S1 SUPPORTING INFORMATION Structural anisotropy of cyanido-bridged {Co II 9 W V 6 } Single-Molecule Magnets induced by bidentate ligands: towards the rational enhancement of energy barrier Szymon Chorazy, a,b Michał Rams, c Anna Hoczek, a Bernard Czarnecki, a Barbara Sieklucka, a Shin-ichi Ohkoshi* b , and Robert Podgajny* a a Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland. E-mail: robert.podgajny@uj.edu.pl b Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-0033 Tokyo, Japan. E-mail: ohkoshi@chem.s.u-tokyo.ac.jp c Institute of Physics, Jagiellonian University, Łojasiewicza 11, 30-348 Krakow, Poland. Experimental details. S2 Figure S1. Infrared spectrum of 1 in the 4000–500 cm -1 range. S4 Figure S2. Thermogravimetric curve of 1 with the step related to the loss of solvent molecules. S4 Table S1. Crystal data and structure refinement for 1. S5 Figure S3. Asymmetric unit of 1 with the detailed insight into the asymmetric parts of cluster A realized with two different Co5 coordination spheres, and of cluster B. S6 Table S2. Detailed structure parameters of 1. S7 Table S3. Results of Continuous Shape Measure Analysis for [W V (CN) 8 ] 3- units in 1. S9 Figure S4. Deformations of the {Co II 8 } pseudo-cubic moieties of the cluster cores of 1 (clusters A and B) in respect to the purely solvated {Co II 9 W V 6 (MeOH) 24 } molecule. S10 Figure S5. Deformations of the {W V 6 } pseudo-octahedral moieties of the cluster cores of 1 (clusters A and B) in respect to the purely solvated {Co II 9 W V 6 (MeOH) 24 } molecule. S11 Figure S6. Comparison of the directional deformations of the {Co II 8 } pseudo-cubic, and the {W V 6 } pseudo- octahedral fragments of the cluster cores of 1 (clusters A and B). S12 Figure S7. The supramolecular arrangement of {Co II 9 W V 6 } molecules in 1 with the insight into four main types of intercluster interactions, and the closest metal-metal intermolecular distances. S13 Figure S8. The supramolecular arrangement of cyanido-bridged clusters and crystallization solvent molecules of water, methanol, and acetonitrile in the crystal structure of 1. S14 Figure S9. Experimental and calculated (from single crystal X-ray model) powder X-ray diffraction patterns of 1 in the representative 3–30° range of 2Θ angle. S15 Figure S10. UV-Vis-NIR diffuse reflectance spectrum of 1 in the 200–1600 nm range. S16 Table S4. Analysis of UV-Vis-NIR diffuse reflectance spectrum of 1. S16 Detailed discussion on the dc magnetic properties of 1. S17 Figure S11. Reduced magnetization versus field curves of 1 in the 1.8–6 K range. S19 Figure S12. Temperature dependences of in-plane χ M ’ and out-of-plane χ M ” magnetic susceptibility of 1 under ac magnetic field of 3 Oe with the frequency of 1500 Hz, and various indicated dc magnetic fields. S19 Figure S13. Comparison of ac magnetic data of 1 measured at 0 Oe and 2000 Oe dc external fields. S20 Table S5. Parameters obtained by fitting the Cole–Cole χ M ”–χ M ’ plots of 1 using the generalized Debye model. S21 Figure S14. The detailed insight into χ M ”(ν) plot of 1 at zero dc field at the lowest temperatures. S21 Detailed discussion on the structural anisotropy influencing the SMM behaviour of clusters A and B of 1 S22 Table S6. Analysis of the elongation of Co II complexes in 1 S23 Figure S15. Comparison of the zero dc field χ M ”–T plots at the frequency of 1000 Hz for 1 with the purely solvated {Co II 9 W V 6 (MeOH) 24 } clusters, and other reported eightfold capped {Co II 9 W V 6 } clusters. S24 Table S7. Comparison of ac magnetic dynamics in 1 with other reported [M(CN) 8 ]-based Single-Molecule Magnets S25 References to Supporting Information. S26 Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2016