Magnetic Metal-Organic Framework Exhibiting Quick and. Selective Solvatochromic Behavior Along With The Reversible

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1 Magnetic Metal-Organic Framework Exhibiting Quick and Selective Solvatochromic Behavior Along With The Reversible Crystal-to-Amorphous-to-Crystal Transformation Peng Hu,, Lei Yin,, Angelo Kirchon,, Jiangli Li, Bao Li,*, Zhenxing Wang,*, Zhongwen Ouyang, Tianle Zhang, and Hong-cai Zhou*, Key laboratory of Material Chemistry for Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei , People s Republic of China. Wuhan National High Magnetic Field Centre & School of Physics, Huazhong University of Science and Technology, Wuhan, Hubei , People s Republic of China. Department of Chemistry, Department of Materials Science and Engineering, Texas A&M Energy Institute, Texas A&M University, College Station, Texas , United States. Experimental sections Materials and General Methods. All starting materials were obtained commercially and were used without further purification. Elemental analyses for C, H, N were performed on a Perkin-Elmer 240Q elemental analyzer. The IR spectra were recorded in range of cm 1 on a Nicolet 5DX spectrometer (KBr pellets). Magnetic susceptibility measurements were carried out in the temperature range of K with a magnetic field of 1000 Oe on Quantum Design MPMS XL-7 magnetometer. High frequency electron paramagnetic resonance (HF-EPR) measurements were performed on a locally developed instrument with the pulsed-magnetic field. The

2 tetrapyridyl ligand was synthesized by a literature method (CrystEngComm, 2012, 14, 6049). Synthesis of [Co(NCS) 2 (L)] 2(H 2 O) CH 3 OH (1): CoSO 4 7H 2 O (0.1 mmol) and KSCN (0.2 mmol) were stirred in 5 ml methanol for 5 minutes, then the solution was filtered and 1 ml water was added to the filtrate. The resulting solution was placed in a test tube, above which layered 5 ml methanol, and then 5 ml methanol containing mmol L was layered on the top. After one week, glittering pink crystal were obtained (30% based on L). Anal. Calcd for dyhydrated C 28 H 32 CoN 6 O 7 S 2 : C, 48.91%, H, 4.69%, N, 12.22%; found C, 48.11%, H, 3.98%, N, 12.98%. Synthesis of [Co(NCS) 2 (L)] (CH 3 OH) 2 (2): The fresh sample of 1 was exposed in air, immediately, the pink sample became blue. After 1h, the blue sample was immersed in pure methanol solution and obtained the crystal sample re-loaded methanol molecules. Anal. Calcd for C 29 H 32 CoN 6 O 6 S 2 : C, 50.95%, H, 4.72%, N, 12.29%; found C, 49.98%, H, 5.15%, N, 13.01%. X-Ray Structural Determination. Diffraction data for 1 ( mm) and 2 ( mm) were collected were obtained via BL17B at Shanghai Synchrotron Radiation Facility (Shanghai, China) and processed with HKL3000.The structures of complexes were solved by direct methods, and the non-hydrogen atoms were located from the trial structure and then refined anisotropically with SHELXTL using a full-matrix leastsquares procedure based on F 2 values. The hydrogen atom positions were fixed geometrically at calculated distances and allowed to ride on the parent atoms. CCDC (1), and CCDC (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via

3 Table S1. Crystal data of fresh sample and sample with methanol.

4 Fresh (1) With methanol (2) Chemical formula C 27 H 24 CoN 6 O 4 S 2 CH 4 O 2(H 2 O) C 27 H 24 CoN 6 O 4 S 2 2(CH 4 O) Formula Mass Crystal system Tetragonal Tetragonal a/ Å (3) (3) b/ Å (3) (3) c/ Å (9) (9) α/ β/ γ/ Unit cell volume/å (5) 14480(5) Temperature/K 173(2) 173(2) Space group I4 1 /a I4 1 /a Z No. of reflections measured No. of independent reflections R int Final R 1 values (I > 2σ(I)) Final wr(f 2 ) values (I > 2σ(I)) Final R 1 values (all data) Final wr(f 2 ) values (all data) Table S2. Selected Bond Lengths (Å) and Angles ( ) for fresh sample and sample with methanol.

5 Fresh (1) Co1 N (2) Co1 N (2) Co1 N (2) Co1 N (2) Co1 N (3) Co1 N (3) Co2 N (3) Co2 N (3) Co2 N (6) Co2 N (6) Co2 N (3) Co2 N (3) N4 1 Co1 N (12) N4 2 Co1 N (9) N4 1 Co1 N (9) N4 2 Co1 N (10) N4 1 Co1 N (10) N1 Co1 N (13) N5 Co1 N (9) N5 3 Co1 N (9) N5 3 Co1 N (10) N5 Co1 N (10) N5 Co1 N (10) N5 3 Co1 N (10) N5 3 Co1 N (10) N5 Co1 N (13) N4 1 Co1 N (10) N3 6 Co2 N (16) N2 Co2 N (16) N2 4 Co2 N (18) N2 Co2 N (12) N2 4 Co2 N (12) N2 Co2 N (18) N6 4 Co2 N (16) N6 Co2 N (16) N6 4 Co2 N (17) N6 Co2 N (17) N6 Co2 N (18) N6 Co2 N (17) N6 4 Co2 N (17) N6 4 Co2 N (17) N6 Co2 N (17) With methanol (2)

