Pulse EPR and ENDOR Study of Manganese Doped - ACS Publications

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Pulse EPR and ENDOR Study of Manganese Doped [(CH)NH][Zn(HCOO)] Hybrid Perovskite Framework 3

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Mantas Šim#nas, Lucyna Macalik, Kestutis Aidas, Vidmantas Kalendra, Daniel Klose, Gunnar Jeschke, Miroslaw Maczka, Georg Völkel, Juras Banys, and Andreas Pöppl J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b09990 • Publication Date (Web): 17 Nov 2017 Downloaded from http://pubs.acs.org on November 17, 2017

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The Journal of Physical Chemistry

Pulse EPR and ENDOR Study of Manganese Doped [(CH3)2NH2][Zn(HCOO)3] Hybrid Perovskite Framework Mantas Šim˙enas,∗,† Lucyna Macalik,‡ Kęstutis Aidas,† Vidmantas Kalendra,† Daniel Klose,¶ Gunnar Jeschke,¶ Mirosław Mączka,‡ Georg Völkel,§ J¯uras Banys,† and Andreas Pöppl§ Faculty of Physics, Vilnius University, Sauletekio av. 9, LT-10222 Vilnius, Lithuania, Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box-1410, PL-50-950 Wroclaw 2, Poland, ETH Zürich, Department of Physical Chemistry, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland, and Faculty of Physics and Earth Sciences, Universität Leipzig, Linnestrasse 5, D-04103 Leipzig, Germany E-mail: mantas.simenas@ff.vu.lt Phone: +370 5 2234537. Fax: +370 5 2234537

∗

To whom correspondence should be addressed Faculty of Physics, Vilnius University, Sauletekio av. 9, LT-10222 Vilnius, Lithuania ‡ Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box-1410, PL-50-950 Wroclaw 2, Poland ¶ ETH Zürich, Department of Physical Chemistry, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland § Faculty of Physics and Earth Sciences, Universität Leipzig, Linnestrasse 5, D-04103 Leipzig, Germany †

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Abstract We present a pulse electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) study of a manganese doped [(CH3 )2 NH2 ][Zn(HCOO)3 ] dense metal-organic framework which exhibits a structural phase transition at 163 K. The echo-detected field sweep Mn2+ EPR spectrum of the low-temperature phase is in a perfect agreement with the previous continuous-wave EPR results, while the spectrum of the disordered phase reveals a significant EPR transition dependent relaxation. The 1H

ENDOR pattern indicates several protons in the vicinity of the Mn2+ ion. The

experimental ENDOR spectrum is successfully simulated using the proton hyperfine tensors calculated by the density functional theory. A multifrequency electron spin echo envelope modulation (ESEEM) spectroscopy shows a peculiar signal which is unaffected by the external magnetic field. The modulation depth of this signal starts to decrease above 40 K coinciding with the temperature at which the methyl groups of the (CH3 )2 NH2+ cations start to rotate. We also relate the methyl group motion to the decrease of the phase memory time of the Mn2+ ions. The temperature dependence of the longitudinal relaxation time indicates a coupling between the Mn2+ electron spins and a hard optical phonon mode. This mode undergoes a damping at the phase transition point.

Introduction Metal-organic frameworks (MOFs) draw significant attention of the scientific community due to their broad potential applicability. 1,2 These hybrid crystalline compounds contain metal ion nodes that are connected by organic linkers into various porous structures. 3 Usually transition metal or lanthanide cations are used as metal centers due to their high coordination number and the ability to adapt different coordination geometries. 4 Most of the exceptional MOF properties originate from their pronounced porosity which can be utilized for gas adsorption and similar applications. 5–8

