Structural dependence of the Ising type magnetic. anisotropy and of the relaxation time in mononuclear

Transcription

1 Supporting Information for Inorganic Chemistry. Structural dependence of the Ising type magnetic anisotropy and of the relaxation time in mononuclear trigonal bipyramidal Co(II) Single Molecule Magnets Feng Shao, a Benjamin Cahier, a Eric Rivière, a Régis Guillot, a Nathalie Guihéry, b * Victoria E. Campbell, a * and Talal Mallah a * a Institut de Chimie Moléculaire et des Matériaux d Orsay, CNRS, Université Paris Sud, Université Paris Saclay, Orsay Cedex, France. b Laboratiore de Chimie et Physique Quantiques, Université Toulouse III, 118 route de Narbonne, 31062, Toulouse, France. EXPERIMENTAL SECTION General. Unless otherwise stated, all starting materials were obtained commercially and were used without further purification. The ligand 2-(tert-butylthio)-N-(2-(tert-butylthio)ethyl)-N- ((neopentylthio)methyl)ethan-1-amine (NS tbu 3 ) was synthesized according to a modified literature procedure. 1 NMR spectra were recorded on a Bruker Aspect 300 NMR spectrometer. Electrospray ionization mass spectrometry (ESI-MS) spectra were recorded on a Thermo Scientific 2009 mass spectrometer. IR spectra were recorded on a Bruker TENSOR-27 FT-IR spectrometer equipped with an attenuated total reflectance (ATR) sample holder in the cm 1 range. Elemental analyses for C, H, N were performed on a Thermo Scientific Flash analyzer. 1

2 Scheme 1. Schematic representation of the synthesizes of the ligand NS tbu. Synthesis of: NS tbu 3. Tris(2-chloroethyl)amine hydrochloride (i). A 250 ml two-necked round-bottom flask, which was fitted with a dropping funnel and a reflux condenser, was charged with thionyl chloride (52 ml, 0.70 mol) and chloroform (80 ml). A solution of triethanolamine (29.80 g, 0 mol) in 50 ml of chloroform was added dropwise to this solution. The addition was carried out at ambient temperature for 1 h. The reaction continued at room temperature until gas evolution stopped, and then the mixture was heated at reflux for 4 h. After cooling to room temperature, a white solid precipitate was formed, which was filtered and washed with CHCl 3 (50 3 ml) and dried overnight in a vacuum oven. Tris(2-chloroethyl)amine hydrochloride (i) was obtained in 80 % yield, g. Tris(2-chloroethyl)amine (ii). Sodium hydroxide (2.00 g, 0.05 mol) was added portionwise to a solution of compound i (12.05 g, 0.05 mol) and 30 ml of water. The reaction was stirred for 1 h. The solution was extracted with CHCl 3 (20 3 ml) and the organic layer was further washed with (20 3 ml) distilled water, dried over anhydrous MgSO 4. The solvent was removed and the heavy oil product was obtained by vacuum-distillation (7.26 g, 71% yield). 2-(tert-butylthio)-N-(2-(tert-butylthio)ethyl)-N-((neopentylthio)methyl)ethan-1-amine (NS tbu 3 ). (Cautions: The tert-butylmercaptan used in this synthesis is a poisonous gas with an obnoxious odor. All procedures must be carried out in an efficient fume hood. The apparatus must be connected to a series of washing bottles charged with chromic acid mixture or other absorbing solutions.) All glassware must be previously dried. A two-necked flask was equipped with a reflux condenser topped with a drying tube (CaCl 2 ) and a 500-mL dropping funnel with external warming bath. With stirring, anhydrous tert-butyl alcohol (200 ml) was added and refluxed at 360 K, followed by sodium (2.30 g, 0.10 mol) in small portions. Upon reaction of all the sodium, the flask was allowed to cool to room temperature. 2-Methyl-2- propanethiol (11.28 ml, 0.10 mol), and 50 ml of warm anhydrous tert-butyl alcohol were poured into 2

