Supplementary Materials for

Transcription

1 Supplementary Materials for Tristability in a Light Actuated Single-Molecule Magnet Xiaowen Feng, 1 Corine Mathonière, 2,3 Ie-Rang Jeon, 2,3,4,5 Mathieu Rouzières, 4,5 Andrew Ozarowski, 6 Michael L. Aubrey, 1 Miguel I. Gonzalez, 1 Rodolphe Clérac, 4,5 * Jeffrey R. Long 1,7 * 1 Department of Chemistry, University of California, Berkeley, California 94720, USA. 2 CNRS, ICMCB, UPR 9048, Pessac, F-33600, France. 3 Univ. Bordeaux, ICMCB, UPR 9048, Pessac, F-33600, France. 4 CNRS, CRPP, UPR 8641, Research team for Molecular Magnetic Materials, F Pessac, France. 5 Univ. Bordeaux, CRPP, UPR 8641, F Pessac, France. 6 National High Magnetic Field Laboratory, Tallahassee, Florida 32310, USA. 7 Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. Correspondence to: clerac@crpp-bordeaux.cnrs.fr, jrlong@berkeley.edu S1

2 Table of Contents Materials and Methods p. S3-S4 1.1 Synthesis of [Fe(ptz) 6 ](BF 4 ) Magnetic Measurements 1.3 EPR Measurements 1.4 Other Physical Measurements Supplementary Figures S1-S14 p. S5-S15 S2

3 Materials and Methods 1.1 Synthesis of [Fe(ptz) 6 ](BF 4 ) 2 : The synthesis of 1-propyltetrazole (ptz) was performed as previously reported with slight modifications. 1,2 Equimolar amounts of n- propylamine, sodium azide and triethyl orthoformate were dissolved in 30 M equiv. of 99.5% acetic acid and stirred at 90 C overnight. 80 M equiv. of 4 N HCl solution was added after removing the solvent under vacumm. The resulting solution was extracted three times with ethyl acetate. The organic phase was neutralized with NaHCO 3. Then, the organic phase was filtered and dried with MgSO 4 overnight. Afterwards, the solvent was removed under vacumm. The resulting oil was distilled in a Kugelrohr apparatus at 150 C and a pressure of 1 hpa yielding colourless oil. All other reagents were obtained from commercial sources and used without further purification. The synthesis of [Fe(ptz) 6 ](BF 4 ) 2 was performed under nitrogen atmosphere according to the literature, using Schlenk technique as described in the following procedure. 1 mmol of Fe(BF 4 ) 2 6H 2 O was dissolved in 3 ml of ethanol. A solution of 6 mmol of 1- propyltetrazole in 3 ml of ethanol was then added drop-wise. The resulting colorless solution was allowed to stir for 1 h to afford white crystalline powder of [Fe(ptz) 6 ](BF 4 ) 2. The white precipitate was collected by filtration, washed with successive aliquots of Et 2 O and dried in air to afford 0.62 g (69%) of product. Anal. Calcd for FeC 24 N 24 H 48 B 2 F 8 : C, 31.94; N: 37.26; H: Found: C, 32.02; N: 37.75; H: IR (300 K): ν (C-H ring ) 3146 cm -1, ν (C-H alkyl ) 2972 cm -1, 2941 cm -1, 2883 cm -1 Previous Reported: ν (C-H ring ) 3144 cm -1, ν (C-H alkyl ) 2980 cm -1, 2940 cm -1, 2882 cm Magnetic Measurements: The magnetic susceptibility measurements were obtained with the use of a Quantum Design SQUID magnetometer MPMS-XL housed at the Centre de Recherche Paul Pascal. This magnetometer works between 1.8 and 400 K for dc applied fields ranging from -7 to 7 T. Static magnetic measurements were performed on a polycrystalline sample of mg introduced in a polyethylene bag ( cm). For these experiments, the magnetic data were corrected for the sample holder (plastic bag) and the diamagnetic contribution. The photomagnetic experiments were performed with different light sources coupled through an optical fiber directed into the magnetometer cavity. Powdered samples of and 6.87 mg were packed in thermoformed straw maintained at 3 mm to the optical fiber. For all these experiments, the magnetic data were corrected for the sample holder and the diamagnetic contribution. The irradiation is obtained with two LEDs at 505 nm (10 and 25 mw/cm 2 ) and 850 nm (10, 25 and 40 mw/cm 2 ). The thermal heating of the compound under irradiation was systematically corrected and did not exceed 0.2 K. 1.3 Electron Paramagnetic Resonance: High-field EPR data were collected in a transmission-type spectrometer based on a 17-T superconducting magnet at National High Magnetic Field Laboratory. A phase-locked Virginia Diodes 13-GHz solid-state oscillator, followed by a cascade of frequency multipliers, was employed as the microwave source. Frequencies over the range GHz were generated. Ushio lamp USH-102D was used for sample irradiation with a Newport glass filter FSR-BG39. In X- band EPR a powder sample was placed in a standard 3-mm Quartz tube and was irradiated through the cavity window for a few minutes. In high-field EPR a hexagonally S3