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Recently, a new subclass of these materials called dense MOFs emerged. 9 In these compounds the pores are densely occupied with organic cations that cannot leave the framework. Representatives of dense MOFs are [A][M(HCOO)3 ] formate frameworks where A+ is a molecular cation (e.g. (CH3 )2 NH2+ ) and M2+ is usually a transition metal ion. 10–14 In such compounds the metal nodes are interconnected by the formate HCOO– linkers into semicuboid pores. In the center of each cuboid, a single A+ cation is situated and H-bonded with oxygen atoms of the MO6 octahedra. Many members of the formate frameworks demonstrate structural phase transitions some of which are from the paraelectric to the ferroelectric phase. 14–16 In addition, some of these compounds containing paramagnetic transition metal ions show a long-range magnetic order making them potential single-phase multiferroics 11,13,17–20 - a rare and highly attractive material property. 21 The first reported and the most thoroughly studied members of the hybrid metal formate frameworks are [(CH3 )2 NH2 ][M(HCOO)3 ] (DMAM) compounds, where M is one of the following cations: Mn2+ , Fe2+ , Co2+ , Ni2+ , Cu2+ , Zn2+ or Mg2+ . 10,11,22 These compounds exhibit a structural phase transition at the transition temperature Tc of about 160-180 K (except for the Mg2+ analogue for which the much higher Tc of 270 K was observed). The X-ray diffraction (XRD) data of the high temperature (HT) phase (T > Tc ) indicates that these compounds crystallize into the perovskite topology. 10,11 Here each dimethylammonium cation (CH3 )2 NH2+ (DMA+ ) occupies one of the three positions within a metal-formate cavity (see Figure 1a). Due to a significant degree of crystal twinning, the XRD methods encounter challenges while determining the low temperature (LT) structure (T < Tc ) of these frameworks. Sánchez-Andújar et al. managed to solve the LT structure of DMAMn and assigned it to the monoclinic Cc space group which is noncentrosymmetric as necessary for the ferroelectricity to occur. 23,24 In this phase each DMA+ cation occupies a single position within a cavity (see Figure 1b), and the system exhibits the long-range electric order. However, it was found that the monoclinic centrosymmetric C2/c group can also relatively well describe the XRD data. 23

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(a)

(b) O C H N Mn

Figure 1: The (a) HT and (b) LT structures of DMAMn. In (a) the DMA+ cation is represented as a superposition of three orientations (hydrogen atoms are omitted for clarity). Structures taken from Ref. 23 The ordering in these compounds was investigated using various other experimental techniques such as heat capacity, 10,11,25 heat flow 24,26 and pyrocurrent 18,27,28 measurements, second-harmonic generation, 29 dielectric, 10,11,19,23,30,31 infrared, Raman, 32 NMR 31,33–35 as well as electron paramagnetic resonance (EPR) 36–38 spectroscopies. Most of these methods detected a first-order order-disorder phase transition at Tc . However, a proper ferroelectric hysteresis loop was obtained only for the deuterated DMACo compound. 39 In addition, our recent single crystal continuous-wave (CW) EPR study with the applied external electric field raised serious concerns about the ferroelectric origin of the ordered phase in DMAZn. 38 The uncertain nature of the LT phase in these compounds stimulates further attention to this problem. In our previous CW EPR studies of the manganese doped DMAZn framework we have successfully shown that the paramagnetic Mn2+ probes replace Zn2+ ions in the lattice and form MnO6 octahedra. 37,38 The spin Hamiltonian parameters of the Mn2+ ions were found to be sensitive to the structural changes occurring at Tc . The temperature dependence of the axial zero-field splitting (zfs) parameter revealed a strong first-order phase transition. 37 The single crystal EPR study confirmed the crystal twinning model proposed by the XRD study. 38 The CW EPR methods can probe only the first coordination sphere of the paramagnetic 4


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center, and thus the much weaker hyperfine (hf) interactions of the distant nuclei are usually not resolved. Such interactions can be detected by the more powerful pulse EPR and pulse electron nuclear double resonance (ENDOR) spectroscopies. 40,41 This allows investigating a much broader spatial region around the paramagnetic probe. In this study we use these pulse techniques as well as the density functional theory (DFT) calculations to further investigate the LT structure, dynamics and motion of the DMA+ cations in the manganese doped DMAZn framework.

