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Piezochromic porous metal-organic framework Micha# Andrzejewski, and Andrzej Katrusiak J. Phys. Chem. Lett., Just Accepted Manuscript • Publication Date (Web): 16 Dec 2016 Downloaded from http://pubs.acs.org on December 16, 2016

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The Journal of Physical Chemistry Letters

Piezochromic Porous Metal-Organic Framework Michał Andrzejewski, Andrzej Katrusiak* Department of Materials Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznan, Poland, [email protected], Tel: +48 618291590. AUTHOR INFORMATION Corresponding Author *[email protected]

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Abstract

Pressure changes the color of a new type of metal-organic porous hybrid material CoBbcDabcoH2O. It is built of Co cations linked by 1,4-benzenedicabroxylate (Bdc) anions and 1,4-diazabicyclo[2.2.2]octane

(Dabco)

molecules

into

2-dimensional

grid-like

sheets,

interconnected through OH···O bonds of water to carboxylate H-acceptors. This first piezochromic MOF, stable in air and in many solvents, is an ideal ultra-precise sensor for pressure calibration. The color changes are due to strains generated by pressure in the highly asymmetric crystal field of Co2+-coordination, involving four different ligand types: a dabco amine (twice), a monodentate carboxylate, a chelating carboxylate and a water molecule. At 0.33 GPa/296 K and below 225 K/0.1 MPa a phase transition reduces the crystal symmetry from monoclinic to triclinic system and changes the conformation and orientation of linkers.

KEYWORDS piezochromism, metal-organic framework, high pressure, porous material


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Various properties of metal-organic frameworks (MOFs),1,2 mainly of 3-dimensional architecture, have been intensively investigated in the search for novel functional materials.3-7 Very unusual elastic properties, like negative area compressibility (NAC)8 or positively related pressure and temperature effects, have been reported for MOFs.9-11 It was shown recently that 3dimensional (3-D) MOFs of the general formula Me2Bdc2Dabco (Me=metal cation, Bdc=1,4benzenedicarboxylate,

C8H6O4,

Dabco=1,4-diazabicyclo[2.2.2]octane,

C6H12N2)

strongly

respond to the external stimuli of pressure and temperature, as well as to the exchange of guest molecules.12 A counterintuitive behavior was reported for Zn2Bdc2Dabco, which shrinks when up-taking guests and expands on their release.13 Low-temperature studies of this compound with its pores adsorbing DMF and benzene, or evacuated, revealed guest-dependent phase transitions.12 A new type of microporous materials responding by softening on adsorption were found and modeled by molecular simulations.14 Presently we have synthesized at ambient pressure and room temperature a new type of porous MOF, CoBdcDabcoH2O, labeled AMU-1, where AMU abbreviates Adam Mickiewicz University (Figure 1). It is built of 2-D polymeric grid layers, of Co2+ cations coordinated each by three O-atoms of two Bdc dianions, two N-atoms of two Dabco molecules, and one O-atom of one water molecule; these grids are interconnected by water-mediated hydrogen bonds OH···O. The cobalt minerals (eg. Co2+ bearing erithrite and lusakite),15 as well as inorganic and organic complexes of cobalt16,17,18 are textbook examples of compounds of spectacular colors and after succeeding in the synthesis of AMU-1 we have investigated its polychromic properties. We found that the AMU-1 crystals display an exceptionally strong and reversible piezochromism, the property desired for versatile applications, for example in pressure sensors and mechanooptical transducers. Because of this demand, new piezochromic materials are intensively sought



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and investigated. Piezochromism, coupled to pressure-induced conductivity was recently reported in layered perovskites.19,20 Strong effect of pressure on the absorption edge and the energy gap was described for organometalhalide perovskite photovoltaic materials FAPbBr3 (FA=formamidinium)21 and MAPbI3 (MA=methylammonium).22 Piezochromic fluorescence was evidenced in carbazole-substituted CNDSB (1,4-bis(1-cyano-2-phenylethenyl)benzene) crystals, an organic porous material.23 The pressure-induced photomagnetic effect combined with the spin-crossover-related piezochromism24 as well as piezochromic luminescence induced by grinding25 were reported. Naphthalenediimine (NDI) based ligands were used for designing new MOFs in order to introduce the chromophore molecules of known behavior. Banerjee et. al. reported

