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 430074, People s Republic of China. Wuhan National High Magnetic Field Centre & School of Physics, Huazhong University of Science and Technology, Wuhan, Hubei 430074, 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 77843-3255, 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 400-4000 cm 1 on a Nicolet 5DX spectrometer (KBr pellets). Magnetic susceptibility measurements were carried out in the temperature range of 2 300 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
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 0.025 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 (0.1 0.1 0.1 mm) and 2 (0.1 0.1 0.1 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-1815174 (1), and CCDC-1815175 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/datarequest/cif.
Table S1. Crystal data of fresh sample and sample with methanol.
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 687.65 683.66 Crystal system Tetragonal Tetragonal a/ Å 18.142(3) 18.096(3) b/ Å 18.142(3) 18.096(3) c/ Å 43.988(9) 44.219(9) α/ 90 90 β/ 90 90 γ/ 90 90 Unit cell volume/å 3 14478(5) 14480(5) Temperature/K 173(2) 173(2) Space group I4 1 /a I4 1 /a Z 16 16 No. of reflections measured 9701 7380 No. of independent reflections 9701 7380 R int 0.0874 0.0667 Final R 1 values (I > 2σ(I)) 0.0874 0.0682 Final wr(f 2 ) values (I > 2σ(I)) 0.2723 0.2114 Final R 1 values (all data) 0.0981 0.0885 Final wr(f 2 ) values (all data) 0.2852 0.2275 Table S2. Selected Bond Lengths (Å) and Angles ( ) for fresh sample and sample with methanol.
Fresh (1) Co1 N4 1 2.142(2) Co1 N4 2 2.142(2) Co1 N1 3 2.146(2) Co1 N1 2.146(2) Co1 N5 3 2.123(3) Co1 N5 2.123(3) Co2 N2 2.132(3) Co2 N2 4 2.132(3) Co2 N6 2.125(6) Co2 N6 4 2.125(6) Co2 N3 5 2.140(3) Co2 N3 6 2.140(3) N4 1 Co1 N4 2 91.59(12) N4 2 Co1 N1 89.35(9) N4 1 Co1 N1 3 89.36(9) N4 2 Co1 N1 3 175.92(10) N4 1 Co1 N1 175.92(10) N1 Co1 N1 3 89.97(13) N5 Co1 N4 1 87.48(9) N5 3 Co1 N4 2 87.48(9) N5 3 Co1 N4 1 90.62(10) N5 Co1 N1 88.54(10) N5 Co1 N1 3 93.38(10) N5 3 Co1 N1 93.38(10) N5 3 Co1 N1 3 88.54(10) N5 Co1 N5 3 177.28(13) N4 1 Co1 N1 175.92(10) N3 6 Co2 N3 5 92.61(16) N2 Co2 N2 4 90.60(16) N2 4 Co2 N3 5 176.48(18) N2 Co2 N3 5 88.49(12) N2 4 Co2 N3 6 88.50(12) N2 Co2 N3 6 176.48(18) N6 4 Co2 N2 4 91.08(16) N6 Co2 N2 91.08(16) N6 4 Co2 N2 88.25(17) N6 Co2 N2 4 88.25(17) N6 Co2 N6 4 179.06(18) N6 Co2 N3 5 88.36(17) N6 4 Co2 N3 6 88.36(17) N6 4 Co2 N3 5 92.29(17) N6 Co2 N3 6 92.29(17) With methanol (2)
Co1 N5 2.168(3) Co1 N5 1 2.168(3) Co1 N4 2 2.150(3) Co1 N4 3 2.150(3) Co1 N1 1 2.148(3) Co1 N1 2.148(3) Co2 N3 4 2.142(3) Co2 N3 3 2.142(3) Co2 N2 2.129(3) Co2 N2 5 2.129(3) Co2 N6 5 2.122(4) Co2 N6 2.122(4) N5 1 Co1 N5 178.96(13) N4 2 Co1 N5 88.45(10) N4 2 Co1 N5 1 92.28(10) N4 3 Co1 N5 1 88.45(10) N4 3 Co1 N5 92.28(10) N4 2 Co1 N4 3 90.07(13) N1 1 Co1 N5 1 87.89(10) N1 1 Co1 N5 91.38(10) N1 Co1 N5 1 91.37(10) N1 Co1 N5 87.90(10) N1 1 Co1 N4 2 89.53(10) N1 Co1 N4 2 176.31(10) N1 1 Co1 N4 3 176.31(10) N1 Co1 N4 3 89.53(10) N1 Co1 N1 1 91.11(13) N3 3 Co2 N3 4 91.59(15) N2 5 Co2 N3 3 176.62(13) N2 Co2 N3 4 176.62(13) N2 Co2 N3 3 88.94(10) N2 5 Co2 N3 4 88.94(10) N2 Co2 N2 5 90.73(14) N6 5 Co2 N3 3 88.04(12) N6 Co2 N3 3 92.10(13) N6 5 Co2 N3 4 92.10(13) N6 Co2 N3 4 88.04(12) N6 5 Co2 N2 5 88.60(13) N6 Co2 N2 88.61(13) N6 5 Co2 N2 91.25(13) N6 Co2 N2 5 91.25(13) N6 Co2 N6 5 179.79(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 ;