Experimental and Computational Methods Sample Preparation ZnCl2 (99%, Fluka), MnCl2 (99%, Sigma-Aldrich), 2.0 M solution of (CH3 )2 NH in methanol (Sigma-Aldrich), methanol (99.8%, Sigma-Aldrich) and formic acid (98%, Fluka) were commercially available and used without further purification. DMAZn: 0.05 Mn2+ mol% powder sample (1) was obtained by a slow diffusion method. In a typical experiment, 16 mL methanol solution containing 12.8 mmol of (CH3 )2 NH and 12.8 mmol of formic acid was placed at the bottom of a glass tube (9 mm inner diameter). 16 mL methanol solution containing 1.5992 mmol of ZnCl2 and 0.0008 mmol of MnCl2 was gently added on this solution. The tube was sealed, and after 5 days colorless crystals were harvested. The previously reported powder XRD study 37 of 1 confirmed that this compound corresponds to DMAZn (see Figure S1 in the Supporting Information, SI).

EPR and ENDOR Spectroscopy A Bruker E580 EPR spectrometer was used for pulse EPR and ENDOR measurements at Xband microwave (mw) frequency (∼ 9.5 GHz). Pulse EPR experiments at Q (∼ 34 GHz) and W-band (∼ 95 GHz) frequencies were performed with Bruker E600 and E680 spectrometers. The two pulse (2p) echo-detected field sweep, 2p (pulse sequence: π/2 −τ −π −τ −echo) and 5



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three-pulse (3p) (π/2 − τ − π/2 − τ ′ − π/2 − τ − echo) electron spin echo envelope modulation (ESEEM) 42 experiments were recorded using nonselective mw pulses. The typical π/2 mw pulse length was tπ/2 = 16 ns. The baselines of the obtained ESEEM time domain (TD) patterns were corrected by subtracting exponential decays. The remaining signals were Fourier transformed to the frequency domain (FD) spectra. The longitudinal relaxation time T1 was determined using the inversion recovery pulse sequence. 41 The temperature dependent relaxation time measurements were performed on heating. For most of the ENDOR experiments, the Mims pulse sequence 43 was used with the mw and radiofrequency pulse lengths of tπ/2 = 16 ns and tRF = 10 µs, respectively. To avoid the suppression effects (blind spots), 41 the 3p ESEEM and Mims ENDOR experiments were performed using different values of the interpulse delay τ . The interpulse delay τ in 2p experiments was 100 ns. All simulations of the spectra were performed using EasySpin 5.1.5 simulation software 44 .

DFT Calculations All computations of the proton hf coupling tensors were carried out using the unrestricted DFT framework as implemented in the Orca 3.0.3 program. 45 The experimental LT crystal structure of DMAMn MOF 23 was used for calculations. Figure S2 depicts the used geometry which includes a single Mn2+ ion coordinated by six formate linkers and surrounded by eight nearest DMA+ cations. The total charge of this system is +4. The PBE0 exchange-correlation functional 46 along with the EPR-II double-zeta basis set 47 was selected for the organic moieties, whereas the aug-cc-pVDZ basis set 48 was adopted for the metal atom. The resolution of the identity approach, the so-called RIJCOSX method 49 as implemented in Orca, was utilized using the auxiliary aug-cc-pVDZ basis set in order to speed up the hybrid DFT calculations. The Lebedev 770 points grid was selected for the computation of the two-electron integrals. The tight criterion for the SCF procedure was chosen. The Fermi contact and spin dipolar contributions to the hf coupling tensors were computed, so that we did not account for the spin-orbit contribution. 6


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Results and Discussion Echo-Detected Field Sweep The X-band echo-detected field sweep EPR spectra of 1 recorded at 170 K and 6 K are presented in Figure 2. They correspond to the powder patterns of the Mn2+ ions with the 3d5 electronic configuration and the high-spin 6 S5/2 ground state (electron and nuclear spins are S = 5/2 and IMn = 5/2). The 6 K spectrum is in a perfect agreement with our previous CW EPR studies and corresponds to the LT phases of 1. We simulated this spectrum using the previously determined electron Zeeman, hf and fine structure (fs) parameters of the Mn2+ center in DMAZn (see Figure 2b). 37,38 Simulation parameters are presented in SI. (a) 170 K

mS = ±1/2, ±3/2, ±5/2

Simulation

mS = ±1/2

Simulation Experiment

(b) 6 K

Simulation Experiment

250

300 350 400 Magnetic field B (mT)