4 shaped crystal of ca. 6-mm length/width and 1 mm height was placed in the waveguide with its hexagonal plane perpendicular to the magnetic field. 3 The same lamp and filter as in the X-band experiment were used and the light followed the waveguide that normally transmits the microwaves, irradiating the hexagonal crystal plane. The time of irradiation was 2 hours. EPR spectra were collected afterwards with light turned off. 1.4 Other Physical Measurements. Infrared spectra were obtained on a Perkin-Elmer Spectrum 400 FTIR spectrometer equipped with an attenuated total reflectance (ATR) accessory. Carbon, hydrogen, and nitrogen analyses were obtained from the Microanalytical Laboratory of the University of California, Berkeley. Reference 1. Hassan, N.; Weinberger, P.; Mereiter, K.; Werner, F.; Molnar, G.; Bousseksou, A.; Valtiner, M.; Linert, W. Inorg. Chim. Acta, 2008, 361, Franke, P.L.; Haasnoot, J. G.; Zuur, A. P. Inorg. Chim. Acta, 1982, 59, 5-9 (1982). 3. Ozarowski, A. & McGarvey, B. R Inorg. Chem., 1989, 28, S4

5 Figure S1 Temperature dependence of the χ ΜT product (with χ Μ being the molar magnetic susceptibility defined as M/H per complex at 0.4 K/min) for [Fe(ptz) 6 ](BF 4 ) 2 between 1.8 and 270 K (H = 5000 Oe) before (black) and after (green) 505-nm irradiation (10 mw/cm 2 ) at 10 K for 9 hours (see Fig. S2). The solid lines are guides for the eye. Figure S2 Time evolution of the χ ΜT product (with χ Μ being the molar magnetic susceptibility defined as M/H per complex) for [Fe(ptz) 6 ](BF 4 ) 2 during the 505-nm irradiation (10 mw/cm 2 ) at 10 K (H = 5000 Oe). S5

6 Figure S3 Frequency dependence of the in-phase (χ', top) and out-of-phase (χ", bottom) components of the ac magnetic susceptibility for [Fe(ptz) 6 ](BF 4 ) 2 in its HS α* phase at 1.9 K at different dc field between 0 and 3000 Oe. The solid lines are guides for the eye. S6

7 Figure S4 Temperature dependence of the χ ΜT product (with χ Μ being the molar magnetic susceptibility defined as M/H per complex at 0.4 K/min) for [Fe(ptz) 6 ](BF 4 ) 2 after thermal quenched at 10 K (> 100 K/min; H = 5000 Oe) before (black) and after (green) 505-nm irradiation (10 mw/cm 2 ) at 10 K for 7.5 hours (see Fig. S5). The solid lines are guides for the eye. Figure S5 Time evolution of the χ ΜT product (with χ Μ being the molar magnetic susceptibility defined as M/H per complex) for [Fe(ptz) 6 ](BF 4 ) 2 after thermal quenched at 10 K (> 100 K/min; H = 5000 Oe) during the 505-nm irradiation (10 mw/cm 2 ) at 10 K. S7

8 Figure S6 Temperature dependence of the in-phase (χ', top) and out-of-phase (χ", bottom) components of the ac magnetic susceptibility for [Fe(ptz) 6 ](BF 4 ) 2 in its HS β* phase in zero-dc field at ac frequencies of 1, 10, 100, 1000, 1500 Hz. The solid lines are guides for the eye. S8

9 Figure S7 Frequency dependence of the in-phase (χ', top) and out-of-phase (χ", bottom) components of the ac magnetic susceptibility for [Fe(ptz) 6 ](BF 4 ) 2 in its HS β* phase at 1.9 K at different dc field between 0 and 7000 Oe. The solid lines are guides for the eye. S9

