ARTICLE pubs.acs.org/crystal
Three-Dimensional Robust Porous Coordination Polymer with Schiff Base Site on the Pore Wall: Synthesis, Single-Crystal-to-Single-Crystal Reversibility, and Selective CO2 Adsorption Rajdip Dey,† Ritesh Haldar,§ Tapas Kumar Maji,*,§ and Debajyoti Ghoshal*,† †
Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700 032, India Molecular Materials Laboratory, Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560 064, India
§
bS Supporting Information ABSTRACT: A three-dimensional (3D) robust porous coordination polymer, {[Cu(azpy)(glut)](H2O)2}n (1) (azpy = N,N0 -bis-pyridin-4-ylmethylene-hydrazine, glut = glutarate), has been synthesized and structurally characterized. Single crystal X-ray diffraction analysis reveals that each of paddle-wheel Cu2(CO2)4 units is connected with glutarates in the crystallographic bc plane to form a two-dimensional (2D) sheet which is pillared by an azpy linker to afford a 3D porous framework. Controlled heating of the as-synthesized crystal 1 at ∼150 °C under reduced pressure causes a color change of {[Cu(azpy)(glut)]}n (1a) from deep green to light green. The structure determination of the dehydrated compound shows the same framework structure as that of {[Cu(azpy)(glut)](H2O)2}n (1) with the only difference of the nonexistence of lattice water molecules resulting in a large void in the framework. The dehydrated light green crystal 1a regenerates the virgin as-synthesized crystal 1 with the formula of {[Cu(azpy)(glut)](H2O)2}n upon exposure to water vapor (1a), suggesting complete reversibility upon dehydration and rehydration. Dehydrated compound 1a shows remarkable CO2 selectivity over N2, a typical type I profile with MeOH and EtOH, and gated adsorption behavior with H2O. The selectivity in gas uptake and interesting vapor adsorption profiles was correlated with the polarity of the pore surface in 1a to the corresponding adsorbates molecules.
’ INTRODUCTION Robust metalorganic frameworks (MOFs), having the coordination space in terms of pores or channels, has received extensive attention in the past decade due to its potential application in several areas.1 The study of porous metalorganic frameworks or precisely porous coordination polymers (PCPs)2 is quite ubiquitous nowadays, due to their extensive applications in the field of heterogeneous catalysis,3 gas storage,4 separation5 and ion exchange,6 and sensing applications.7 Construction methodology of functional porous coordination polymers have different ways of accomplishment; for example, the metal ion geometry, binding mode, and stability of the organic struts are keys to obtain a rigid and robust framework. There are two popular ways to functionalize channel surfaces: one is the control of coordinatively unsaturated metal centers,8 that is, tuning the geometry of node,1c,d and the other is the introduction of functional organic sites in the linker.9 The last one is very important because by this way, the active site of catalysts can be functionalized in the pore wall to make it useful in heterogeneous catalysis. The fabrication of the guest accessible functional organic sites on the pore surface is a very challenging task as these functional organic groups tend to coordinate metal ions through a self-assembly process resulting in a framework r 2011 American Chemical Society
where the functional organic sites may become completely nonaccessible.3b,10 The successful design of functional organic sites in the linker can be very useful to fabricate an acid/base catalytic pore.11 There are a variety of organic functional groups that can serve as active acid/base sites in the wall of the pore. In addition to that, such functionalities are also important for selective adsorption. In fact, in recent years selective CO2 adsorption has been one of the major areas of research12 due to the uncontrollable rise of the atmospheric CO2 concentration level which is one of the primary environmental concerns of the present age. On the other hand, adsorption of MeOH/EtOH has become important for their use in separation and purification.5 For the preparation of the porous coordination polymers using base type functional organic sites, here we wish to display the synthesis and structure of a robust porous coordination polymer, where a Schiff base site is affixed on the pore wall. Several selective guest-adsorbing MOFs with acidic functional groups in their channels have been reported so far, but the examples with base functionality are quite rare.13 Received: April 13, 2011 Revised: August 1, 2011 Published: August 03, 2011 3905
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Scheme 1
Here, we report synthesis, reversible single-crystal-to-singlecrystal structural transformation of a 3D robust porous framework, {[Cu(azpy)(glut)](H2O)2}n (1) (where azpy = N,N0 -bispyridin-4-ylmethylene-hydrazine; glut = glutarate), where the pore surfaces are decorated with the CHdN- groups. Controlled heating of 1 at 150 °C leads to the dehydrated species {[Cu(azpy)(glut)]}n (1a) which shows selective CO2 uptake over N2. 1a shows remarkable reversibility to give structure of 1b, similar to parent compound 1, when exposed to water vapor (Scheme 1).