450

Figure 2: X-band two-pulse echo-detected field sweep spectra of 1 recorded at (a) 170 K and (b) 6 K. Simulations indicated in red were obtained by taking into account all fs transitions, while blue simulation corresponds to the central fs transitions. The arrow indicates the field position at which most of the pulse EPR and ENDOR experiments were performed. See SI for simulation parameters. We also tried to simulate the HT spectrum measured at 170 K using the parameters obtained from the CW EPR experiment. 37 A clear mismatch between the spectra can be seen 7



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in Figure 2a, since the experimental pattern does not contain broad spectral wings outside the central EPR transition (ms = − 12 ↔ 12 , here mS denotes the magnetic electron spin quantum number). As discussed in our previous study, these wings correspond to the fs (ms = ± 23 ↔ ± 21 and ± 25 ↔ ± 32 ) which can be described using highly distributed zfs parameters. 37 The hopping motion of the DMA+ cations in the HT phase causes distinct positions of these cations in the vicinity of the MnO6 groups. This leads to differently distorted octahedra (distribution of zfs parameters) and unresolved spectral wings in the CW EPR spectrum above Tc . The outer fs transitions are absent in the experimental echo-detected spectrum, while it simultaneously shows the forbidden hf lines indicating a substantial zfs of the Mn2+ centers. At first glance, these two observations contradict each other. A plausible explanation of this problem is that the phase memory time is substantially shorter for the outer fs transitions. Therefore, these transitions cannot be detected in the echo-detected field sweep experiment. This assumption is supported by simulation of only the central fs transition using the same set of the Mn2+ ion parameters. The spectrum obtained in such a way is in agreement with the experiment (Figure 2a). The EPR transition dependent relaxation time was also recently observed in frozen solutions of Gd3+ . 50 This behavior was assigned to the fluctuating (transient) zfs. The energy levels of the outer fs transitions are much more susceptible to these fluctuations resulting in much shorter relaxation compared with the central transition. In our case, such fluctuations occur due to the DMA+ cation hopping which affects the MnO6 octahedra. The hf interactions between the Mn2+ ions and distant nuclei are too weak to be resolved in the field sweep spectra. Therefore, we performed ENDOR and ESEEM experiments which can detect these small interactions allowing us to further study the LT phase of 1.

ENDOR Spectroscopy We used Mims ENDOR spectroscopy to investigate the local environment of the Mn2+ probes. Figure 3d presents the 1H ENDOR spectrum of 1 recorded at 325 mT, τ = 144 ns 8


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and 6 K. It consists of well resolved hf splittings at the perpendicular edge singularities of the powder pattern indicating several proton species in the close vicinity of the Mn2+ ions. The splittings corresponding to the parallel components of the 1H hf coupling tensors are poorly resolved and thus are not explicitly presented. We also performed the Davies ENDOR measurements of 1, but the recorded 1H spectrum shows much worse signal-to-noise ratio (see Figure S3).

(a)

HCOO‒

Sim.

‒

(b)

(c)

HCOO and + (CH3)2NH2 Sim.

HCOO‒ and + (CH3)2NH2 (modified) Sim. mS = ±½ manifolds

(d)

-4

Exp.

