Supporting information for. Magnetic, Dielectric and Phonon Properties

Transcription

1 Supporting information for Perovskite Metal-Formate Framework of [NH 2 -CH + -NH 2 ]Mn(HCOO) 3 ]: Phase Transition, Magnetic, Dielectric and Phonon Properties Mirosław Mączka,*, Aneta Ciupa, Anna Gągor, Adam Sieradzki, Adam Pikul, Bogusław Macalik, and Marek Drozd Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Box 40, Wrocław 2, Poland Institute of Physics, Wrocław University of Technology, WybrzeŜe, Wyspiańskiego 27, Wrocław, Poland * m.maczka@int.pan.wroc.pl

2 Table S. Crystal data, data collection and refinement results for FMDMn at 355, 295, and 0 K. Crystal Data Chemical formula C 4 H 8 MnN 2 O 6 C 4 H 8 MnN 2 O 6 C 4 H 8 MnN 2 O 6 M r Crystal system, space group Rhombohedral, R-3c Monoclinic, C2/c Monoclinic, C2/c Temperature (K) a, b, c (Å) (2), (2), (8) (7), (4), (4) α, β, γ ( ) 90, 90, () 8.5 () V (Å 3 ) () () () Z Radiation type Mo Kα Mo Kα Mo Kα µ (mm - ) (7), (4), (4) Crystal size (mm) Data Collection T min, T max 0.87, , ,.000 No. of measured, independent and observed [I > 2σ(I)] ref. 4275, 365, , 067, , 06, 984 R int (sin θ/λ) max (Å - ) Refinement R[F 2 > 2σ(F 2 )], wr(f 2 ), S 0.020, 0.067, , 0.076, , 0.050,.06 No. of reflections No. of parameters max, min (e Å -3 ) 0.6, , ,

3 Table S2. Selected angles ( o ) in FMDMn. 355K 295 K 0 K O i Mn O ii 80.0 O I Mn O 80.0 () O I Mn O 80.0 () O i Mn O iii (4) O2 I Mn O (5) O Mn O2 I (3) O ii Mn O iii (4) O2 I Mn O 87.0 (5) O Mn O2 I 93.7 (3) O iv C O 27.2 (2) O2 I Mn O3 I (6) O2 I Mn O3 I (3) N C2 N v 20.0 O2 I Mn O () O2 I Mn O () O2 Mn O3 I 94.7 (6) O2 Mn O3 I (3) O I Mn O3 I 86.6 (6) O I Mn O3 I (3) O Mn O3 I (6) O Mn O3 I (3) O3 I Mn O (2) O3 I Mn O () O3 C O3 III 25.7 (3) O3 C O3 III 25. (2) O C2 O2 IV 27. (2) O C2 O2 IV 25.4 () N C3 N V 24.9 (4) N C3 N V 23.9 (2) N C3 N2 7.5 (2) Symmetry code(s): (i) x-y, x, -z+; (ii) -x+y, -x, z; (iii) -x, -y, -z+; (iv) -x-2/3, -x+y-/3, -z+7/6; (v) -x+y-, -x, z; (I)- x+/2, y-/2, -z+/2; (II) -x+/2, -y+/2, -z; (III) -x+, y, -z+/2; (IV) -x+/2, y+/2, -z+/2; (V) -x, y, -z-/2; 3

4 Table S3. The correlation diagram showing the correspondence between the optical modes in the R 3 c and C2/c structures of FMDMn. The data for the C2/c structure are given in parentheses. Note that for the C2/c structure there are two crystallographically independent HCOO - ions occupying sites of C 2 and C symmetry. Selection rules state that A g and E g (A g and B g ) modes are Raman-active, A 2u and E u (A u and B u ) modes are IR-active whereas A 2g and A u modes are silent. ion vibration Free ion symmetry Site symmetry Factor group symmetry HCOO- C 2v C 2 (C 2 ) D 3d (C 2h ) (C ) ν, ν 2 or ν 3 A A (A) (A) A g +E g +A u +E u (A g +A u ) (A g +B g +A u +B u ) ν 4, ν 5 or ν 6 B B (B) (A) A 2g +E g +A 2u +E u (B g +B u ) (A g +B g +A u +B u ) T A + B + B 2 A+2B (A+2B) (3A) L A 2 + B + B 2 A+2B (A+2B) (3A) A g +2A 2g +3E g +A u +2A 2u +3E u (A g +2B g +A u +2B u ) (3A g +3B g +3A u +3B u ) A g +2A 2g +3E g +A u +2A 2u +3E u (A g +2B g +A u +2B u ) (3A g +3B g +3A u +3B u ) FMD + C 2v C 2 (C 2 ) D 3d (C 2h ) ν s (NH 2 ) A +B A+B (A+B) (A g +B g +A u +B u ) ν as (NH 2 ) A +B A+B (A+B) (A g +B g +A u +B u ) δ(nh 2 ) A +B A+B (A+B) (A g +B g +A u +B u ) ρ(nh 2 ) A +B A+B (A+B) (A g +B g +A u +B u ) ω(nh 2 ) A 2 +B 2 A+B (A+B) (A g +B g +A u +B u ) τ(nh 2 ) A 2 +B 2 A+B (A+B) (A g +B g +A u +B u ) ν s (CN) A A (A) (A g +A u ) 4

