0.06DO0.94, which thus triggers the electron
(2.486(5) for -H and 2.501(2) for -D), the energy transfer and charge disproportionation between the intraunit TTF
barrier in each system is low enough to allow the rapid hydrogen skeletons. This discussion suggests that, in the present system,
or deuterium transfer between the two potential minima by the dO1O2 dierence due to the H/D substitution, that is, the
thermal activation, resulting in the formation of the H- or geometric isotope eect, is one of the key factors determining
D-centered [OH(D)O]1 structure as a time-averaged X-ray whether the phase transition occurs or not. According to the
structure. (2) At 50 K, the dO1O2 in -H decreases to 2.453(5) literature,12,13 the elongation of dOO due to this eect is the most
by shrinking of the unit cell and thus the energy barrier is further remarkable when the dOO is around 2.5 . Actually, the dOO of the
lowered, which enables the hydrogen to continue to transfer present systems -H and -D (2.452.50 ) are in a similar
between the two minima by zero-point vibration or tunneling, to range, which leads to the large elongation in dOO (0.015 at 270
keep the symmetric [OHO]1 structure even at low temp- 293 K and 0.048 at 50 K) upon deuteration. For further detailed
eratures. (3) On the other hand, the dO1O2 in -D at 50 K understanding of this isotope eect, a sophisticated quantum
(2.501(3) ) is almost unchanged from that at 270 K (2.501(2) chemical calculation on the potential energy curve, in which the
) and is signicantly longer than that of -H at 50 K (2.453(5) dierence in the quantum nature of these isotopes is taken into
), which is indicative that the energy barrier in -D at 50 K is consideration,1820,49,50 is needed and is currently underway.
12190 dx.doi.org/10.1021/ja507132m | J. Am. Chem. Soc. 2014, 136, 1218412192
Journal of the American Chemical Society
Article
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