’ EXPERIMENTAL SECTION Materials. N,N0 -Bis-pyridin-4-ylmethylene-hydrazine (azpy) was synthesized following a slightly modified procedure reported earlier.14 High purity copper(II) nitrate trihydrate was purchased from Aldrich Chemical Co. Inc. and used as received. All other chemicals were of AR grade and were used as received. Physical Measurements. Elemental analyses (carbon, hydrogen, and nitrogen) were performed using a PerkinElmer 240C elemental analyzer. Infrared spectra (4000400 cm1) were taken on KBr pellet, using PerkinElmer Spectrum BX-II IR spectrometer. Thermal analysis (TGA) was carried out on a METTLER TOLEDO TGA 850 thermal analyzer under nitrogen atmosphere (flow rate: 50 cm3 min1) at the temperature range 30500 °C with a heating rate of 2 °C/min. X-ray powder diffraction (PXRD) patterns in different states of the sample were recorded on a Bruker D8 Discover instrument using CuKR radiation. Measurement of Adsorption. The adsorption isotherm of CO2 (195 K) and N2 (77 K) were measured by using Quantachrome Autosorb1C adsorption instrument. In the sample chamber (∼17.5 mL) maintained at T ( 0.03 K was placed the adsorbent sample (∼100150 mg), which had been prepared at 353 K for compound 1 under a 1 101 Pa vacuum for about 12 h prior to measurement of the isotherms. Helium gas at a certain pressure was introduced in the gas chamber and allowed to diffuse into the sample chamber by opening the valve. The change in
pressure allowed an accurate determination of the volume of the total gas phase. The amount of gas adsorbed was calculated readily from the pressure difference (Pcal Pe), where Pcal is the calculated pressure with no guest adsorption and Pe is the observed equilibrium pressure. All operations were computer-controlled and automatic. The adsorption of different solvents such as MeOH at 293 K and H2O, EtOH at 298 K were measured in the gaseous state by using BELSORP-aqua-3 analyzer. In all the measurements, in the sample tube adsorbent sample (∼100150 mg) was placed which was prepared at 353 K for about 12 h under a vacuum prior to measurement of the isotherms. The different solvent molecules used to generate the vapor were degassed fully by repeated evacuation. Dead volume was measured with Helium gas. The adsorbate was placed into the sample tube, then the change of the pressure was monitored and the degree of adsorption was determined by the decrease in pressure at the equilibrium state. Here also all operations were computer controlled and automatic. Synthesis of {[Cu(azpy)(glut)](H2O)2}n (1). An aqueous solution (50 mL) of disodium glutarate (Na2glut) (1 mmol, 0.162 g) was mixed with methanolic solution (50 mL) of N,N0 -bis-pyridin-4-ylmethylene-hydrazine (azpy) (1 mmol, 0.210 g), and the resulting solution was stirred for 15 min to mix well. Cu(NO3)2 3 3H2O (1 mmol, 0.241 g) was dissolved in 50 mL of water, and 2 mL of this Cu(II) solution was slowly and carefully layered with the above mixed ligand solution using 1 mL of buffer (1:2 of water and MeOH) solution. After one day, a greenish compound was formed at the bottom of the tube. Shiny green single crystals suitable for X-ray diffraction analysis were obtained at the wall of the tube after two weeks (yield 76%). Anal. Calc. for C11H11CuN2O4, 2H2O: C, 39.44; H, 4.51; N, 8.36. Found: C, 39.41; H, 4.48; N, 8.33. IR spectra (in cm1): ν(OH), 35303170; ν(CO), 1613; ν(CH-Ar), 31002900 and ν(NH), 1566. Synthesis of {[Cu(azpy)(glut)]}n (1a). Single crystal of 1, which was used for X-ray diffraction analysis, was placed in a small roundbottom flask and heated at 150 °C in a oil bath for 6 h under reduced pressure, which yielded 1a. Anal. Calcd. for C11H11CuN2O4. C, 44.20; H, 3.71; N, 9.37. Found: C, 44.18; H, 3.68; N, 9.37. IR spectra (in cm1): ν(CO), 1613; ν(CH-Ar), 31002900 and ν(NH), 1566. 3906
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Table 1. Crystallographic and Structural Refinement Parameters for Complexes 1, 1a, and 1b 1
a
1a
1b
formula
C11H11CuN2O4,2H2O
C11H11CuN2O4
C11H11CuN2O4,2H2O
F.W.