a photochromic Mg-NDI MOF,

which

additionally exhibits a reversible

solvatochromism for a wide range of polar and nonpolar solvents.26 Moreover, electrochromic transparent-to-dark transitions were found in MOFs Mg2(NDISA) and Ni2(NDISA), where NDISA abbreviates naphthalenediimide salicylic acid.27 Compared to other piezochromic materials, the piezochromic MOFs offer new qualities,28 owing to their exceptional softness and to the presence of open pores enabling the adsorption of pressure-transmitting media and their direct interactions with chromophores in the bulk of the crystal. In order to understand these interactions we have studied the single crystals of AMU-1 by VIS spectroscopy and X-ray diffraction as a function of temperature and pressure.


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Figure 1. AMU-1 (CoBdcDabcoH2O) structure: (a) dication Co2+ six-fold coordinated by two Bdc dianions, two Dabco molecules and one water molecule; (b) schematic illustration of the stack of [-Bdc-Co-Dabco-]n grids, linked by water-mediated OH···O hydrogen bonds, and pores penetrating through rings [-Bdc-Co-Dabco-Co-]2 rings in the grids. Experimental details The diffusion method was applied for the simultaneous reaction and crystallization of products conducted at 295 K and ambient pressure. For this purpose two layers of dissolved substrates were separated by a diffusion-zone mixture. The top layer was 1 mmol 1,4diazabicyclo[2.2.2]octane (Dabco) dissolved in 6 ml of methanol (99.9% by POCH), the bottom layer was the solution of 0.5 mmol CoCl2·6H2O and 0.5 mmol of benzene-1,4-dicarboxylic acid 5 ACS Paragon Plus Environment


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(H2Bdc) in 6 ml of DMF (dimethylforamide, >99.8% by POCH), and the separating layer was 2 ml of the methanol:DMF (1:1 vol.) mixture. The liquids were poured into a test tube slowly to form three separate layers and the tube was sealed with a piece of parafilm. Within 24 hours dark blue crystals appeared on the test-tube wall within the middle layer, and during the following week their quantity significantly increased and they spread to the top layer and also fell down to the bottom. These crystals of uniform habit and color, shown in Figure 2, were studied by singlecrystal and by powder X-ray diffraction and turned out to be Co2Bdc2Dabco29 (Figure S9 in Supporting Information, SI). Then the layers of solutions were removed from the test tube one by one with a syringe and stored in separate vials. After few days in the vial containing the bottomlayer solution, new crystals of distinctly different shape and purple color precipitated (Figure 2). We identified their structure by single-crystal X-ray diffraction as CoBdcDabcoH2O, labeled as AMU-1. Among the AMU-1 crystals also few colorless Bdc:Dabco 1:1 co-crystals precipitated in the vial; however they are clearly distinct in morphology and could be manually separated; they also very well dissolve in organic solvents and can be washed out, for example with methanol. The homogeneity of the synthesized AMU-1 samples was confirmed by X-ray powder diffraction (see Figure S9 in the Supporting Information). In contrast to Co2Bdc2Dabco,29 the CoBdcDabcoH2O crystals are stable in air. In this respect the relation between Co2Bdc2Dabco and CoBdcDabcoH2O resembles that between analogous unstable Zn2Bdc2Dabco and stable Zn2TMBdc2Dabco (TMBdc abbreviates 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate).30 Thermogravimetric analysis (TGA) was performed on a DSC X7000 Hitachi High Technologies apparatus with simultaneous thermal analyzer STA 7200 Hitachi High Technologies. 6.741 mg of the AMU-1 sample was heated gradually from 303 K to 873 K (Figure S10 in SI). The evacuated content in gas phase was analyzed by FTIR spectroscopy at


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four temperatures of consecutive decomposition steps (Figure S11a). The IR spectrum at 440 K corresponds to the strongest DMF release (Figure S11b), starting at 403 K, and confirms the presence of DMF in the pores of AMU-1 after the synthesis; the IR spectrum at 513 K shows the release of H2O, starting at 483 K. The spectrum at 817 K marks the oxidation of organic moieties, as the only IR peak at 2354 cm-1 can be associated with the release of CO2.

