Supporting Information. Lacunary Polytungstate Ligands

Transcription

1 This journal is The Royal Society of Chemistry 0 Supporting Information Heterometallic Appended {MMn III } Cubanes Encapsulated by Lacunary Polytungstate Ligands Hai-Hong Wu, Shuang Yao, Zhi-Ming Zhang,* Yang-Guang Li, You Song,* Zhu-un Liu, Xin-Bao Han and En-Bo Wang * CONTENTS Section Section Section Section Experimental Section Supplementary Structural Figures Magnetic properties Supplementary Physical Characterizations

2 This journal is The Royal Society of Chemistry 0 Section Experimental Section. Materials and Methods. All the reagents were commercially purchased and used without further purification. The K 8 [γ-siw 0 O 6 ] H O precursor was synthesized according to the literature S and characterized by IR spectrum. Elemental analyses (C and H were performed on a PerkinElmer 00 CHN element analyzer; Si, W, Mn, Dy, Sm, Er, K and Na were analyzed on a PLASMASPEC(I ICP atomic emission spectrometer. IR spectra were recorded in the range cm - on an Alpha Centaurt FTIR spectrophotometer using KBr pellets. TG analyses were performed on a Perkin Elmer TGA7 instrument in flowing N with a heating rate of 0 C min.. Synthesis of : 0.5 g Dy O was added in 0 ml distilled water, then.0 ml concentrated nitric acid was added in the mixture, which was refluxed for one hour resulting in solution A..0 g K [γ-siw 0 O 8 ] H O was dissolved in 0mL water,.0 g MnCl H O (5.05 mmol and 5 ml solution A were added, followed by addition of ml morpholine and 5 ml M K CO aqueous solution. The resulting mixture with the ph value of 9.5 was further stirred at 60 C for h, Then 0.0 g NaCl was added into the resulting mixtures, which was further stirred for 0 min. Afterwards the solution was cooled down to ambient temperature and a brown residue was filtered off. After three days, brown tubular crystals suitable for X-ray diffraction were obtained (Yields: 7 % based on W. Anal. Found (%: C, 0.8; H, 0.9; Dy,.89; K,.99; Mn,.; Na,.78, Si, 0.95; W, 55.6; Calcd: C, 0.; H, 0.87; Dy,.06; K, 5.6; Mn,.; Na,.60, Si,.06; W, 55.. IR (KBr pellet: νmax/cm -

3 This journal is The Royal Society of Chemistry 0 (s, 6 (s, 6 (w, 65 (w, 989 (w, 90 (w, 86 (m, 78 (m, 707 (m and 507 (w. Synthesis of..0 g K [γ-siw 0 O 8 ] H O was dissolved in 0mL water,.0 g MnCl H O (5.05mmol was added, followed by addition of ml morpholine and 6 ml M K CO aqueous solution, the resulting mixture with the ph value of 9.99 was further stirred at 50 C for h. Then 0.0 g NaCl was added into the resulting mixtures, which was further stirred for 0 min. Afterwards the solution was cooled down to ambient temperature and a brown residue was filtered off. After two days, brown block crystals suitable for X-ray diffraction were obtained (Yield: % based on W. Anal. Found (%: C, 0.7; H, 0.96; K, 7.7; Mn,.0; Na,.79, Si,.8; W, 55.67; Calcd: C, 0.; H, 0.88; K, 7.; Mn,.8; Na,.6, Si,.07; W, IR (KBr pellet: νmax/cm - 0 (s, 67 (s, 59 (w, 78 (w, 986 (w, 99 (m, 860 (s, 787 (m, 700 (s and 50 (s.. X-ray Crystallography. The crystallographic data were performed on an Oxford Diffraction Gemini R CCD for, and a Rigaku R-AXIS RAPID IP diffractometer for. The data were collected at 9 K, and graphite-monochromated Mo-Kα radiation (λ = Å. The structures were solved by the direct method and refined by the Full-matrix least squares on F using the SHELXL-97 software. S During the refinement of compounds and, all hydrogen atoms on water molecules and protonation were directly included in the molecular formula. The restraint command 'isor' was employed to restrain the oxygen atoms so as to avoid the ADP and NPD problems on them. This command leds to the restraint numbers 60 and 8 for the two

4 This journal is The Royal Society of Chemistry 0 compounds, respectively. The crystal data and structure refinements of and are summarized in Table S. CSD reference numbers, 66 for and 68 for, contain the supplementary crystallographic data for this paper. This data may be obtained from the Fachinformationszentrum Karlsruhe, 76 Eggenstein-Leopoldshafen, Germany (fax: ( ; crysdata@fiz-karlsruhe.de. S (a A.Tézé and G. Hervé, Inorg. Synth., 990, 7, 85; (b. Canny, A. Tézé and R. Thouvenot, G. Hervé, Inorg. Chem., 986, 5,. S G. M. Sheldrick, SHELXL97, Program for Crystal Structure Refinement, University of Göttingen: Göttingen, Germany, 997; G. M. Sheldrick, SHELXS97, Program for Crystal Structure Solution, University of Göttingen: Göttingen, Germany, 997.