334.78
298.77
334.78
cryst system
monoclinic
monoclinic
monoclinic
space group
C2/c
C2/c
C2/c
a/Å
27.6739(15)
27.733(2)
27.633(5)
b/Å
13.1598(6)
13.1588(9)
13.153(5)
c/Å
8.6462(4)
8.6333(7)
8.641(5)
R/ ° β/ °
90 95.435(3)
90 95.217(6)
90 95.500(5)
γ/ °
90
90
90
V/ Å3
3134.6(3)
3137.5(4)
3126(2)
Z
8
8
8
Dcalc/ g(cm)3
1.410
1.265
1.414
μ/ mm1
1.416
1.398
1.420
F(000)
1360
1216
1360
θ range/ ° refl collected
1.524.5 14908
1.526.5 23416
1.727.5 12986
unique refls
2520
3231
3556
Rint
0.096
0.092
0.060
no. of refls I > 2σ(I)
1592
2195
2183
goodness-of-fit
1.04
1.07
1.05
R1 (I > 2σ(I))a
0.0503
0.0811
0.0613
wR2a
0.1877
0.2530
0.1908
R1 = Σ||Fo| |Fc||/Σ|Fo|, wR2 = [Σ(w(Fo2 Fc2)2)/Σw(Fo 2)2]1/2.
Table 2. Selected Bond Lengths (Å) and Bond Angles (°) for Compound 1a Cu1O3
1.964(5)
Cu1N1
2.184(5)
Cu1O4a Cu1O1c
1.973(4) 1.969(5)
Cu1O2b
1.977(5)
O3Cu1N1
95.2(2)
O3Cu1O4a
87.0(2)
O2 Cu1O3
89.9(2)
O1cCu1O3
168.2(2)
O4aCu1N1
102.6(2)
O2bCu1N1
89.2(2)
O1 Cu1N1
96.6(2)
O2bCu1O4a
168.0(2)
O1cCu1O4a
90.8(2)
O1cCu1O2b
89.9(2)
b
c
Symmetry code: (a) x, -y, 1/2 + z; (b) 1/2 x, 1/2 + y, 1/2 z; (c) 1/2 x, 1/2 y, z. a
Synthesis of {[Cu(azpy)(glut)](H2O)2}n (1b). The dehydrated single crystal 1a was exposed to water vapors for 7 days which afforded 1b, similar to the parent compound 1. Anal. Calcd C11H11CuN2O4, 2H2O: C, 39.44; H, 4.51; N, 8.36. Found: C, 39.40; H, 4.50; N, 8.35. IR spectra (in cm1): ν(OH), 35303170; ν(CO), 1613; ν(CH-Ar), 31002900 and ν(NH), 1566. Crystallographic Data Collection and Refinement. A suitable green-colored single crystal of compound 1 and the crystals of 1a and 1b after proper preparation were mounted on a thin glass fiber with commercially available super glue. X-ray single crystal data collection of all three crystals was performed at room temperature using a Bruker APEX II diffractometer, equipped with a normal focus, sealed tube X-ray source with graphite monochromated MoKR radiation (λ = 0.71073 Å). The data were integrated using a SAINT15 program and the absorption corrections were made with SADABS. All the structures were solved by SHELXS 9716 using the Patterson method and followed by successive Fourier and difference Fourier synthesis. Full matrix least-squares
refinements were performed on F2 using SHELXL-9717 with anisotropic displacement parameters for all non-hydrogen atoms. During refinement of 1 and 1b, two of the lattice water molecules are found disordered, and thus their occupancy were fixed at 0.5 before final refinement. All the hydrogen atoms except the disordered lattice water hydrogen were fixed geometrically by HFIX command and placed in ideal positions in case of all three structures. All calculations were carried out using SHELXL 97, SHELXS 97, PLATON v1.15,18 ORTEP-3v2,19 and WinGX system Ver-1.80.20 The coordinates, anisotropic displacement parameters, and torsion angles for all three compounds are submitted as Supporting Information in CIF format. Data collection and structure refinement parameters and crystallographic data for all compounds are given in Table 1. The selected bond lengths and bond angles are given in Tables 24.