Figure 2. Three layers of dissolved substrates poured separately into a test tube for the simultaneous synthesis and crystallization of Co2Bdc2Dabco (microscopic view in polarized light in the top-circle inset). Crystals of AMU-1 (CoBdcDabcoH2O, shown in the bottom circle) were obtained from the separated bottom layer. High-pressure experiments were carried out in a Merrill-Bassett diamond-anvil cell (DAC)31 modified by mounting the diamond anvils directly on the steel discs with conical windows. XRay diffraction data were measured with an Xcalibur Eos32 diffractometer and MoKα radiation. A CryoSystem gas-flow attachment was used for measuring the low-temperature single-crystal 7 ACS Paragon Plus Environment


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data. In most experiments methanol was used as the pressure-transmitting medium;33 we also investigated the sample crystals boiled in silicon oil for 6 h at 400 K in order to evacuate them of guest molecules. Pressure inside the DAC was determined by the ruby fluorescence method.34,35 The preliminary experiment on a single crystal of AMU-1, gradually compressed in a membrane diamond-anvil cell (Movie 1 in SI), revealed spectacular gradual color changes from purple to orange at 0.4 GPa and then to light yellow at 1.5 GPa (Figure 3a). We have established that the AMU-1 (CoBdcDabcoH2O) crystals are monoclinic, of spacegroup symmetry Pm (Table 1), and at 0.33 GPa they transform to a triclinic phase of space group P1. These ambient and high-pressure phases have been labeled α and β, respectively. The same transition to phase β has been observed at 225 K in a series of low-temperature single-crystal Xray diffraction measurements. The structures of both phases α and β were solved by direct methods with program Shelxs and refined by the full-matrix least squares with Shelxl,36 using interface Olex2.37 The transition in AMU-1 is ferroelastic and causes a twinning of the β-phase samples. Therefore the low-temperature and high-pressure diffraction data at for phase β were treated with the TWIN instructions of CrysAlis and Shelxl. Disordered contents of the pores in AMU-1 were accounted for by the SQUEEZE routine.38,39 Arene hydrogen atoms were located from the molecular geometry by using instruction AFIX 43 (distance C-H 0.93 Å), ethylene H-atoms by AFIX 23 (0.97 Å) and the geometry of water molecule was fixed by constraining its distances OH to 0.97 Å and H···H to 1.66 Å. The X-ray diffraction studies on the single crystal boiled and maintained in oil showed that they retain the symmetry of space group Pm and the unit-cell dimensions are consistent with those of the samples not treated thermally.


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High-pressure VIS spectra (Figure 5b,c) were measured with a Jasco S-650 spectrometer operated at the 5 nm resolution, with an optical attachment focusing the probing beam at the DAC chamber, filled with the AMU-1 sample and glycerin used as the hydrostatic fluid. The spectra were referred to the signal initially recorded in the same configuration with the DAC chamber without the sample, but it was filled with the hydrostatic fluid and containing a small ruby chip then used for the pressure calibration.34,35 A DSC600 system of Linkam Scientific Instruments was adopted, by installing the beam-condensing optics in the Jasco S-650 spectrometer, for measuring the VIS spectra of AMU-1 as a function of temperature.

Table 1. Selected structural data of AMU-1 phases α and β (cf. SI for detailed crystallographic and experimental details). The volume of pores (Vp) was calculated with program Mercury for the probing-sphere radius 1.2 Å and grid spacing 0.1 Å.40 phase space group p (GPa)/T (K) a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z/Z’ Dx (g·cm-3) Vp (Å3 / %)

Α Pm 0.0001/296 6.1071(2) 7.0985(2) 10.6748(2) 90 95.017(2) 90 460.99(2) 1/0.5 1.272 32.5 / 7.0

β P1 0.0001/100 5.9793(5) 7.0877(5) 10.6426(7) 88.930(5) 96.108(6) 93.520(6) 447.59(6) 1/1 1.310 26.5 / 5.9

β P1 3.59/296 5.571(3) 6.8976(8) 10.411(4) 87.263(18) 100.31(4) 94.672(19) 392.1(2) 1/1 1.496 12.7 / 3.2