3 the dropping funnel, which was heated by warm water. The solution was added dropwise with stirring to the sodium tert-butoxide solution during a 1 h period. The warming bath was then drained off, and a solution of N(CH 2 CH 2 Cl) 3 (ii) (6.81 g, mol) of dissolved in 20 ml of anhydrous tert-butyl alcohol was placed in the dropping funnel. The sodium tert-butoxide solution was heated to K, and slowly added over 4 h. The mixture was then refluxed for 1 h, and cooled to room temperature. The NaCl, which precipitates, was filtered, and the solution was concentrated under reduced pressure. The residue was diluted with diethyl ether, filtered, concentrated, and vacuum-distilled. The ligand was collected at K /2 torr to yield 8.45 g (0.023 mol) of product (70% yield). 1 H NMR (CDCl 3, 300 MHz, ppm from TMS): (27H, (CH 3 ) 3 CS-); 2.54 (6H, Me 3 CSCH 2 CH 2 -); 2.62 (6H, Me 3 CSCH 2 CH 2 -). MS-ESI: m/z calcd for C 18 H 39 NS 3 : 365.3, found: Synthesis of [Co(NS tbu 3 )Cl]ClO 4 : Complex 1. To a hot solution of CoCl 2 (65.1 mg, 0.5 mmol) in 1- butanol (2 ml) sulfur NS tbu 3 (219.4 mg, 0.6 mmol) in 1-butanol (2 ml) were added followed by [Bu 4 N]ClO 4 (170.6 mg, 0.5 mmol) in ethanol (1 ml). Then the stirred solution was cooled down to room temperature at ambient condition. A purple precipitate was formed, it was filtered, washed with 1-butanol and petroleum ether, and dried in vacuum at room temperature. Yield, 32%, 89.5 mg. X-ray quality crystals were obtained by vapor diffusion of diethyl ether into an ethanol/acetone (v/v 1:1) solution of 1. Elem Anal. Calcd: C, 38.64; H, 7.02; N, Found: C, 38.66; H, 7.14; N, IR (KBr): 3436 (m), 2960 (m), 2865 (w), 1464 (m), 1370 (m), 1162 (m), 1103 (s), 623 (m) cm -1. tbu Synthesis of [Co(NS 3 )Br]ClO 4 : Complex 2. To a hot solution of CoBr 2 H 2 O (118.4 mg, 0.5 mmol) in 1-butanol (2 ml) sulfur NS tbu 3 (219.4 mg, 0.6 mmol) in 1-butanol (2 ml) were added followed by [Bu 4 N]ClO 4 (170.6 mg, 0.5 mmol) in ethanol (1 ml). Then the stirred solution was cooled down to room temperature at ambient condition. A purple precipitate was formed, it was filtered, washed with 1-butanol and petroleum ether, and dried in vacuum at room temperature. Yield, 29.8%, 90 mg. X-ray quality crystals were obtained by vapor diffusion of diethyl ether into an ethanol/acetone (v/v 1:1) solution of 2. Elem Anal. Calcd: C, 35.79; H, 6.51; N, Found: C, 35.81; H, 6.49; N, IR (KBr): 3436 (m), 2959 (m), 2865 (w), 1464 (m), 1370 (m), 1161 (m), 1102 (s), 623 (m) cm -1. Synthesis of [Co(NS tbu 3 )NCS]ClO 4 : Complex 3. To a hot solution of Co(NCS) 2 (88 mg, 0.5 mmol) in 1- butanol (2 ml) sulfur NS tbu 3 (219.4 mg, 0.6 mmol) in 1-butanol (2 ml) were added followed by [Bu 4 N]ClO 4 (170.6 mg, 0.5 mmol) in ethanol (1 ml). Then the stirred solution was cooled down to room temperature at ambient condition. A purple precipitate was formed, it was filtered, washed with 1-butanol and petroleum ether, and dried in vacuum at room temperature. Yield, 5.1%, 15 mg. X-ray quality crystals were obtained by vapor diffusion of diethyl ether into an ethanol/acetone (v/v 1:1) solution of 3. 3

4 Elem Anal. Calcd: C, 39.20; H, 6.75; N, Found: C, 39.08; H, 6.78; N, IR (KBr): 3436 (m), 2960 (m), 2863 (w), 2067 (s), 1457 (w), 1365 (w), 1159 (w), 1099 (w), 623 (m) cm -1. Single Crystal X-ray Diffraction Studies. X-ray diffraction data were collected by using a Kappa X8 APPEX II Bruker diffractometer with graphite-monochromated Mo Kα radiation (λ = Å). Crystals were mounted on a CryoLoop (Hampton Research) with Paratone-N (Hampton Research) as cryoprotectant and then flashfrozen in a nitrogen-gas stream at 100 K. The temperature of the crystal was maintained at the selected value (100 K) by means of a 700 series Cryostream cooling device to within an accuracy of ±1 K. The data were corrected for Lorentz polarization, and absorption effects. The structures were solved by direct methods using SHELXS-97 2, and refined against F 2 by full-matrix least-squares techniques using SHELXL with anisotropic displacement parameters for all non-hydrogen atoms. Hydrogen atoms were located on a difference Fourier map and introduced into the calculations as a riding model with isotropic thermal parameters. All calculations were performed by using the Crystal Structure crystallographic software package WINGX 4. The crystal data collection and refinement parameters are given in Table S1. CCDC contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via Figure S1: ORTEP drawing of 1. Hydrogen atoms and anions are omitted for clarity. Thermal ellipsoids are shown at 30% probability. 4

