Supplementary Material

for

Hierarchical cobalt-formate framework series with (412·63)(49·66)n (n = 1−3) topologies exhibiting slow dielectric relaxation and weak ferromagnetism

Ran Shang, Sa Chen, Ke-Li Hu, Ze-Chun Jiang, Bing-Wu Wang, Mohamedally Kurmoo, Zhe-Ming Wang, and Song Gao

Element analyses, powder X-ray diffraction (PXRD), FTIR spectra, UV-Vis reflectance spectra, and thermal analyses Element analyses of C/H/N were performed on an Elementar Vario EL analyzer. PXRD data of the three compounds were collected at room temperature for the bulk samples on a Rigaku Dmax 2000 diffractometer, and for the pressed tablet samples on an Agilent SuperNova Dual Atlas CCD diffractometer, all using Cu Kα radiation. FTIR spectra were recorded against pure samples on a Nicolet Magna 750 FT/IR spectrometer and UV-Vis reflectance ones on a SHIMADZU UV-VIS-3100 spectrometer using a BaSO4 background. Thermal analyses were performed on a TA SDT Q600 instrument at a rate of 5 °Cmin−1 under air atmosphere, and accurate DSC measurements on a TA Q100 DSC analyzer at a rate of 5 °Cmin−1 in nitrogen flow.

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Table S1. Detailed crystallographic data for the three compounds at room temperature Compound Formula Fw Temperature, K Crystal system Space group a, Å b, Å c, Å α, ° β, ° γ, ° V, Å3 Z Dc, g/cm3 μ (Mo Kα), mm−1 Crystal size, mm3 Tmax, Tmin θmin, θmax , ° No. of total reflections. No. of unique reflections Rint No. of observations [I≥2σ(I)] No. of parameters a R1,bwR2 [I≥2σ(I)] a R1,bwR2 (all data) Goodness of fit c Δρ, e/Å3 d Δ/σ, max., mean

bnCo C10H20Co2N2O12 478.14 293 Trigonal P⎯31c 8.5322(2) 8.5322(2) 13.3228(3) 90 90 120 839.94(3) 2 1.891 2.042 0.49×0.27×0.25 0.608, 0.507 4.12, 27.48 15334 649 0.0574 554 54 0.0238, 0.0668 0.0306, 0.0691 1.096 0.269, −0.364 0.000, 0.000

dptaCo C15H29Co3N3O18 716.20 293 Trigonal R⎯3c 8.4069(2) 8.4069(2) 61.921(3) 90 90 120 3790.0(2) 6 1.883 2.037 0.24×0.20×0.12 0.792, 0.713 3.84, 27.47 13053 969 0.0731 518 74 0.0300, 0.0710 0.0790, 0.0811 0.908 0.291, −0.564 0.000, 0.000

tptaCo C21H40Co4N4O24 968.29 290 Trigonal P⎯31c 8.3617(1) 8.3617(1) 28.3983(5) 90 90 120 1719.52(4) 2 1.870 1.996 0.25×0.23×0.23 0.641, 0.554 3.54, 27.49 25884 1329 0.0526 873 110 0.0260, 0.0705 0.0493, 0.0773 1.037 0.307, −0.298 0.000, 0.000

a. R1 = ∑||Fo|−|Fc||/∑|Fo|; b. wR2 = [∑w(Fo2−Fc2)2/∑w(Fo2)2]1/2; c. Maximum and minimum residual electron density; d. Maximum and mean shift/sigma.

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Table S2. Selected bond distances (Å) and bond angles (°), the N···O distances (Å) between the ammonium and the anionic framework, and the Co···Co distances (Å) via anti-anti formate bridges. Compound a Co−O b Co−O

bnCo 2.096(1)×6 2.100(1)×6

dptaCo 2.086(2)×6 2.103(2)×3, 2.105(2)×3

O−C C/N−C cis- O−Co−O trans- O−Co−O Co−O−C O−C−O N···O Co···Co

1.236(2)−1.237(2) 1.200(5)−1.605(7) 85.46(5)−94.54(5) 177.63(8)−180.00 125.6(1)−126.9(1) 126.7(2) 2.88−3.25 5.946

1.231(3)−1.243(3) 1.22(1)−1.55(1) 85.51(8)−94.49(8) 174.70(8)−180.00 124.6(2)−127.5(2) 124.9(4), 126.2(3) c 2.90−3.17, d3.42 5.927, 5.960

tptaCo 2.091(1)×6 2.092(1)×3, 2.110(1)×3 2.108(1)×6 1.228(2)−1.240(2) 1.224(6)−1.57(1) 85.78(5)−94.22(5) 174.26(5)−180.00 126.5(1)−129.3(1) 126.4(2), 126.5(2) 2.94−3.14 5.970, 6.015

a. for (412·63) node; b. for (49·66) nodes; c. for terminal NH3; d. for middle NH2.