Discussion AMU-1 is a novel porous material displaying several remarkable and potentially practically useful properties. The Co(II) cation is six-fold coordinated: at the opposite sides along one direction by two Dabco molecules, approximately perpendicular to two benzenedicarboxylate 9 ACS Paragon Plus Environment


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(Bdc) anions, with three carboxylate oxygens involved, and by one water molecule complementing the distorted octahedron (Figure 1, cf. Figure S1 in SI). The AMU-1 crystal has an unique layered structure of metal-organic polymeric grids parallel to crystal plane (100). The grids are interconnected via H-bonds OH···O between the coordinating water molecule and the H-accepting atoms O2 and O3 of Bdc anions in the next grid along the crystal [x] axis. The channel pores run along the [x] direction, nearly perpendicular to the grids through their [-CoBdc-Co-Dabco-]2 rings (Figures 1 and 4). When phase α transforms to phase β, the Bdc anions rotate by 15.4° off the (010) plane to a new position and atom O3 approaches the Dabco molecule, which changes its conformation by twisting the ethylene bridges, planar in phase α, to the propeller-like conformation in phase β. A phase transition involving a rotation of the Bdc benzene rings was observed in MIL-53 and in {Cu[(4,4’-(1,4-(trans-2butene)diyl)bis(1,2,4)triazole)](ClO4)}·DMF·H2O, where the rotation of phenyl rings results in closing the pores.41,42 In phase α of AMU-1 torsion angles N-C-C-N are equal to zero and the molecular symmetry of Dabco is close to D3h. In phase β the ethylene bridges become twisted and torsion angles N-C-CN increase to about 15° at 100K and the molecular pseudosymmetry is reduced to D3 (Figures 3, S1 and S7 in SI). The water molecules also adjust their positions to the rotated Bdc anions, as they are connected via the OH···O hydrogen bonds. The positions of Dabco linkers coincide with the least compressed and thermally least expanding unit-cell parameter b (Figures 4 and S5 in SI). The shear strain of unit-cell angle γ changes from 90° in monoclinic phase α to about 95° in triclinic phase β, and it contributes to the reduced distance between the neighboring grids. The grids are relatively rigid and the crystal is softest along the pores, down axis [x] (Figures 5, S1 and S5), due to the compression of hydrogen bonds OH···O. Consequently, the perpendicular


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cross-section of pores is their least affected dimension. The pores close only at approximately 3.5 GPa due to the Bdc rotations (Figures 1, 3 and S8 in SI).

Figure 3. Crystal structures of AMU-1 phases α and β projected along crystal axes a (left) and b (right). Red dotted lines indicate hydrogen bonds OH···O between layers.



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Figure 4. Unit-cell volume (a) and parameters (b) of AMU-1 as a function of pressure (circles) and temperature (triangles). The unit-cell angles are plotted in Figure S5 in SI. 12 ACS Paragon Plus Environment

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The revealed piezochromism of AMU-1 involves several predominantly monotonic changes in its spectrum, illustrated in Figure 5. The spectrum is dominated by a broad absorption between 430 and 630 nm, consisting of two overlapping bands at 480 and 560 nm, and a weaker shoulderlike band at about 690 nm. The pressure-induced changes in the spectrum can be conveniently described by the shifts of the long-wavelength slope (LWS) and short-wavelength slope (SWS) of the overlapped bands (measured at the half maximum of the broad peak, shown in Figure 5), as well as by the shift of the long-wavelength slope of the weaker absorption band, at about 700 nm. This latter peak is shifted by about 100 nm between 0.1 MPa and 3.5 GPa. The LWS and the narrowing of the dominant absorption peak measured as its full width at half maximum (FWHM), they both shift at a considerable rate of -20 nmGPa-1, which is about 55 times larger than the ruby-fluorescence shift used for the pressure calibration (Table S1).34,35 Moreover, there are several features of the absorption of AMU-1 which can be applied as independent parameters for pressure calibration. Particularly the LWS and FWHM of the dominant absorption peak appear especially convenient (Figure S12). The pressure in a DAC can be even roughly determined by visually assessing the color changes. The temperature-dependent color changes (thermochromism) of the AMU-1 crystals are much weaker than those induced by pressure. The VIS spectra of AMU-1 measured as a function of temperature are shown in Figure S3. We have established that d(LWS)/dT = -0.125nmK-1, and d(FWHM)/dT = -0.15nmK-1, so for example an unaccounted temperature change of 8K would cause an error in the pressure measurement of about 0.05 GPa; in the ruby scale this error would be about three times larger. Although the pressure and temperature dependences of the shifts in AMU-1 spectra are not linear, their values can be tabulated or fitted with polynomial functions in order to easily calculate the pressure magnitude (Figures 5 and S12). The strong piezochromism



