Magnetic Ordering in TCNQ-Based Metal-Organic Frameworks With Host-Guest Interactions

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1 Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers. This journal is the Partner Organisations 215 Magnetic Ordering in TCNQ-Based Metal-Organic Frameworks With Host-Guest Interactions Xuan Zhang, Mohamed Saber, Andrey P. Prosvirin, Joseph H. Reibenspies, Lei Sun, Maria Ballesteros-Rivas, Hanhua Zhao, Kim R. Dunbar * Department of Chemistry, Texas A&M University, College Station, TX , United States

2 Single crystal X-ray crystallography Single-crystal X-ray data were collected at 11 or 1 K on a Bruker APEX CCD diffractometer equipped with a graphite monochromated MoKα radiation source (λ=.7173 Å) or a Synchrotron source (λ= Å), respectively. Suitable crystals were affixed onto a nylon loop with Paratone oil and place in a cold steam of N 2 (g). The data sets were recorded by the -scan method and integrated followed by an absorption correction in the Bruker APEX II software package. Solution and refinement of the crystal structures were carried out using the SHELXT 1 and SHELXL 2 programs and the graphical interface Olex2. 3 Hydrogen atoms were placed at calculated positions. A summary of pertinent information relating to unit cell parameters are provided in Tables S1. CCDC , contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via The structure of 1 C 6 H 5 NO 2 was determined with a similar unit cell (tetragonal, a = , c = ) to the reported one at room temperature, 4 but was best refined in a different tetragonal space group namely P However, it should be noted that this space group is still somewhat ambiguous and the structure could only be refined isotropically due to twinning and disorder. Several data sets were collected on single crystals of 1 C 6 H 5 NO 2 from different batches of reactions but the same problem persisted. It is interesting to note from the electron density difference maps that, unlike the cases of benzene, toluene and aniline containing frameworks of 1 and 2 C 6 H 6 where the plane of the aromatic molecules are situated vertical to the M-TCNQ plane (Figure 3, left), the nitrobenzene molecule exhibits a face-to-face contact with the TCNQ moiety of the Fe-TCNQ network (Figure 3). Such a positioning indicates the presence of π-π stacking/electrostatic interactions between the TCNQ 2- anions and the polar nitrobenzene molecules. The perpendicular orientation of the nitrobenzene dipole moment to the TCNQ 2- molecule suggests an electrostatic interaction.

3 Table S1. Pertinent crystallographic data for 1 solvent. Compound 1 C 6 H 6 1 C 6 H 5 NH 2 1 C 6 H 5 CH 3 3 Empirical formula C 42 FeN 6 H 32 C 34 H 26 FeN 8 C 36 H 28 FeN 6 C 24 H 32 FeN 8 O 4 Formula weight Temperature/K Crystal system tetragonal tetragonal tetragonal triclinic Space group I4/mcm I4/mcm I4/mcm P-1 a/å (6) 12.34(2) (3) (15) b/å (6) 12.34(2) (3) (18) c/å (15) (4) (6) (2) α/ (3) β/ (3) γ/ (3) Volume/Å (4) 348.(13) 353.3(19) 685.(3) Z ρ calc g/cm μ/mm F() Crystal size/mm Radiation synchrotron (λ = MoKα (λ = synchrotron(λ = Mo Kα (λ =.41328).7173).41328).7173) 2Θ range for data collection/ to to to to 5.16 Index ranges Reflections collected Independent reflections -14 h 14, -14 k 14, -27 l h 14, -14 k 14, -27 l h 13, -13 k 13, -25 l [R int =.635, R sigma =.152] 838 [R int =.343, R sigma =.112] 689 [R int =.352, R sigma =.78] -8 h 8, -1 k 1, -13 l [R int =.546, R sigma =.745] Data/restraints/ parameters 835//6 838/59/6 689/11/ //172 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 =.598, wr 2 =.1639 R 1 =.774, wr 2 =.242 R 1 =.592, wr 2 =.1632 R 1 =.887, wr 2 =.2517 Final R indexes [all data] R 1 =.638, wr 2 =.1781 R 1 =.884, wr 2 =.2294 R 1 =.69, wr 2 =.1676 R 1 =.159, wr 2 =.268 Largest diff. peak/hole / e Å -3.65/ / / /-1.5 R 1 = Σ F o - F c / Σ F o. wr 2 = [Σw( F o - F c ) 2 / Σw(F o ) 2 ] 1/2. w =.75/(σ 2 (F o )+.1F o2 ).