’ RESULTS AND DISCUSSION Structural Description of {[Cu(azpy)(glut)](H2O)2}n (1). Compound 1 crystallizes in monoclinic C2/c space group, and the single crystal X-ray diffraction analysis reveals that the 3D coordination framework of copper(II) bridged by the dicarboxylate (glut) and a linear Schiff base linker azpy (Figure 1). Here each penta-coordinated Cu(II) ion with CuO4N chromophore shows nearly square planar geometry with a Addison parameter (tau) value of 0.01.21 Each Cu(II) atom is ligated to the four oxygen atoms (O3, O4a, O2b, and O1c where a = x, y, 1/2 + z, b = 1/2 x, 1/2 + y, 1/2 z, c = 1/2 x, 1/2 y, z) of glutarate which occupy the equatorial positions [bond length lies in between 1.964(5) Å and 1.977(5) Å], and the axial site is occupied by one nitrogen atom (N1) of azpy ligand with a bond distance of 2.184(5) Å. The other selected bond length and bond angles are reported in Table 2. Four different carboxylate units 3907
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connect two Cu(II) centers to form a paddle-wheel Cu2(CO2)4 dinuclear secondary building unit, which are connected by the glutarate to form 2D brick wall arrangements (Figure 2) in the crystallographic bc plane. Further, each dinuclear paddle-wheel unit is connected to four adjacent paddle-wheel units (Figure 2). In each dinuclear unit, the Cu(II) centers are separated by 2.631 Å and the intrasheet coppercopper distance lies in between 6.89(1) Å and 8.89(1) Å. The 2D sheet formed by the glutarate is further associated by azpy linker to form a threedimensional pillared-layer structure with 1D channel along the Table 3. Selected Bond Lengths (Å) and Bond Angles (°) for Compound (1a)a Cu1O3
1.975(4)
Cu1N1
2.181(5)
Cu1O4a
1.987(4)
Cu1O2b
1.960(4)
Cu1O1c
1.959(4)
O3Cu1N1
89.28(19)
O3Cu1O4a
89.03(18)
O2 Cu1O3 O4aCu1N1
90.16(18) 97.21(19)
O1cCu1O3 O2bCu1N1
168.17(19) 94.99(19)
O2bCu1O4a
167.77(18)
O1cCu1O2b
87.14(18)
b
O1cCu1N1 O1 Cu1O4 c
102.4(2) a
91.17(18)
crystallographic c axis, occupied by the guest water molecules. In the 3D framework azpy linkers are criss-crossed and canted, resulting in honeycomb-like arrangements viewed along the c axis (Figure 3). The dimension of the channel is about 5.8 7.8 Å2 and upon removal of the water molecules the framework suggests about 34% void space to the total crystal volume as suggested by the PLATON18 crystallographic software. Framework Stability. Thermogravimetric analysis of the powder sample of 1 performed in the temperature range of 30500 °C is shown in Figure 4. There is a weight loss around 90 °C, and the percentage weight loss (∼10.8%) corresponds to the loss of two lattice water molecules. The dehydrated framework of {[Cu(azpy)(glut)]}n (1a) is stable up to 250 °C without further weight loss and then decomposes to an unidentified product. The X-ray powder diffraction pattern (Figure 5) also supports the stability of the framework in the dehydrated state. The PXRD pattern after complete removal of the water molecules shows a pattern similar to that of 1 which clearly suggests
Symmetry code: (a) x, 1 y, 1/2 + z. (b) 3/2 x, 1/2 + y, 3/2 z. (c) 3/2 x, 1/2 y, 1 z. a
Table 4. Selected Bond Lengths (Å) and Bond Angles (°) for Compound 1ba Cu1O3
1.970(4)
Cu1N1
2.180(4)
Cu1O4a
1.976(3)
Cu1O2b
1.968(4)
Cu1O1c
1.977(4)
O3Cu1N1
89.20(15)
O3Cu1O4a
89.12(15)
O2 Cu1O3
89.84(15)
O1cCu1O3
167.98(17)
O4aCu1N1
96.71(14)
O2bCu1N1
95.28(15)
O1 Cu1N1
102.68(15)
O2bCu1O4a
167.95(15)
O1cCu1O4a
91.28(15)
O1cCu1O2b
87.26(15)
b
c
Symmetry code: (a) x, y, 1/2 + z. (b) 1/2 x, 1/2 + y, 3/2 z. (c) 1/ 2 x, 1/2 y, 2 z.