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of AMU-1 can be associated with the remarkably low symmetry of the crystals (Table 1) and with the distortions of pseudo-octahedral coordination of cations Co2+, located in the highly asymmetric crystal field composed of four types of ligands. High pressure increases the interactions with the Bdc, Dabco and water ligands embedded in the low-symmetry crystal environment and enhances the distortions of the pseudo-octahedral crystal field around Co2+.

Figure 5. Piezochromism in AMU-1: (a) a single crystal changing color from purple (phase α) to orange and yellow (phase β); (b) selected high-pressure VIS spectra of AMU-1; and (c) the plot


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shows shifts of LWS and SWS of the dominant peak fitted with polynomial functions (cf. SI). The changes of FWHM as a function of pressure is plotted in Figure S12. These changes are intrinsically connected to the distortions of the framework and they are fully reversible: we detected no spectroscopic nor structural differences induced by aging the sample or by cycling it 10 times between 0.1 MPa and 3.0 GPa (Figures S9, S12, Tables S4, S5 and S6). The calculations of excited states of AMU-1, by applying semiempirical methods and crystalfield theory, aimed at reproducing the VIS spectra and understanding the origin of piezochromic properties of AMU-1, are in progress. The initial model optimized within method ZINDO and VSTO-6G basis set is insufficient for this purpose and more advanced CIS and TDDFT basis sets are currently applied. It can be concluded that to our knowledge AMU-1 is the first strongly piezochromic porous MOF. It responds reversibly to the pressure stimuli so strongly that it can be used for visually assessing pressure in the DAC according to the color changes or as a superprecise sensor for spectroscopic pressure measurements. Apart from the applications for monitoring pressure, AMU-1 can be also used as a pressure-controlled multistable switch operated by photodetectors with spectral filters. Such pressure switches can be used for various technological applications in traditional pressure devices, as well as in the DAC. It is also important that AMU-1 can be synthesized in the form of single crystals at ambient conditions and stored in the open air, which facilitates the production, installation and operation of the pressure sensors stable at a considerable range of environments. AMU-1 demonstrates the potential of MOF crystals as pressure sensors, opening a whole new alley of their applications.

ASSOCIATED CONTENT 15 ACS Paragon Plus Environment


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Electronic Supplementary Information (ESI) available: detailed structural data CCDC: 14928641492894, 1505328-1505329. The following files are available free of charge. crystal structures (CIF) piezochromic effect in AMU-1 when increasing pressure and the reverse transition (MPG) AUTHOR INFORMATION Notes The authors declare no competing financial interests. ACKNOWLEDGMENT The authors are grateful to Prof. Andrzej Maciejewski for helpful discussions and for granting access to the Jasco spectrometer, to Mr. Szymon Sobczak for support and advices and to Mrs. Róża Tomikowska from Haas (haas.com.pl) for performing the TGA/FTIR measurements on apparatus DSC X7000 Hitachi High Technologies with simultaneous thermal analyzer STA 7200. This work was supported by the Polish National Science Center, research grant Preludium 2014/15/N/ST5/00748. References (1) Furukawa, H.; Cordova, K.E.; O'Keeffe, M.; Yaghi, O.M. The Chemistry and Applications of Metal-Organic Frameworks Science 2013, 341, 1230444. (2) Tranchemontagne, D.J.; Mendoza-Cortés, J.L.; O’Keeffe, M.; Yaghi, O.M. Secondary Building Units, Nets and Bonding in the Chemistry of Metal–Organic Frameworks Chem. Soc. Rev., 2009, 38, 1257-1283. 16 ACS Paragon Plus Environment

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