4 Table S2. Summary of the structural parameters of 1 guest from single crystal X-ray studies. Guest Space group Fe-N(cyano) /Å Fe-N(pyridyl) /Å Fe-N-C(cyano) / TCNQ dihedral angle / Methanol [a] P-42 1 c 2.144(2) 2.184(2) 16.(1) 3.84 Benzene I4/mcm 2.139(2) 2.192(4) 166.(2) Aniline I4/mcm 2.128(4) 2.192(8) 164.5(4) Toluene I4/mcm 2.139(3) 2.196(4) 165.7

5 1 methanol. Figure S1. ZFC and FC of the as-synthesized Fe(TCNQ)(4,4 -bpy) guest.

6 Figure S2. ZFC and FC of 3.

7 Figure S3. The magnetization hysteresis of the Fe(TCNQ)(4,4 -bpy) MOFs at 1.8 K in different aromatic solvents.

8 Magnetization (B.M Magnetization at 1.8 K Magnetic field (Oe) Figure S4. The magnetization of the Fe(TCNQ)(4,4 -bpy) C 5 H 5 NO 2 at 1.8 K This is shown as an example and other samples of Fe(TCNQ)(4,4 -bpy) guest showed similar behavior.

9 Figure S5 The in-phase (solid symbol) and out-of-phase (hollow symbol) ac susceptibilities of 2 CH 3 OH.

10 Methanol T (emu K/mol) (emu/mol) Temperature (K) Figure S6 The fitting of temperature dependent molar magnetic susceptibility of 1 CH 3 OH to Eq. 2. The symbols are the experimental data and the dotted lines are the fitted data.

11 Aniline T (emu K/mol) (emu/mol) Temperature (K) Figure S7 The fitting of temperature dependent molar magnetic susceptibility of 1 C 6 H 5 NH 2 to Eq. 2. The symbols are the experimental data and the dotted lines are the fitted data.

12 Benzene T (emu K/mol) (emu/mol) Temperature (K) Figure S8 The fitting of temperature dependent molar magnetic susceptibility of 1 C 6 H 6 to Eq. 2. The symbols are the experimental data and the dotted lines are the fitted data.

13 Toluene T (emu K/mol) (emu/mol) Temperature (K) Figure S9 The fitting of temperature dependent molar magnetic susceptibility of 1 C 6 H 5 CH 3 to Eq. 2. The symbols are the experimental data and the dotted lines are the fitted data.

14 Nitrobenzene T (emu K/mol) (emu/mol) Temperature (K) Figure S1 The fitting of temperature dependent molar magnetic susceptibility of 1 C 6 H 5 NO 2 to Eq. 2. The symbols are the experimental data and the dotted lines are the fitted data.

15 Figure S11. Left: Ball and stick model of the crystal structure of Mn(TCNQ)(4,4 -bpy) C 6 H 6 with the disordered pyridyl and benzene rings. Right: A fragment of the structure of Fe(TCNQ)(4,4 - bpy) C 6 H 5 NO 2 with the TCNQ and nitrobenzene species highlighted in a space-filling model.

16 Table S3. A summary of pertinent polarity, 5 IR and magnetic data for 1 guest. guest Snyder polarity index (C N) /cm -1 T c Methanol , Aniline , Nitrobenzene , Benzene , Toluene , ,

17 Figure S12. Temperature dependence of the AC magnetic susceptibility of Fe(TCNQ)(4,4 -bpy) after being dried under vacuum.

18 Figure S13. Temperature dependence of the AC magnetic susceptibility of Fe(TCNQ)(4,4 - bpy) CH 3 OH.

Figure S14. PXRD of the dried powder of Fe(TCNQ)(DMF) 2 and the simulated pattern from the crystal structure. References 1. Sheldrick, G. Acta Crystallogr A 215, 71, 3. 2. Sheldrick, G. Acta Crystallogr A 28, 64, 112.

19 Figure S14. PXRD of the dried powder of Fe(TCNQ)(DMF) 2 and the simulated pattern from the crystal structure. References 1. Sheldrick, G. Acta Crystallogr A 215, 71, Sheldrick, G. Acta Crystallogr A 28, 64, Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Crystallogr. 29, 42, Shimomura, S.; Yanai, N.; Matsuda, R.; Kitagawa, S. Inorg. Chem. 21, 5, Snyder, L. R. Journal of Chromatography A 1974, 92, 223.

Supplementary Material. An improved, gram-scale synthesis of protected 3-haloazetidines: Rapid diversified synthesis of azetidine-3-carboxylic acids

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