a
Figure 2. 2D brick-wall arrangements constructed by paddle-wheel units (azpy ligand removed for clarity).
Figure 1. Penta-coordinated copper(II) units showing the coordination environment of Cu(II) where a dicarboxylate (glutarate) and a linear Schiff base ligand are used as the building blocks. 3908
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Figure 3. 3D honeycomb-like structure with water molecules encapsulated in the nest of the honeycomb.
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Figure 6. The space filling model of the dehydrated species 1a showing the 3D honeycomb-like empty channels.
Figure 4. TGA of the compound 1 under nitrogen atmosphere. Figure 7. Gas adsorptiondesorption isotherms for 1; CO2 (green) at 195 K; N2 (blue) at 77 K. Adsorption: (filled shape), desorption: (half filled shape).
Figure 5. PXRD patterns of 1 in different states. (a) Simulated from X-ray single crystal data; (b) bulk as-synthesized compound; (c) at 150 °C; (d) exposed to the water vapor for seven days.
the rigid nature of the framework. It is worth mentioning that the PXRD pattern of the rehydrated compound 1b exhibits peak positions identical to the as-synthesized compound 1 (Figure 5). The reversible nature of the framework is also justified by the IR spectra of 1, 1a, and 1b. Single-Crystal-to-Single-Crystal Structural Transformation. The water molecules present in the channels are quite weakly held as these are not associated even by H-bonding, to the host framework. As a result, the 3D framework of 1 is rigid and
stable without the guest water molecules, and the processes of removal of the guest water molecules are reversible. Moreover, high thermal stability of the framework inspired us to determine the corresponding crystal structure after removal of all the guest water molecules from the framework by controlled heating. Single-crystal-to-single-crystal transformation experiment was performed, which gives the single crystal X-ray structure of dehydrated (1a) and rehydrated (1b) species with very similar cell parameters (Table 1, Scheme 1). The as-synthesized crystals of 1 were heated at around 150 °C under reduced pressure for 6 h to remove the guest water molecules, and the color of the crystals changed from deep green to light green. The light green crystal shows a similar crystal system and space group as that of 1 (Table 1). The structure determination of the dehydrated compound 1a reveals that the same framework structure as that of 1 with the only difference of the nonexistence of lattice water molecules resulting a large void of ca. ∼34%18 in the framework (Figure 6). The bond length and bond angles are almost similar to that of 1 with a very little difference (Table 2). When the dehydrated light green crystals of 1a were exposed to water vapor for seven days, the deep green 3909
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Figure 8. Solvent vapor adsorptiondesorption isotherms for 1; water (blue) at 298 K; inset MeOH (green) at 293 K and EtOH (pink) at 298 K. P0 is the saturated vapor pressure of the respective adsorbate at the corresponding temperature. Adsorption: (filled shape), desorption: (half filled shape).