5 Figure S2: ORTEP drawing of 2. Hydrogen atoms and anions are omitted for clarity. Thermal ellipsoids are shown at 30% probability. Figure S3: ORTEP drawing of 3. Hydrogen atoms and anions are omitted for clarity. Thermal ellipsoids are shown at 30% probability. 5

6 Table S1. Crystallographic data and structure refinement details for compounds 1-3. Compound Formula C 18 H 39 Cl 2 CoNO 4 S C 18 H 39 BrClCoNO C 19 H 39 ClCoN 2 O 4 S Mw (g mol -1 ) , S, , Crystal size / mm x 0.08 x x 0.06 x x 0.04 x 0.03 Crystal system monoclinic monoclinic cubic Space group P 2 1 /n P 2 1 /c P a, Å (5) (13) (5) b, Å (3) (2) (5) c, Å (5) (9) (5) α, β, (10) (3) 90 γ, Cell volume, Å (13) (7) (3) Z 4 ; 1 8 ; 2 4 ; 1/3 T, K 100(1) 100(1) 100(1) F µ / mm θ range / Refl. collected Refl. unique R int GOF Refl. obs. (I>2σ(I)) Parameters wr 2 (all data) R value (I>2σ(I)) Largest diff. peak and hole (e-.å -3 ) ; ; ;

7 Table S2. Selected bond lengths (Å) and bond angles (deg). Compound d(co-n ax. ) d(co-x) S i -Co-S ii S i -Co-S iii S ii -Co-S iii 1 : Co-Cl ; ClO ( (5) (19) (18) (18) 2 : Co-Br ; ClO (4) (10) (5) (5) (5) 2.273(5) (10) (5) (5) (6) 3: Co-NCS ; ClO (6) 2.001(7) (18) 7

8 Magnetic Measurements. The magnetic susceptibility measurements were obtained using a Quantum Design SQUID magnetometer MPMS-XL7 operating between 1.8 and 300 K for dc-applied fields ranging from 0 to 7 T. Dc analysis was performed on polycrystalline samples wrapped in eicosane under a field between 0.1 and 1 T and between 1.8 and 300 K. Ac susceptibility measurements were carried out under an oscillating field of 3 Oe and ac frequencies ranging between 0.1 and 1400 Hz within an optimal dc filed. Diamagnetic corrections were applied for the sample holder and the eicosane. Figure S4. χt vs. T at Oe for 1, experimental data ( ) and fit ( ). 8

9 Figure S5. χt vs. T at Oe for 2, experimental data ( ) and fit ( ). Figure S6. χt vs. T at Oe for 3, experimental data ( ) and fit ( ). 9

10 Table S3. Cole-cole fit parameters for 1-3. Compound T / K χ 0 χ α τ The fit of the χ = f(ν), χ = f(ν) and χ = f(χ ) were carried out using the following equations using a home made program: (χ χ "(ν ac ) = 0 χ )(2πν ac τ ) 1 α cos(απ / 2) 1+ 2(2πν ac τ ) 1 α sin(απ / 2)+ (2πν ac τ ) 2(1 α ) 10

11 Where χ is the adiabatic susceptibility (at ν ac! ), χ 0 is the isothermal susceptibility (at ν ac! 0) and τ is the average relaxation time of magnetization K K 0.6 χ' / cm 3 mol χ'' / cm 3 mol ν / Hz ν / Hz Figure S7. A.c. magnetic susceptibility data. χ and χ as a function of wave frequency at variable temperatures, experimental data ( ) and fit ( ), and d.c. applied field = 3000 Oe for K K 0.7 χ' / cm 3 mol χ'' / cm 3 mol ν / Hz ν / Hz Figure S8. A.c. magnetic susceptibility data. χ and χ as a function of wave frequency at variable temperatures, experimental data ( ) and fit ( ), and d.c. applied field = 3000 Oe for 2. 11