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Table S3. IR absorption bands (cm−1) and their assignments for bnCo, dptaCo and tptaCo (s: strong, m: medium, w: weak, vw: very weak, sh: shoulder, br: broad) Assignment ν (N−H)

bnCo 3004 br, 2934 br

νs C−H stretch νs/as (N−H)

2852 m 2712 w, 2612 w, 2515 w 2102 w 1585 s, 1524 sh 1456 m 1372 m 1356 m 1270 w, 1171 w 1099 w, 1057 w, 1033 w 889 w, 803 m 744 w

2ν6 ν4 OCO stretch, asym ν −CH2− ν5 OCO deformation, asym ν2 OCO stretch, sym ν C−N ν6 out-of-plane deformation

ν3 OCO deformation, sym δ (N−H)

dptaCo 3103 br, 3009 br, 2931 w 2855 m 2715 w

1583 s 1464 w 1371 m 1358 m 1172 w 1078 w, 1028 w, 997 w 806 m 751 w

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tptaCo 3016 br, 2936 br 2854 m 2701 w

1581 s 1467 m, 1412 s 1370 m 1353 m 1163 w 1080 w, 1025 w 804 m 759 w

Table S4. Summary of the dielectric and magnetic properties of bnCo, dptaCo, and tptaCo. Magnetic data were reduced to per mole Co. Compound

bnCo

dptaCo

tptaCo

Dielectric properties (from ε’ data at 50 kHz if not specified, L/H: low/high temperature relaxations) 32.2 17.6 27.1 ε’300 K 270, 220−315 220, 190−240 215, 180−250 Tm, Tm range (500−1M Hz) (K) 5.0 6.0 6.5 ε’lowest T L: 190, 145−225 215, 182−249 TP, TP range (ε’’, 500−1M Hz) (K) 271, 229−316 H: 230, 189−256 −16 0.44, 1.7×10−16 0.54, 3.0×10 L: 0.32, 1.6×10−14 Ea (eV), τ0 (s), for relaxation H: 0.43, 1.4×10−15 Magnetic properties (from data under 100 Oe field if not specified) 3.85 3.75 C (cm3Kmol−1), Curie constant −60.5 −54.4 Θ (K), Weiss constant 3 −1 3.21 3.16 (χT)300 K (cm Kmol ) 3 −1 0.79, 10.7 0.84, 13 (χT)min (cm Kmol ), Tmin (K) 3 −1 10.81, 8.0 7.87, 10 (χT)max (cm Kmol ), Tmax (K) 3 −1 3.71 1.80 (χT)2 K (cm Kmol ) 3 −1 163 76 MFC (cm Gmol ) at 2 K, 10 Oe 3 −1 0.52, 0.16 0.15, 0.009 χ′p, χ′′p (cm mol ) at 10 Hz 9.9 12.5, 11.0 TN (K), based on ZFC/FC data 10.00 12.5, 11.3 Tp (K), on χ′ and χ′′ at 10 Hz 9.95 12.5, 11.3 0.97, 18 1.52, 20 HC (kOe), HSP (kOe) at 2 K 0.033, 0.60 0.017, 0.52 MR (Nβ), M50 kOe (Nβ) at 2 K g factor, derived from C values 2.87 2.83 −4.0 −3.6 J/kB (K), J/kB = 3Θ/[2zS(S+1)]

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3.90 −63.9 3.21 0.72, 11.5 0.76, 10.6 0.17 3.7 0.063, noisy 10.9 12.0 broad − 0.39, 33 0.0035, 0.49 2.88 −4.3

Fig. S1. PXRD patterns for the as-prepared and pressed samples of the three compounds and the simulated one based on their single crystal structures at room temperature.

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Fig. S2. The FTIR spectra (a) and UV-Vis reflectance spectra (b) of the three compounds.

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Fig. S3. Combined TGA-DSC (a) runs and DSC cycles (b) for the three compounds.

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Fig. S4. The atomic thermal ellipsoid presentation of the non-H atoms of polyammoniums in the framework cavities (metal ions and the formato linkages in thin red bonds), showing the thermal motions of the constituent atoms. Color scheme is the same as that in Fig. 1.

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Fig. S5. Additional magnetic data for the three compounds: (a) the 1/χ vs T plots for the data under 100 Oe field, with the Curie-Weiss fittings in black lines; (b) the χT vs T plots under 10 kOe field, and inset, the dFC/dT plots for FC data under 10 Oe field; (c and d) their temperature-dependent traces of ac susceptibilities at 10 Hz under zero dc field. The ac data at 100 and 1000 Hz are not included because the ac responses of the three materials are not frequency-dependent.

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