Light Switchable Magnetism in a Coordination Polymer

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Light switchable magnetism in a coordination polymer heterostructure combining the magnetic potassium chromiumhexacyanochromate with the light-responsive rubidium cobalthexacyanoferrate Olivia N. Risset, Tatiana V. Brinzari, Mark W Meisel, and Daniel R. Talham Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.5b02785 • Publication Date (Web): 27 Aug 2015 Downloaded from http://pubs.acs.org on September 3, 2015

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Chemistry of Materials

Light switchable magnetism in a coordination polymer heterostructure combining the magnetic potassium chromiumhexacyanochromate with the light-responsive rubidium cobalthexacyanoferrate Olivia N. Risset †, Tatiana V. Brinzari ‡, Mark W. Meisel ‡,*and Daniel R. Talham †,* †

Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, USA Department of Physics and the National High Magnetic Field Laboratory, University of Florida, Gainesville, FL 32611-8440, USA

‡

ABSTRACT: Core-shell particles with the Prussian blue analogues rubidium cobalthexacyanoferrate as core and potassium chromiumhexacyanochromate as shell, {Rb0.2Co[Fe(CN)6]0.7}0.8@{K0.1Cr[Cr(CN)6]0.7}0.2·4H2O, are prepared and shown to exhibit light-switchable magnetism, persistent up to 125 K.

Physical properties that can be switched through external stimuli such as temperature, pressure and light are keys to developing novel recording technologies. Magneto-optical effects, for example, could be used in energyassisted magnetic recording1-6 and the use of circularly polarized laser pulses has provided new advances.7,8 One remarkable family of bistable materials whose magnetic properties can be reversibly switched with light is found in the cyanide-bridged coordination polymers.9-15 For example, cobalt-octacyanotungstate and ironoctacyanoniobate networks16-18 as well as Prussian blue analogues cobalt hexacyanoosmate19 and cobalt hexacyanoferrate20 (CoFe-PBA), undergo a charge-transfer induced spin transition (CTIST) that can be either optically or thermally activated. Recently, heterostructures that combine the photoswitchable CoFe-PBA with ferromagnetic components that order at higher temperature were developed,21-29 leading to synergistic effects between the two materials and giving rise to unprecedented behavior. Taking advantage of a structural change associated with the CoFe-PBA CTIST (ΔV/V ~ 10%),30 the elastic process couples across the heterostructure interface to induce a magnetomechanical response31 in the non-light-sensitive component resulting in magnetization changes.29 Using nickel hexacyanochromate as the magnetic component, lightinduced effects have been observed up to 70 K.21-24 Here, this new mechanism is employed to optically switch magnetism at temperatures well above liquid nitrogen temperature, for the first time taking advantage of the entire temperature range over which the CoFe-PBA is photoswitchable. Heterostructure particles of formula {Rb0.2Co[Fe(CN)6]0.7}0.8@{K0.1Cr[Cr(CN)6]0.7}0.2·4H2O comprised of CoFe-PBA and chromium hexacyanochromate (CrCr-PBA), a ferrimagnet with TC = 190 K - 240 K de-

pending upon composition,32 show a persistent photoinduced decrease in magnetization up to 125 K, the temperature above which the CoFe-PBA relaxes to the lowspin ground state. The CoFe-PBA particles used for the cores are synthesized as a self-stabilized suspension in water. Adapting the procedure described by Catala and coworkers33 for the synthesis of PBA nanoparticles, uniform particles are obtained with characteristic lengths of 50 - 500 nm. The absence of stabilizer on the surface of the particles allows the CoFe-PBA to act as a suitable platform for the growth of CrCr-PBA. The conventional method to prepare PBA core@shell structures requires the slow addition of low concentration solutions of the shell precursors to a suspension of the core particles,34 favoring heterogeneous precipitation while preventing side nucleation. However, the CrCr-PBA does not immediately precipitate under these conditions, presumably due to a higher solubility than other PBAs previously grown as shells.24,26,34-36 Nevertheless, the CoFe-PBA@CrCr-PBA heterostructures are obtained after the CoFe-PBA particles are left stirring for three days in an aqueous solution containing the CrCrPBA precursors. Infrared spectroscopy shows features for two distinct PBAs while conveying the valence states of the metal ions in the CoFe-PBA core (Supporting information, Figure S1). Specifically, the FT-IR spectrum of uncoated CoFe-PBA in the cyanide stretching region displays characteristic bands at 2165, 2110 and 2098 cm-1, assigned to CoII-NC-FeIII (high spin), CoIII-NC-FeII (low spin) and CoII-NC-FeII (reduced) sites, respectively,20,37-38 and the presence of mixed valences is in agreement with the cobalt:iron ratio in the cores (Co:Fe = 1.4). After depositing the shell, an additional shoulder appears at 2185 cm-1, characteristic of CrCr-PBA.32 At the same time, the distribution of the