12 K K χ' / cm 3 mol χ'' / cm 3 mol ν / Hz ν / Hz Figure S9. A.c. magnetic susceptibility data. χ and χ as a function of wave frequency at variable temperatures, experimental data (!) and fit ( ), and d.c. applied field = 1600 Oe for χ'' / cm 3 mol K χ' / cm 3 mol -1 Figure S10. Cole-cole plot for 1 (d.c. applied field = 3000 Oe), experimental data (!) and fit ( ). 12

13 χ'' / cm 3 mol K χ' / cm 3 mol -1 Figure S11. Cole-cole plot for 2 (d.c. applied field = 3000 Oe), experimental data (!) and fit ( ). 0.5 χ'' / cm 3 mol K χ' / cm 3 mol -1 Figure S12. Cole-cole plot for 3 (d.c. applied field = 1600 Oe), experimental data (!) and fit ( ). 13

14 Computational information Experimental structures were used in the calculations. The position of hydrogen atoms were optimized using DFT calculations (UB3LYP/6-311g). For CASSCF and CASPT2 calculations, the active space contains 7 electrons in 10 orbitals (the five 3d orbitals plus five diffuse 4d orbitals). The ground electronic state was described by a state-specific calculation while excited states (9 quartets and 40 doublets) were obtained using state-average calculations. ANO-RCC basis sets were used with the following contraction scheme: 6s5p4d2f1g for Co, 6s5p4d1f for Br, 5s5p3d1f for Cl and S, 6s3p2d1f for N, 6s3p for C and 2s for H. All the calculated electronic states were included in the SO-RASSI calculations. CASPT2 results Figure S13. Calculated CASPT2 energies for compounds 1, 2a, 2b and 3. The CASPT2 spectrum Table S4. D and E values obtained for CASPT2 calculations. 1 2a 2b 3 D (cm -1 ) E (cm -1 ) The CASPT2 calculations strongly overestimate the D values. As such an overestimation has already been observed in other complexes with large negative D values, a methodological study is actually performed. Table S5. composition of the 3d molecular orbitals for compounds 1, 2a, 2b and 3 in terms of real 3d atomic orbitals. 1 2a x2-y2 xy xz yz x2-y2 xy xz yz 14

15 φ φ φ φ b 3 φ φ φ φ Model complexes Calculations have been performed on the model complex [Co(NCH) 5 Br] + in order to determine the structural factor responsible for the strong degeneracy lift of the φ 3 and φ 4 orbitals and the small energy difference between φ 1 and φ 3 in complex 2b. Two geometrical factors distinguish this complex from complex 2a: the inclination of the Br - ligand and the closure of one SCoS angle. Starting from a C 3v symmetry point group and fixing the same closure angle N!" CoN!" (82 ) between axial and equatorial N atoms as NCoS in 2b complex (model complex 4), we defined two distorded model complexes. For the first model (5), we have decreased the N!" CoBr angle from 180 to 175. For the second model (6), we have closed one N!" CoN!" angle between two equatorial N atoms up to 110 while the two other angles N!". CoN!". were opened up to 122. The physical content of the magnetic orbitals is detailed in Table S6 while the molecular orbital diagram is depicted in Figure S14. It can be seen that the inclination of the Br - has no qualitative effect. On the contrary the angular distortion induces the same features on both the orbital diagram and the content of the orbitals. Indeed, as well as in complex 2b, the coefficients of the d x2-y2 and d xy orbitals in φ 3 decrease in favor of d xz and d yz while the energy of φ 3 is lowered by the distortion. 15

16 Figure S14. structure and 3d orbital splitting of model complexes 4, 5 and 6. Table S6. Decomposition of the magnetic orbitals on the 3d atomic orbitals of the Co(II). As we do not have access to the overlap matrix, the squared coefficients have been renormalized by their sum and multiplied by 100 to reach 100% of contribution. 5 is mainly spread over d Z2. Complexes AO 2 2 d X -Y d XZ 2 2 d X -Y d XZ 2 2 d X -Y d XZ MO d XY d YZ d XY d YZ d XY d YZ 4 57% 43% 58% 42% 73% 27% 3 57% 43% 57% 43% 43% 57% 2 43% 57% 44% 56% 28% 72% 1 43% 57% 43% 57% 57% 43% 16

17 Uncategorized References (1) Fallani, G.; Morassi, R.; Zanobini, F., Inorg. Chim. Acta 1975, 12, (2) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Solution, University of Göttingen: Göttingen, Germany, (3) Sheldrick, G. M., Acta Crystallogr. Sect. A: Found. Crystallogr. 2008, 64, (4) Farrugia, L., J. Appl. Crystallogr. 1999, 32,