10 Figure S8 Field dependence of the characteristic relaxation frequency of the magnetization for [Fe(ptz) 6 ](BF 4 ) 2 in its HS β* phase at 1.9 K. This plot is deduced from Figures S7. The solid line is a guide for the eye. Figure S9 Scaled frequency dependence of the out-of-phase component of the ac susceptibility normalized by the zero-frequency in-phase susceptibility (taken experimentally at 1 Hz) at different temperatures between 1.9 and 5 K (with H ac = 5 Oe and H = 2000 Oe) for [Fe(ptz) 6 ](BF 4 ) 2 in its HS β* phase. β is the scaling parameter equals to 1 for the data at 1.9 K. S10

11 Figure S10 High-field EPR spectra of a crystal sample of [Fe(ptz) 6 ](BF 4 ) 2, collected at 10 K and 216 GHz in its LS β phase (blue spectrum) and in its HS β* phase (red spectrum). The resonance observed at ca. 1.6 T after irradiation moves with the microwave frequency (for example with ν = GHz it is observed at 4.85 T) showing an almost constant g effective value of Accordingly, it can be assigned to a M S = 4 transition with an intrinsic g value of ~2.3. This observation provides unambiguous evidence of negative sign of zero-field splitting parameter D (see Figure S11). No other resonances, which could be attributable to Fe 2+, were observed. The signal marked with an * is due to frozen O 2, often encountered in HF EPR spectra. Magnetic field was perpendicular to the hexagonal crystal plane, which appears to be the z orientation. S11

12 Figure S11 Energy levels of the HS β* phase for [Fe(ptz) 6 ](BF 4 ) 2, calculated with the magnetic field parallel to z axis (with D = cm -1 (-21.3 K), E = cm -1 (-1.4 K) and g z = 2.3). An arrow of thermal energy k B T at 5 K demonstrates that only M S = ±2 can be populated at 5 K in the case of negative D. The only transition to be observed is the M S = 4 transition. It is also seen that a huge microwave frequency would be required to invoke an allowed transition from M S = ±2 to M S = ±1. If the sign of D were positive, this diagram would be reversed and M S = 4 transition could not be observed. Also, the energies that allowed to observe M S = 4 transition in high-field EPR and X-band EPR are marked out. S12

13 Figure S12 X-band EPR spectra collected for [Fe(ptz) 6 ](BF 4 ) 2 at 5 K. In the LS β phase (blue), only traces of high-spin Co(II) and Mn(II) are seen. Note: the trace amount of Co(II) and Mn(II) impurities are from starting materials and haven t been introduced intentionally. The red plot represents the spectrum of the HS β* phase after light irradiation (details in section 1.3). The M S = 4 transition in Fe 2+, which was observed in high-field EPR shows up again nicely below 0.1 T. The purple plot is the spectrum of HS α* phase after light irradiation (details in section 1.3). In this case, the resonance shifts to a lower resonance field and becomes more complicated, which can be interpreted as an increase of transverse anisotropy E due to lower symmetry. S13

14 Figure S13 Frequency dependence of the in-phase (χ', top) and out-of-phase (χ", bottom) components of the ac magnetic susceptibility for [Fe(ptz) 6 ](BF 4 ) 2 after thermal quenched at 10 K (> 100 K/min), measured at 1.9 K under 2000 Oe before irradiation at 505 nm or after irradiation at 850 nm (25 mw/cm 2, 8 hours) (red) and after irradiation at 505 nm (green, 10 mw/cm 2, 3 hours). The solid lines are guides for the eye. S14

15 Figure S14 Illustration of a ternary information storage scheme utilizing light actuated singlemolecule magnets. Starting with all molecules in the low-spin or 0 state (blue), a 1 or 2 could be written by application of the light-induced electron spin state trapping (LIESST) effect in the presence of an external magnetic field, resulting in a high-spin state magnetized in either an up (green) or down (red) direction. The data could then be read using the magneto-optical Kerr effect (MOKE), by detecting the change of phase of the applied polarized light, with no phase shift indicating a 0, a positive phase shift representing a 1, and a negative phase shift representing a 2. Data could be erased by application of the reverse LIESST effect (i.e., irradiation with lower-frequency light) to return all molecules to their low-spin configuration. S15