-2 0 2 4 Frequency ν – νH (MHz)

Figure 3: (a-c) Simulated and (d) measured (6 K) X-band 1H Mims ENDOR pattern of 1 at 325 mT and τ = 144 ns. The simulation in (a) was performed by taking into account only protons from the HCOO– linkers, while in (b) protons from the (CH3 )2 NH2+ cations were also included. The 1H hf couplings used in (a) and (b) simulations were obtained from the DFT calculations. The simulation in (c) was performed using slightly adjusted 1H hf couplings of the methyl groups (lines indicated by the arrows). The bottom spectrum in (c) was obtained taking into account only the ms = − 21 ↔ 12 transition and neglecting the zfs. 9



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The obtained ENDOR pattern was simulated using the 1H hf coupling tensors obtained by the DFT calculations (see Computational Methods). The calculated tensors are listed in Table S1 (SI). In the simulations we also used spin Hamiltonian parameters of the Mn2+ centers previously determined in the CW EPR studies. 37,38 First of all, the simulation was performed by using only the protons from the formate HCOO– linkers. The corresponding ENDOR pattern is presented in Figure 3a indicating that the strongest experimentally observed hf coupling originates from these linkers. Note that the same hf splitting was observed in our previous studies of manganese doped [NH3 (CH2 )4 NH3 ][Zn(HCOO)3 ]2 and [CH3 NH2 NH2 ][Zn(HCOO)3 ] dense MOFs which also contain MnO6 octahedra connected via the formate anions. 51,52 This demonstrates that such hf coupling could be used as a fingerprint to identify whether the Mn2+ centers successfully replaced the diamagnetic ions in similar frameworks. The simulation was further improved by including protons from the DMA+ cations surrounding the Mn2+ probe. The simulated pattern is presented in Figure 3b revealing a satisfactory agreement with the experiment. An even better match was obtained after we slightly adjusted the calculated hf couplings of protons from the methyl groups of the DMA+ cations (see Figure 3c and SI for more details). This modification corresponds to a decrease of the Mn-H distance by about 0.08 Å. The small adjustment of the 1H hf couplings could be justified, since the crystal structure of DMAMn 23 MOF was determined at 100 K while the ENDOR pattern was recorded at 6 K. Another possible origin of this discrepancy is that our DFT calculations are based on the LT structure of DMAMn compound, while the experiments are performed for the manganese doped DMAZn framework. We also simulated the ENDOR spectrum using a spin system with an effective S = 1/2 electron spin to account for only the ms = − 21 ↔

1 2

transition. The obtained results are

presented in Figure 3c revealing an absence of the lines at |ν − νH | & 3 MHz (here νH is the Larmor frequency of protons). This indicates that the origin of these lines is not the strongly coupled 1H species, but the nuclear transitions in the |mS | > 1/2 spin manifolds. 10


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Slight changes of the central part of the spectrum are also observed although the agreement with the experimental pattern remains acceptable. The comparison between the pulse ENDOR experiment and the DFT-based simulations confirms the successful incorporation of the Mn2+ probes at the Zn2+ lattice sites in DMAZn framework. More importantly, our ENDOR data verifies the proton positions determined by the XRD. This confirms the refinement of the LT space group of these frameworks as the monoclinic noncentrosymmetric Cc. 23

ESEEM Spectroscopy The local environment of the Mn2+ ions in 1 was further probed using 2p and 3p ESEEM spectroscopy. The 2p ESEEM TD and FD signals recorded at 325 mT and 10 K are presented in Figure 4a and c. The TD pattern shows superimposed short and long period oscillations. The corresponding FD spectrum reveals three peaks at about 2.1, 13.8 and 27 MHz. The line at 13.8 MHz corresponds to protons, while the high-frequency bump at roughly 2νH is the proton combination peak. 41 The 2p ESEEM TD signal decays with a relatively short phase memory time resulting in broad and poorly resolved FD lines. In contrast, the TD signal in a 3p ESEEM experiment is limited by the much longer transverse nuclear or longitudinal electron relaxations providing narrower FD lines. 41 The 3p ESEEM TD traces and FD spectra obtained at 325 mT and 10 K are presented in Figure 4b and d. Measurements were performed using the interpulse delays τ = 108 ns and 144 ns. The obtained TD decay for τ = 108 ns also exhibits superimposed modulations of short and long period oscillations. The corresponding FD spectrum consists of much narrower lines, although the internal structure of the proton line is still hardly resolved. The width of the proton peak is about 3 MHz which is in agreement with the 1H hf couplings determined by the ENDOR spectroscopy. The low-frequency signal consists of several lines below 3 MHz with the most intense peak at 1.85 MHz. The TD decay recorded for τ = 144 ns reveals only the long period modulation, since the proton signal is absent due 11