Figure S1. IR spectra of fresh sample, amorphous state and recovered sample with methanol. 1.6 M (Nµ B ) 1.2 0.8 0.4 0.0 2 K 3 K 4 K 5 K 0 1 2 3 4 5 6 7 H (T) 1.6 M (Nµ B ) 1.2 0.8 0.4 0.0 2 K 3 K 4 K 5 K 0 1 2 3 4 5 6 7 H (T) Figure S2. Field dependence of the magnetization for the suspensions of 1 (top) and
polycrystalline samples of 2 (bottom) at 2, 3, 4, 5 K. Solid lines indicate the best fits with the PHI program. 1.0 0.8 9 Hz 997 Hz 0.20 0.15 1.2 0.9 9 Hz 997 Hz 0.20 0.15 ' (cm 3 mol 1 ) 0.6 0.4 0.2 H ac = 2.5 Oe H dc = 0 Oe 0.10 0.05 '' (cm 3 mol 1 ) ' (cm 3 mol 1 ) 0.6 0.3 H ac = 2.5 Oe H dc = 0 Oe 0.10 0.05 '' (cm 3 mol 1 ) 0.0 0.00 0.0 0.00 2 4 6 8 10 T (K) 2 4 6 8 10 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 ) 0.25 0.20 0 Oe 200 Oe 400 Oe 600 Oe 800 Oe 1000 Oe 1500 Oe 2000 Oe 0.15 2500 Oe 3000 Oe 0.10 '' (cm 3 mol 1 ) 0.10 0.08 0.06 0.04 0 Oe 200 Oe 400 Oe 600 Oe 800 Oe 1000 Oe 1500 Oe 2000 Oe 2500 Oe 3000 Oe 0.05 0.02 0.00 1 10 100 1000 Frequency (Hz) 0.00 1 10 100 1000 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.
' (cm 3 mol 1 ) 0.8 0.6 0.4 '' (cm 3 mol 1 ) 0.25 2.0 K 2.2 K 2.4 K 0.20 2.6 K 2.8 K 3.0 K 3.3 K 0.15 3.6 K 4.0 K 4.5 K 0.10 5.0 K 5.5 K 6.0 K 0.05 0.2 1 10 100 1000 Frequency (Hz) 0.00 1 10 100 1000 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 ) 0.8 0.6 0.4 0.2 1 10 100 1000 Frequency (Hz) '' (cm 3 mol 1 ) 0.10 0.08 0.06 0.04 0.02 2.0 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 0.00 1 10 100 1000 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.
100 90 80 1 2 Weight / % 70 60 50 40 30 20 100 200 300 400 500 600 700 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 2.0 0.14402 0.79461 3.35529E-4 0.20942 2.2 0.1037 0.71114 2.51163E-4 0.20475 2.4 0.07356 0.65315 1.98127E-4 0.19668 2.6 0.05215 0.60248 1.60439E-4 0.17893 2.8 0.01099 0.56145 1.21819E-4 0.18798 3.0 4.30195E-10 0.52597 1.04377E-4 0.17017 3.3 7.27217E-10 0.47753 8.58819E-5 0.13618 3.6 6.71084E-10 0.44133 7.35215E-5 0.10986 4.0 9.72278E-10 0.39907 6.12731E-5 0.06428
4.5 2.40705E-9 0.35817 5.15367E-5 0.01126 5.0 7.51693E-9 0.32708 4.25943E-5 1.39468E-16 5.5 1.06801E-8 0.30114 3.56366E-5 1.87888E-16 6.0 1.44381E-8 0.27931 3.12655E-5 1.89186E-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 2.0 0.57269 0.79033 3.4225E-4 0.15634 2.2 0.4964 0.70479 2.36069E-4 0.16714 2.4 0.42769 0.65099 1.57869E-4 0.21522 2.6 0.38291 0.60132 1.24044E-4 0.19617 2.8 0.28443 0.56127 6.38423E-5 0.2421 3.0 0.25722 0.52143 5.74062E-5 0.18108 3.3 9.78967E-8 0.48095 1.6181E-5 0.26782 3.6 1.5518E-7 0.44411 1.61721E-5 0.23628 4.0 1.51716E-7 0.39724 2.01361E-5 0.1049 4.5 1.35096E-7 0.35676 2.0446E-5 0.0567 5.0 7.93731E-7 0.32344 2.14075E-5 4.35808E-16 5.5 1.08323E-6 0.29645 2.0223E-5 5.92369E-16 6.0 1.43048E-6 0.27436 1.92042E-5 7.68386E-16