5 ν as (CN) B B (B) (B g +B u ) δ(cn) A A (A) (A g +A u ) ν(ch) A A (A) (A g +A u ) δ(ch) B B (B) (B g +B u ) γ(ch) B 2 B (B) (B g +B u ) T A + B + B 2 A+2B (A+2B) (A g +2B g +A u +2B u ) L A 2 + B + B 2 A+2B (A+2B) (A g +2B g +A u +2B u ) Mn 2+ S 6 (C i ) D 3d (C 2h ) A u (A u ) E u (2A u ) A u +A 2u (A u +B u ) 2E u (2A u +2B u ) 5

6 Table S4. IR and Raman frequencies (in cm - ) of FMDMn and suggested assignments. a Raman Raman IR IR assignment 400 K 5 K 470 K 5 K 3069w, 3028w 3063vw, 3034vw 3253m 3287sh, 3203m ν(nh 2 ) 350w,34w ν(nh 2 ) ν(ch) 3060m 3035m, 3003sh ν(nh 2 ) 2960w 2972sh, 2940vw combination bands 2864m, 2854sh 287m, 2860w 2854w 2870w, 2860w ν (HCOO - ) 2723w 2727vw 2722vw 2735vw, 2724vw, 2703vw, 2664vw 2ν 2 (HCOO - ) 732m 752sh, 74s δ(nh 2 ) 684w 689w ν as (CN) 575w,b 597vs 600vs, 559m ν 4 (HCOO - ) 428m 434m δ(ch) 37m 380w, 373s 374s 377s ν 5 (HCOO - ) 360s 365s, 357s 359s 365s, 36s ν 2 (HCOO - ) 343vw 343w combination band 322w 35w 322w 36s ρ(nh 2 ) 53w 52w 45vw 54vw ν s (CN) 083w 09w ρ(nh 2 ) 062w 063sh, 057w ν 6 (HCOO - ) 878vw, 858vw combination bands 82w γ(ch) 6

7 792m 797m 793m 798s ν 3 (HCOO - ) 777w 774w δ(cn) 737w,b 76m ω(nh 2 ) 589m 602m 582w 604m τ(nh 2 ) 286s 3s, 293sh T (Mn 2+ ) 245m 274m, 264vw, 249m 235m 272w, 260m, 252m, 246m T (Mn 2+ ) and T (HCOO - ) 22w 234m, 228m, T (Mn 2+ ) and T (HCOO - ) 220m 86sh 2w, 20w, 90w 77m 95w, 82sh, 76m T (HCOO - ) 52s 66w, 59m, 50vw 62w L(HCOO - ) 4w, 33w T (FMD) 22w, 3vw L(FMD) 86s 05m 02vw L(HCOO - ) 45w 46w L(HCOO - ) a Key: s, strong; m, medium; w, weak; vw, very weak; sh, shoulder; b, broad 7

8 Figure S. Powder XRD patterns for the as-prepared bulk sample of FMDMn with the calculated one based on the single crystal structures at 295 K. 8

9 Figure S2. DSC traces for FMDMn in heating (red) and cooling mode (blue). 9

10 Figure S3. (a) The molecular diagram for FMDMn in the high temperature phase, T=355 K, R 3 c space group. Atoms from the asymmetric unit are labelled. (b) The content of the asymmetric unit in FMDMn with the atom numbering scheme, T=0K, C2/c space group.

11 Figure S4. FT-Raman spectra of FMDMn recorded at various temperatures corresponding to the whole spectral range cm -.

12 Figure S5. IR spectra of FMDMn recorded at various temperatures corresponding to the spectral range cm -.

13 Figure S6. IR spectra of FMDMn recorded in Apiezon N suspension (CsI pellet) at temperatures K ( K) corresponding to the spectral range cm - ( cm - ).

14 Figure S7. Temperature evolution of 434, 35 and 602 cm - mode Raman frequencies. The vertical lines indicate the temperature at which FMDMn undergoes the phase transition.

15 Figure S8. Temperature evolution of selected IR frequencies. The vertical lines indicate the temperature at which FMDMn undergoes the phase transition.

16 Figure S9. Temperature evolution of FWHM of (a) lattice (b) C-H and (c) ν 2 (HCOO - ) and ν 5 (HCOO - ) Raman modes. The vertical lines indicate the temperature at which FMDMn undergoes the phase transition.

17 Figure S0. Temperature evolution of (a) ν 3 (HCOO - ), (b) ω(nh 2 ) and (c) τ(nh 2 ) mode IR frequencies. The vertical lines indicate the temperature at which FMDMn undergoes the phase transition.