6 Co1 N (3) Co1 N (3) Co1 N (3) Co1 N (3) Co1 N (3) Co1 N (3) Co2 N (3) Co2 N (3) Co2 N (3) Co2 N (3) Co2 N (4) Co2 N (4) N5 1 Co1 N (13) N4 2 Co1 N (10) N4 2 Co1 N (10) N4 3 Co1 N (10) N4 3 Co1 N (10) N4 2 Co1 N (13) N1 1 Co1 N (10) N1 1 Co1 N (10) N1 Co1 N (10) N1 Co1 N (10) N1 1 Co1 N (10) N1 Co1 N (10) N1 1 Co1 N (10) N1 Co1 N (10) N1 Co1 N (13) N3 3 Co2 N (15) N2 5 Co2 N (13) N2 Co2 N (13) N2 Co2 N (10) N2 5 Co2 N (10) N2 Co2 N (14) N6 5 Co2 N (12) N6 Co2 N (13) N6 5 Co2 N (13) N6 Co2 N (12) N6 5 Co2 N (13) N6 Co2 N (13) N6 5 Co2 N (13) N6 Co2 N (13) N6 Co2 N (16) S y m m e t r y t r a n s f o r m a t i o n s : 1 1-X,1/2-Y,+Z; 2-1/4+Y,3/4-X,-1/4+Z; 3 5/4-Y,-1/4+X,1/4+Z; 4 3/4+Y,7/4-X,-1/4+Z; 5 2-X,3/2-Y,+Z; 6 3 / 4 - Y, 1 / 4 + X, 1 / 4 + Z ;

7 Figure S1. IR spectra of fresh sample, amorphous state and recovered sample with methanol. 1.6 M (Nµ B ) K 3 K 4 K 5 K H (T) 1.6 M (Nµ B ) K 3 K 4 K 5 K H (T) Figure S2. Field dependence of the magnetization for the suspensions of 1 (top) and

8 polycrystalline samples of 2 (bottom) at 2, 3, 4, 5 K. Solid lines indicate the best fits with the PHI program Hz 997 Hz Hz 997 Hz ' (cm 3 mol 1 ) H ac = 2.5 Oe H dc = 0 Oe '' (cm 3 mol 1 ) ' (cm 3 mol 1 ) H ac = 2.5 Oe H dc = 0 Oe '' (cm 3 mol 1 ) T (K) T (K) Figure S3. Temperature dependence of the in-phase (χ') and out-of-phase (χ'') ac magnetic susceptibility for complex 1 (left) and 2 (right) under zero-dc field at 9 and 999 Hz. '' (cm 3 mol 1 ) Oe 200 Oe 400 Oe 600 Oe 800 Oe 1000 Oe 1500 Oe 2000 Oe Oe 3000 Oe 0.10 '' (cm 3 mol 1 ) Oe 200 Oe 400 Oe 600 Oe 800 Oe 1000 Oe 1500 Oe 2000 Oe 2500 Oe 3000 Oe Frequency (Hz) Frequency (Hz) Figure S4. Frequency dependence of out-phase (χ'') ac susceptibility under various dc fields at 2 K for complex 1 (left) and 2 (right). The solid lines are for eye guide.

9 ' (cm 3 mol 1 ) '' (cm 3 mol 1 ) K 2.2 K 2.4 K K 2.8 K 3.0 K 3.3 K K 4.0 K 4.5 K K 5.5 K 6.0 K Frequency (Hz) Frequency (Hz) Figure S5. Frequency dependence of in-phase (χ') (left) and out-phase (χ'') (right) ac susceptibility at various temperatures under 800 Oe for complex 1. The solid lines are for eye guide. ' (cm 3 mol 1 ) Frequency (Hz) '' (cm 3 mol 1 ) K 2.2 K 2.4 K 2.6 K 2.8 K 3.0 K 3.3 K 3.6 K 4.0 K 4.5 K 5.0 K 5.5 K 6.0 K Frequency (Hz) Figure S6. Frequency dependence of in-phase (χ') (left) and out-phase (χ'') (right) ac susceptibility at various temperatures under 800 Oe for complex 2. The solid lines are for eye guide.

10 Weight / % Temperature / Figure S7. TGA curves of complex 1 (red line) and 2 (blue line). Table S3. The parameters obtained by fitting Cole-Cole plot under 0.8 KOe for 1. T (K) χ S χ T τ α E E E E E E E E E E E E E

11 E E E E E E E E E E E-16 Table S4. The parameters obtained by fitting Cole-Cole plot under 0.8 KOe for 2. T (K) χ S χ T τ α E E E E E E E E E E E E E E E E E E E E E E E-16

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