color reappears, and structure determination of rehydrated compound 1b reveals that 1a returned to the virgin assynthesized compound 1 with the formula of {[Cu(azpy)(glut)](H2O)2}n (Figure 3), suggesting complete reversibility of the framework. The bond lengths and angles of 1b are also comparable to that of 1 (Table 4). Adsorption Property. To evaluate the porosity and adsorption capacity of compound 1a, we have carried out N2 (kinetic diameter, 3.64 Å)22 and CO2 (3.3 Å) gas adsorption measurements at 77 and 195 K, respectively (Figure 7). Activated framework 1a shows no uptake of N2, although the pore aperture is large enough compared to the kinetic diameter of N2. This may be due to the one-dimensional channel system in 1a, as there are no additional channels along the crystallographic a- and b-axis (Figure SI, Supporting Information). Therefore, at low measuring temperature (77 K) window of the channels are blocked by the entering N2 molecules which inhibits further diffusion of the N2 molecules. But at 195 K, 1a shows a type-I adsorption curve for CO2 with an apparent Langmuir surface area of 131 m2 g1. The adsorption amount of CO2 at saturation is ≈34 mL g1 (STP), which corresponds to an uptake of 6 wt % of CO2. The CO2 isotherm was analyzed with the DubininRadushkevich equation,23 which suggests moderate hostguest interaction (isosteric heat of adsorption, qst ≈ 27 kJ mol1). Selectivity of CO2 over N2 arises due to the high quadrapole moment of CO2 and can interact effectively with the base functionalities (CHdN- group) in the pore surfaces. Again the small hysteresis in adsorptiondesorption isotherm in CO2 also suggests the occurrence of such interactions. We have also performed solvent vapor adsorption studies (H2O, EtOH at 298 K and MeOH at 293 K) for compound 1a (Figure 8). Interestingly, the H2O adsorption profile shows a stepwise uptake; at relative vapor pressure P/P0 ∼ 0.25 it shows a steep uptake followed by attainment of saturation capacity of 236 mL g1 which corresponds to 3H2O molecules per formula. The existence of a pressure threshold is less common in MOFs since most MOFs show a high affinity for H2O due to the presence of hydrophilic sites in their framework. But the present case indicates to
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hydrophobic surfaces,24 and this behavior suggests the formation of only weak guest-wall interactions as a consequence of the presence of pyridyl rings and aliphatic chains of glutarate on the pore walls. MeOH and EtOH vapors also diffuse into the micropores of compound 1a and the uptake amounts are in accordance with the kinetic diameter (H2O - 2.65 Å, MeOH 3.8 Å, EtOH - 4.3 Å) of the molecules. Unlike the H2O adsorption profile MeOH and EtOH vapors show type-I adsorption profile and a steep uptake at low pressure regions suggesting strong interactions with the pore surface. This can be correlated to the polarity of the pore surfaces, as the framework is decorated with the aliphatic hydrophobic chains of glutarate and base functionalities (CHdN-) of azpy. It shows higher affinity toward MeOH and EtOH which contain both an aliphatic hydrophobic part and hydrophilic OH groups. The type-I adsorption profiles for MeOH and EtOH clearly indicate the same, whereas highly polar water molecules show low uptake at low pressure indicating hydrophobic nature of the pore surface. The final uptake volume indicates 1.4 and 0.6 molecules of MeOH and EtOH occluded respectively per formula of 1a.
’ CONCLUSION We have successfully synthesized a 3D porous framework of copper(II) where the channel surfaces are decorated with Schiff base nitrogen sites. The dehydration and rehydration of the framework reveal complete reversibility and robustness of the framework. Upon removal of guest water molecules, it shows high selectivity toward CO2 over N2. Solvent vapor adsorption study of 1 shows the hydrophobic nature of the pore surface. All these phenomena suggesting that the observation may contribute to the development of new types of catalyst constructed from MOFs, which can additionally function to remove gaseous CO2 from the environment which is becoming the most devastating waste on the globe. Moreover, the pore is accessible toward the solvent, and that is why this can function as a base catalytic pore for heterogeneous catalysis. ’ ASSOCIATED CONTENT
bS
Supporting Information. X-ray crystallographic data in CIF format for the structures reported in this paper and the space filling diagrams of the compounds are available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*(D.G.) E-mail:
[email protected]. Fax: +9133 2414 6223. (T.K.M.) E-mail:
[email protected]. Fax: +9180 2208 2766.
’ ACKNOWLEDGMENT Authors gratefully acknowledge the financial assistance given by the DST, Govt. of India, under the SERC Fast Track Scheme to D.G. (Grant No. SR/FT/CS-015/2008). The X-ray diffractometer facility of Dept. of Chemistry, Jadavpur University, under the DST FIST program is also gratefully acknowledged. ’ REFERENCES (1) (a) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31, 474. (b) Batten, S. R. Curr. Opin. Solid State 3910
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