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observed due to the photo-generated high spin CoII-FeIII pairs in the CoFe-PBA core (Figure 2, Figure S5).20 Above the ordering temperature of the CoFe-PBA, TC ~ 25 K, a crossover occurs and a decrease in magnetization is observed for the light state.

-5

5

0.8

0.4 0.0 0

hν 0

50

Dark Light 50

100 150 200 250 300 Temperature [K]

100 150 200 250 300 Temperature [K]

Figure 2. Field-cooled magnetization vs. temperature for CoFe-PBA@CrCr-PBA under an applied field of 100 G in the dark state (black) and in the light state after irradiation at 5 K (red). Data in the light state are collected after the light is II turned off. Magnetic ordering of the photo-generated Co III Fe moments induces an increase in magnetization up to 25 K, above which the change in magnetization becomes negative. The photo-induced decrease in magnetization is attributed to magnetomechanical coupling, mediated by the interface between CoFe-PBA and CrCr-PBA. The changes are thermally reversed above 140 K.

1.0 0.8

hν

Dark Light B = 100 G

-5

The TEM images provide insights into the morphology of the particles (Figure 1) while EDS results confirm the chemical assignments and component segregation within the heterostructures (Supporting Information). The CoFe-PBA forms as well defined cubic particles, nearly uniform in size, 172 ± 13 nm (Supporting information, Figure S2 and S3). After being exposed to the CrCr-PBA precursors, the CoFe-PBA seeds become coated with nanoparticles, 9 ± 2 nm in size, identified as CrCr-PBA by EDS (Supporting information, Figures S3 and S4). While the heterogeneous growth of CrCr-PBA nanoparticles on the surface of the CoFe-PBA cores is evident, Figure 1 also pictures a few small aggregates identified as the single phase CrCr-PBA. Current synthetic efforts are directed toward controlling the precipitation of CrCr-PBA to prevent side nucleation. The following magnetic measurement studies were performed on the as-prepared samples. Magnetic data provide direct evidence that the two materials are coupled and behave cooperatively due to a shared interface. The magnetic response of the CoFePBA@CrCr-PBA heterostructures in the dark state and after irradiation with white light is shown in Figures 2 and 3. In the dark state, the temperature dependent field-cooled magnetization shows a first feature around TC ~ 205 K in agreement with the ferrimagnetic ordering of the CrCr-PBA.32 A second increase in magnetization around 15 K is attributed to the ordering of remaining high spin sites in CoFe-PBA, as is often observed for this system as a result of an incomplete high spin to low spin conversion when cooling through the thermal CTIST. Upon irradiation at 5 K, an increase in magnetization is

B = 100 G

1.2

-5

10

0

Figure 1. TEM images of CoFe-PBA@CrCr-PBA heterostructures. Well-defined and uniform CoFe-PBA cubes are coated with CrCr-PBA. Along with heterogeneous precipitation, side nucleation of CrCr-PBA occurs as indicated by the presence of nanosized particles aggregates (red arrow). Scale bars are 200 nm for the left frame and 100 nm for the right frame.