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2p ESEEM

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3p ESEEM τ = 108 ns

0.5 1.0 Time τ (μs) 1

τ = 144 ns

(b)

(a) 1.5

0

2 4 Time τʹ (μs) 1

(d)

(c)

6

H

H 1

τ = 108 ns

H

τ = 144 ns

0

10 20 Frequency ν (MHz)

0

30

5 10 15 Frequency ν (MHz)

Figure 4: X-band 2p and 3p ESEEM (a)-(b) TD and (c)-(d) FD signals of 1 recorded at 325 mT and 10 K. 3p ESEEM experiments were performed at τ = 108 ns and 144 ns. The proton signals are indicated in the FD spectra.

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to the suppression effect at the 1H Larmor frequency. 41 The resulting FD spectrum consists of the low-frequency signal which coincides with the τ = 108 ns case. A possible origin of the low-frequency signal could be nitrogen

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N nuclei (IN = 1) of the

DMA+ cations. To investigate this, we performed 3p ESEEM measurements at X, Q and W-band mw frequencies. The obtained spectra are presented in Figure 5. They reveal that the observed lines are independent on the external magnetic field. This surprising result indicates that this signal cannot originate from the nitrogen nuclei, since one would expect a significant nuclear Zeeman effect for a system with nuclear spin I > 0.

X-band 325 mT Q-band 1195 mT W-band 3350 mT

0

1


5

Figure 5: Low-frequency 3p ESEEM signal recorded at 325, 1195, 3350 mT and 10 K. Several NMR studies revealed that the motion of the DMA+ cations persists in the ordered phase of DMAZn. 33–35 Thus, we performed ESEEM experiments at different temperatures to check whether we can observe the influence of these motional effects on the echo modulation. The temperature dependent 2p and 3p ESEEM spectra are presented in Figure 6 (see SI for the TD traces) indicating that the low-frequency signal starts to diminish above 40 K and completely disappears at about 70 K. Figure 7 reveals the temperature dependence of the modulation depth parameter k of this signal, which was determined from the 3p ESEEM TD traces at 400 ns (see inset for the definition of k). A sudden decrease of the modulation depth is observed above 40 K, while k = 0 above 70 K. Note that Besara et 13



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al. 33 observed a glassy behavior in DMAZn below 40 K, while Asaji et al. 34 reported a small anomaly in the spin-lattice relaxation time of 1H at 79 K.

(a)

1

(b)

H 2p ESEEM

1

H

80 K

3p ESEEM 80 K

70 K 60 K

70 K

50 K

60 K 50 K

40 K 40 K 30 K 30 K 20 K

20 K

10 K 10 K

0


0


Figure 6: Temperature dependent X-band (a) 2p and (b) 3p ESEEM FD spectra of 1 recorded at 325 mT. 3p ESEEM experiments performed at τ = 108 ns. Spectra are normalized to the proton line. The hopping motion of the DMA+ cation should be frozen on the ESEEM time scale below Tc as demonstrated by dielectric 30 and NMR 34,35 spectroscopies. However, the reorientation of the methyl groups around the C3 symmetry axes is still expected in the ordered phase. 34 As determined by NMR, the characteristic time of this motion is about 10−7 s at 70 K. 33,34 The highest peak of the low-frequency ESEEM signal is roughly at 2 MHz which is in a good agreement with the time scale of the methyl group rotation. Thus, we speculate that the decrease of the modulation depth of the low-frequency signal may be related to the averaging of some anisotropic magnetic interactions due to the onset of the methyl group rotations. The precise origin of this unusual low-frequency ESEEM signal remains unknown and will be thoroughly investigated in a separate study using samples with different isotopes.

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Modulation depth k

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0.15 1.0 a

0.10 0.5

b

0.05

k=

0

0 0

a a+b

1 τʹ (μs)

2

20 40 60 80 Temperature T (K)

Figure 7: Temperature dependence of the modulation depth k of the low-frequency X-band 3p ESEEM signal of 1. The inset explains the definition of the parameter k.

