Supporting Information

Transcription

1 Supporting Information Correlating Bridging Ligand with Properties of Ligand- Templated [Mn II 3X 3 ] 3+ Clusters (X = Br -, Cl -, H -, MeO - ) Kevin J. Anderton, 1 David M. Ermert, 1 Pedro A. Quintero, 2 Mackenzie W. Turvey, 2 Majed S. Fataftah, 3 Khalil A. Abboud, 1 Mark W. Meisel, 2 Erik Čižmár*,4, and Leslie J. Murray,*,1 1 Department of Chemistry, Center for Catalysis and Center for Heterocyclic Compounds, University of Florida, Gainesville, Florida 32611, United States 2 Department of Physics and the National High Magnetic Field Laboratory, University of Florida, Gainesville, Florida 32611, United States 3 Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States 4 Institute of Physics, Faculty of Science, Pavel Jozef Šafárik University, Košice, Slovakia Electronic Supplementary Information Figure S1 Infrared spectrum of Cl 3 L (2) 2 Figure S2 Infrared spectrum of H 3 L (3) 3 Figure S3 Infrared spectrum of (OCH 3 ) 3 L (4) 4 Figure S4 ESI/MS(+) analysis on (OCH 3 ) 3 L (4) in dichloromethane 5 Figure S5 UV-visible spectrum of Cl 3 L (2) in tetrahydrofuran 6 Figure S6 UV-visible spectrum of H 3 L (3) in tetrahydrofuran 7 Figure S7 UV-visible spectrum of (OCH 3 ) 3 L (4) in tetrahydrofuran 8 Figure S8 Isothermal, field-dependent magnetization data for Cl 3 L (2) at 8 K 9 Figure S9 Isothermal, field-dependent magnetization data for H 3 L (3) at 8 K 10 Figure S10 Isothermal, field-dependent magnetization data for (OCH 3 ) 3 L (4) at 8 K 11 Figure S11 5 K and 293 K X-Band EPR spectra of Cl 3 L (2) in PhMe 12 Figure S12 5 K and 293 K X-Band EPR spectra of H 3 L (3) in PhMe 13 Figure S13 5 K and 293 K X-Band EPR spectra of (OCH 3 ) 3 L (4) in 1:1 DCM:PhMe 14 Figure S14 Cyclic voltammogram of Br 3 L (1) in isobutyronitrile 15 Figure S15 Cyclic voltammogram of Cl 3 L (2) in isobutyrontrile 16 Table S1 Summary of crystallographic details for Cl 3 L (2) 17 Table S2 Summary of crystallographic details for H 3 L (3) 18 Table S3 Summary of crystallographic details for (OCH 3 ) 3 L (4) 19 1

2 Figure S1. Infrared spectrum of Cl 3 L (2). 2

3 Figure S2. Infrared spectrum of H 3 L (3). 3

4 Figure S3. Infrared spectrum of (OCH 3 ) 3 L (4). 4

5 Figure S4. ESI/MS(+) data for (OCH 3 ) 3 L (4) in dichloromethane. Capillary voltage: 3000 V. Fragmentation voltage: 120 V. Desolvation temperature: 100 C. 5

6 Figure S5. Ultraviolet-visible spectrum of Cl 3 L (2) in THF. 6

7 Figure S6. Ultraviolet-visible spectrum of H 3 L (3) in THF. 7

8 Figure S7. Ultraviolet-visible spectrum of (OMe) 3 L (4) in THF. 8

9 18 16 Cl 3 L, 2 Magnetization (10 3 G cm 3 mol -1 ) g J (cm -1 ) J' (cm -1 ) D (cm -1 ) Field (T) Cl 3 L, M T (cm 3 mol K) g J (cm -1 ) J' (cm -1 ) D (cm -1 ) Temperature (K) Figure S8. Isothermal, field-dependent magnetization data (top) at 8 K and temperaturedependent magnetic susceptibility data taken at 100 G (bottom) for Cl 3 L (2) and the corresponding simulations (blue and black lines) generated using the inset parameters. The black lines correspond to a simulation in which D was unrestrained. 9

10 8 7 H 3 L, 3 Magnetization (10 3 G cm 3 mol -1 ) g J (cm -1 ) J' (cm -1 ) D (cm -1 ) Field (T) H 3 L, 3 5 M T (cm 3 mol K) g J (cm -1 ) J' (cm -1 ) D (cm -1 ) Temperature (K) Figure S9. Isothermal, field-dependent magnetization data (top) at 8 K and temperaturedependent magnetic susceptibility data taken at 100 G (bottom) for H 3 L (3) and the corresponding simulations (red and black lines) generated using the inset parameters. The black lines correspond to a simulation in which D was unrestrained. 10