Magnetization [10 emu G]

15 Magnetization [10 emu G]

different charge states of the CoFe-PBA core changes, as illustrated by an increase in intensity of the bands attributed to the low spin and reduced species accompanied by a diminished high spin state signal. These observations suggest a partial reduction of the CoFe-PBA by the Cr II precursor, consistent with the electrochemical potentials of the hexaaquachromium (II) ions and the ferricyanide within the PBA structure. Surprisingly, CoFe-PBA treated only with CrCl2 does not undergo a similar change in oxidation state, suggesting that the redox process occurs as the CrCr-PBA grows at the surface of the CoFePBA particles.

Magnetization [10 emu G]

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0.6 0.4 0.2 100

150 200 250 Temperature [K]

300

Figure 3. Field-cooled magnetization vs. temperature for CoFe-PBA@CrCr-PBA under an applied field of 100 G in the dark state (black) and in the light state after irradiation at 80 K (red). Data in the light state are collected after the light is turned off. Irradiation induces a persistent decrease in magnetization indicative of a photo-response in the normally light-insensitive CrCr-PBA. This new behavior arises from magnetomechanical effects at the interface between CoFePBA and CrCr-PBA. The bistable heterostructures relax to the ground state upon warming above CoFe-PBA TCTIST.

The magnetization decrease is attributed to the CrCrPBA in response to the spin state transition in the CoFePBA and is the first time photo-induced magnetization


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changes have been observed in this high-ordering temperature PBA. The photomagnetic response in the normally light insensitive component is attributed to magnetomechanical effects31 mediated by the interface between the two materials.21,24,25,29,39 Upon irradiation, the structural changes associated with the CTIST in CoFe-PBA are transmitted to the CrCr-PBA nanoparticles coating the surface, thereby altering the local anisotropy of the magnetically ordered lattice and resulting in the distortion/realignment of the CrCr-PBA magnetic domains. The persistent changes in the CrCr-PBA are maintained up to 125 K, the temperature at which the CoFe-PBA high spin state begins a thermally-assisted dynamical relaxation to the low-spin ground state,40 as shown in Figure 4 which plots the change in magnetization, Mdark – Mlight, normalized to the magnetization in the dark state. The mechanism requires efficient mechanical coupling, so a physical mixture of the two components does not exhibit similar photomagnetic behavior.24,25 The heterostructure is required. Taking advantage of the high ordering temperature of CrCr-PBA, the heterostructure allows light-switchable magnetization above liquid nitrogen temperature and over the full temperature range of the light-induced state of the CoFe-PBA core. For example, Figure 3 shows a significant decrease in magnetization upon irradiation at 80 K (Figure 3, Figure S5). The lightinduced effects are still persistent until thermally reversed starting at 125 K. 0.4

(Mdark-Mlight)/Mdark

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Irradiation at 5 K Irradiation at 80 K

0.3 B = 100 G 0.2 0.1 0.0 50

100 150 Temperature [K]

200

Figure 4. ΔMagnetization (dark - light), normalized to the magnetization in the dark state, Mdark, plotted as a function of temperature when irradiated at 5 K or at 80 K.

In summary, a new light-switchable material, designed from coordination polymers, shows photomagnetic switching at temperatures well above liquid nitrogen. Bistable CoFe-PBA@CrCr-PBA heterostructures exhibit a persistent light-induced decrease in magnetization that can be recovered by thermal treatment above the CTIST thermal relaxation temperature of T ~ 140 K. New strategies such as this for materials that switch magnetism with light open up new avenues toward the design of technologically viable magneto-optical sensors and switches.

ASSOCIATED CONTENT

Supporting Information. Experimental details, FTIR spectra, TEM of the starting core particles, particle size dispersions, EDS data and time dependent magnetization upon irradiation are available as Supporting Information.

AUTHOR INFORMATION Corresponding Author * [email protected] * [email protected]

ACKNOWLEDGMENT This work was supported by the National Science Foundation via DMR-1005581 and DMR-1405439 (DRT), DMR-1202033 (MWM) and DMR-1157490 (NHMFL), and by the UF Division of Sponsored Research. Technical assistance from M. W. Turvey during data acquisition is gratefully acknowledged as are contributions of Matthieu F. Dumont and Elisabeth S. Knowles to the early stages of this work.

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Light Switchable Magnetism in a Coordination Polymer

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