Relaxation Time Measurements We also performed measurements of the phase memory time Tm and the longitudinal relaxation time T1 of the Mn2+ centers to further investigate the low-temperature phase of 1. Figure 8a reveals a monotonous decrease of Tm with increasing temperature. The relaxation time starts to diminish at about the same temperature as the modulation depth of the low-frequency 3p ESEEM signal. Thus, we relate the decrease of Tm to the methyl group rotations that cause fluctuations of the Mn2+ ion magnetic environment. The phase memory time at the phase transition point exhibits anomalous behavior which is related to the critical dynamics of the order parameter fluctuations or enhanced motion of the DMA+ cations above Tc (see Figure S5). The anomaly of Tm was previously observed in tris-sarcosine calcium chloride (TSCC), 53 KH3 (SeO3 )2 54 and similar materials. Note that we were unable to reliably measure Tm above 180 K due to too fast relaxation. The phase memory relaxation rate exhibits the Arrhenius-type behavior and can be described using the following equation: −1 −Ea /kB T Tm−1 = Tm,∞ e ,

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(1)


−5.0

5.8 meV

−5.5 −6.0

300

8 16 24 −1 1000/T (K )

Tc

150 (a) 0

40

80 120 160 Temperature T (K)

2.4∙10

−3

2.1∙10

−3

1.8∙10 155 160 165 170 T (K)

−3

Tc

−1

17 meV

−2

10

−3

10

−4

(b)

−1

450

10

Longitudinal relaxation −1 −1 rate T 1 (ns )

ln(Tm−1, ns−1)

−4.5

T 1 (ns )

600

Phase memory time Tm (ns)

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

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–1

( 2khνT )

2

T1 = B csch

opt

B

–1

10

T1 = A T

−5

200

40 80 120 160 Temperature T (K)

Figure 8: Temperature dependence of (a) the phase memory time and (b) the most probable longitudinal relaxation rate of the Mn2+ centers in 1. The inset in (a) shows the Arrheniustype behavior of Tm−1 below Tc . The curves in (b) are the total (black) and separate (blue and red) contributions to the longitudinal relaxation rate. The inset in (b) emphasizes the behavior of the longitudinal relaxation rate about Tc . If not indicated, the error bars are smaller than data points. Measurements performed at 325 mT and X-band mw frequency. −1 where Ea denotes the activation energy of the motional process and Tm,∞ is the phase memory

relaxation rate at infinite temperature. In the LT phase, we identified two processes with the activation energies Ea = 17(1) meV and Ea = 5.8(4) meV. The inset in Figure 8a presents the corresponding fits. Note that the same analysis provided Ea of 15 meV in the related Mn2+ doped [CH3 NH2 NH2 ][Zn(HCOO)3 ] perovskite. 52 We also observed a third process in the HT phase with an activation energy of about 78 meV (see Figure S5b). The obtained activation energy in the HT phase is similar to the values obtained by NMR for the methyl group rotations in DMAZn framework. 33–35 However, the energies of the LT phase are significantly smaller. Such activation energies are frequently observed for quantum tunnelling motion of the methyl groups. 55 This may indicate a substantial contribution of such process to the observed low-temperature phase memory relaxation in 1. This effect will be investigated in more detail in a separate study using deuterated compounds. The longitudinal relaxation time T1 was determined by the inversion recovery pulse sequence. The measured magnetization kinetics were fit using a recovery function for the

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continuously distributed relaxation times (see Refs. 52,56 for more details). The obtained temperature dependence of the most probable longitudinal relaxation rate T1−1 is presented in Figure 8b. The experimental data was approximated using the following equation: 54