11 3.0 (OMe) 3 L (4) Magnetization (10 3 G cm 3 mol -1 ) g J (cm -1 ) J' (cm -1 ) D (cm -1 ) Field (T) Figure S10. Isothermal, field-dependent magnetization data at 8 K for (OMe) 3 L (4) and the corresponding simulations (black line) generated using the inset parameters. 11

12 Intensity (a.u.) Field (G) Cl 3 L 5K Intensity (a.u.) Field (G) Cl 3 L RT Figure S11. X-Band EPR spectra of toluene solutions of Cl 3 L (2) at 5 K (top) and 293 K (bottom). 12

13 Intensity (a.u.) H 3 L 5K Field (G) 10 5 Intensity (a.u.) H 3 L RT Field (G) Figure S12. X-Band EPR spectra of toluene solutions of H 3 L (3) at 5 K (top) and 293 K (bottom). 13

14 3 2 Intensity (a.u.) (OMe) 3 L 5K Field (G) Intensity (a.u.) (OMe) 3 L RT Field (G) Figure S13. X-Band EPR spectra of 1:1 DCM:toluene solutions of (OCH 3 )L (4) at 5 K (top) and 293 K (bottom). 14

15 Figure S14. Histogram of the 1774 data points for Mn II -Cl bond distances in the Cambridge Structural Database. The bin containing the longer bonds of the asymmetric Mn II -Cl bridges of Cl 3 L (2) is highlighted in red. Search criteria: Mn-Cl bond AND text manganese(ii). 15

16 Table S1. Crystal data and structure refinement for Cl 3 L (2). Identification code erm16 Empirical formula C57 H75 Cl2.40 Mn3 N6 O0.30 Formula weight Temperature 100(2) K Wavelength Å Crystal system Triclinic Space group P ī Unit cell dimensions a = (7) Å = (10). b = (7) Å = (10). c = (9) Å = (11). Volume (3) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1154 Crystal size x x mm 3 Theta range for data collection to Index ranges -16 h 15, -17 k 17, -21 l 21 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 646 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [10389] R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 R1 = ( Fo - Fc ) / Fo wr2 = [ w(fo 2 - Fc 2 ) 2 ] / w Fo 2 2 ]] 1/2 S = [ w(fo 2 - Fc 2 ) 2 ] / (n-p)] 1/2 w= 1/[ 2 (Fo 2 )+(m*p) 2 +n*p], p = [max(fo 2,0)+ 2* Fc 2 ]/3, m & n are constants. 16

17 Table S2. Crystal data and structure refinement for H 3 L (3). Identification code erm4 Empirical formula C69 H90 Mn3 N6 Formula weight Temperature 100(2) K Wavelength Å Crystal system Hexagonal Space group P6 3 /m Unit cell dimensions a = (2) Å = 90. b = (2) Å = 90. c = (18) Å = 120. Volume (10) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1242 Crystal size x x mm 3 Theta range for data collection to Index ranges -22 h 20, -22 k 22, -16 l 16 Reflections collected Independent reflections 2511 [R(int) = ] Completeness to theta = % Absorption correction Analytical Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 2511 / 0 / 126 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [1804] R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 R1 = ( Fo - Fc ) / Fo wr2 = [ w(fo 2 - Fc 2 ) 2 ] / w Fo 2 2 ]] 1/2 S = [ w(fo 2 - Fc 2 ) 2 ] / (n-p)] 1/2 w= 1/[ 2 (Fo 2 )+(m*p) 2 +n*p], p = [max(fo 2,0)+ 2* Fc 2 ]/3, m & n are constants. 17

18 Table S3. Crystal data and structure refinement for (OCH 3 ) 3 L (4). Identification code erm8 Empirical formula C66.50 H101 Cl5 Mn4 N8 O4 Formula weight Temperature 100(2) K Wavelength Å Crystal system Trigonal Space group P -3 Unit cell dimensions a = (4) Å = 90. b = (4) Å = 90. c = (3) Å = 120. Volume 10590(3) Å 3 Z 6 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 4638 Crystal size x x mm 3 Theta range for data collection to Index ranges -28 h 28, -28 k 28, -25 l 25 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Analytical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 3 / 818 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = [9011] R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 R1 = ( Fo - Fc ) / Fo wr2 = [ w(fo 2 - Fc 2 ) 2 ] / w Fo 2 2 ]] 1/2 S = [ w(fo 2 - Fc 2 ) 2 ] / (n-p)] 1/2 w= 1/[ 2 (Fo 2 )+(m*p) 2 +n*p], p = [max(fo 2,0)+ 2* Fc 2 ]/3, m & n are constants. 18