T1−1 = AT + Bcsch2 (hνopt /2kB T ),

(2)

where the first term describes a direct (one-phonon) relaxation process with the acoustic lattice phonons. The second term takes into account a Raman (two-phonon) process which involves the optical phonon branch of frequency νopt . A and B are constants. The best fit provided νopt = 3.5(3) × 1012 Hz which corresponds to 118(10) cm−1 . Note that IR and Raman study reports a similar frequency of the lattice phonons that involve metal-oxygen octahedra in the DMAZn and DMAFe frameworks. 32 The behavior of the longitudinal relaxation rate around the phase transition point is presented in the inset of Figure 8b. A small dip of T1−1 is observed at Tc , which we verified by several measurements. Such a minimum of the longitudinal relaxation rate at the phase transition was measured for many other ferroelectric or related compounds such as rochelle salt, 56 KH3 (SeO3 )2 , 54 betaine phosphite, 57 TSCC, 58 triglycine sulfate (TGS) 59 and lead titanate. 60 Note that in our previous study of the Mn2+ doped [CH3 NH2 NH2 ][Zn(HCOO)3 ] framework we also observed indications of the same behavior. 52 A minimum of T1−1 occurs due to the enhanced damping of the optical phonon mode νopt which governs the longitudinal relaxation. The observed increase of the mode damping may originate from the coupling with the relaxational mode responsible for the phase transition 56 or due to the structural changes occurring at Tc .

Summary and Conclusions We used pulse EPR and ENDOR spectroscopies to study the Mn2+ doped [(CH3 )2 NH2 ][Zn(HCOO)3 ] perovskite framework which exhibits a structural order-disorder phase transition. The pulse 17



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methods allowed us to probe a much wider environment of the Mn2+ ions compared to the CW EPR spectroscopy. The echo-detected field sweep EPR spectra of Mn2+ centers were recorded for the HT and LT phases of the framework. The LT spectrum was simulated using the spin Hamiltonian parameters taken from previous CW EPR studies. Analysis of the HT phase spectrum revealed much faster phase memory relaxation of the outer fs transitions. This behavior was assigned to the fluctuating zfs of the Mn2+ ions in the HT phase of the framework. These fluctuations are caused by the hopping motion of the DMA+ cations confirming a tight interaction between the two subsystems of the material. The X-band 1H Mims ENDOR spectrum displayed several proton species in the vicinity of the Mn2+ probes. We simulated the experimental spectrum using the proton hf coupling tensors obtained by the DFT calculations of the DMAMn framework. A good agreement between the experimental and simulated ENDOR patterns verifies the structural framework model and the proton positions that are often difficult to determine accurately by the XRD methods. The ESEEM spectroscopy revealed a signal of weakly coupled protons in agreement with the ENDOR results. We also observed a remarkable low-frequency ESEEM signal which is unaffected by the external magnetic field. The modulation depth of this signal starts to decrease above 40 K and reaches zero at 70 K. This temperature range and the frequency of the signal suggest that the modulation disappears due to the rotations of the methyl groups of the DMA+ cations. However, the precise origin of this peculiar ESEEM signal remains obscured and demands further attention. The relaxation time measurements of the Mn2+ ions revealed further information about the motion of the DMA+ cations and the dynamics of the metal-formate lattice. We observed a monotonous decrease with increasing temperature of the phase memory time in the ordered phase of the framework. This behavior was assigned to the methyl group motion which causes fluctuations of the local Mn2+ ion environment. We identified two motional mechanisms in

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the LT phase with the activation energies of 17(1) meV and 5.8(4) meV. Indication of a third process with much higher activation energy was observed in the HT phase. We found that the longitudinal relaxation of the Mn2+ ions is dominated by the direct process with the acoustic lattice phonons and the two-phonon Raman process with the optical lattice mode of 118(10) cm−1 frequency. We also observed a small anomalous dip of the longitudinal relaxation rate at Tc which is caused by the increased damping of the hard optical mode governing the relaxation.

Acknowledgement This work was supported by the COST Action MP1308-TO-BE (STSM grant) and by the Research Council of Lithuania (Project TAP LLT-4/2017). The authors thank High Performance Computing Center "HPC Sauletekis" of Vilnius University Faculty of Physics for the computational resources.

Supporting Information Available Additional XRD, DFT, EPR and ENDOR data.

This material is available free of charge

via the Internet at http://pubs.acs.org/.

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