5 This journal is The Royal Society of Chemistry 0 Table S Crystal Data and Structure Refinement for and. Empirical formula CH 6 DyK 7 Mn Na 6 CH 6 K 0 Mn Na 6 O 9 Si O 9 Si W 6 W 6 M λ/å T/K 9( 9( Crystal dimensions/mm Crystal system Monoclinic Triclinic Space group P(/c P- a/å 7.957(5 5.69( b/å.86( 9.5( c/å.8507( 9.( α/ ( β/ (0 88.0( γ/ ( V/Å 909.6( 86.7(7 Z D c /Mg m μ/mm F( θ Range/ Data/restraints/param eters 97 / 60 / /8/9 R (I > σ(i a wr (all data a Goodness-of-fit on F a R = F 0 - F C / F 0 ; wr = [w(f 0 -F C ]/ [w(f 0 ] /

6 This journal is The Royal Society of Chemistry 0 Table S. Bond valence sum calculations of compounds and. [S,S] Bonds Bond length (Å BVS Bonds Bond length (Å BVS Compound Compound Mn(-O(5.98( Mn(-O(57.99( 0.6 Mn(-O(0.9( Mn(-O(7.97( Mn(-O(.98( Mn(-O(6.97( Mn(-O(5.95( Mn(-O(.9(6 0.9 Mn(-O(.7( Mn(-O(.66( 0.56 Mn(-O(.7( Mn(-O(.99( 0.6 V Mn( =. V Mn( =.99 Mn(-O(57 Mn(-O( Mn(-O(55.9( Mn(-O(5 Mn(-O( Mn(-O(57.97( Mn(-O(0 Mn(-O( Mn(-O(56.970( Mn(-O(60 Mn(-O( Mn(-O(.0( Mn(-O( Mn(-O( Mn(-O(5.8( Mn(-O(7 Mn(-O( Mn(-O(6.85( 0.89 V Mn( =.07 V Mn( =.99 Mn(-O(5.907( Mn(-O(.87( Mn(-O(5.9( Mn(-O(.899( Mn(-O(5.9(7 0.6 Mn(-O(0.97( Mn(-O(5.90( Mn(-O(57.97( Mn(-O(.7( Mn(-O(6.098( Mn(-O(7.77( Mn(-O(6.70( 0.59 V Mn( =.8 V Mn( =. Mn(-O(7.90( Mn(-O(.86( Mn(-O(5.98( Mn(-O(5.99( Mn(-O(5.99( Mn(-O(.966( Mn(-O(.055( Mn(-O(6.05( Mn(-O(7.076( Mn(-O(5.( Mn(-O(.68(7 0.5 Mn(-O(.86( 0. V Mn( =.05 V Mn( =.0 [S] The valence sum calculations are performed on a program of bond valence calculator, version.00 February 99, written by C. Hormillosa, with assistance from Healy, S. distributed by I. D. Brown. [S] I. D.Brown, Altermatt, D. Acta Crystallogr., 985, B,.

7 Electronic Supplementary Material (ESI for Dalton Transactions This journal is The Royal Society of Chemistry 0 Section Supplementary Structural Figures Fig. S. (a Ball-and-stick representation of the {DyMn} cluster in ; (b ball-and-stick representation of the {KMn} cluster in. Fig. S. (a Appended {LnMn} cubane core of and (b appended {KMn} cubane core of.

8 This journal is The Royal Society of Chemistry 0 Fig. S. The D packing agreement of along b-axis. The K +, Na + and water molecules are omitted for clearity. Fig. S. The D packing agreement of along c-axis. The K +, Na + and water molecules are omitted for clearity.

9 This journal is The Royal Society of Chemistry 0 Fig. S5. The D packing agreement of along a-axis. The K +, Na + and water molecules are omitted for clearity. Fig. S6. The D packing agreement of. The K +, Na + and water molecules are omitted for clearity.

10 This journal is The Royal Society of Chemistry 0 Section Magnetic properties Fig. S7. Temperature dependence of magnetic susceptibilitites in the form of χ M for. 0 M / cm G mol H / koe Fig. S8. Field dependence of magnetization for.

11 This journal is The Royal Society of Chemistry 0 Energy / cm S T Fig. S9. The energy diagram for. The energy was calculated by the fitting results, and as described in main text. 9 M / N B koe 60 koe 50 koe 0 koe 0 koe 0 koe 0 koe fit HT - / koe K - Fig. S0. Plot of reduced magnetization measurement of randomly oriented powder sample of and the fit curve by ANISOFIT.

12 This journal is The Royal Society of Chemistry 0 ' / cm mol T / K Hz 0 Hz 00 Hz 500 Hz khz.5 khz '' / cm mol Hz 0 Hz 00 Hz 500 Hz khz.5 khz T / K Fig. S. Temperature dependence of the AC magnetic susceptibilities of. Fig. S. Temperature dependence of magnetic susceptibilitites in the form of χ M for.

13 This journal is The Royal Society of Chemistry 0 0 M T / cm K mol T / K Fig. S. Low-temperature products of χ M T ( - χ M T (. M / N B H / koe Fig. S. Field dependence of magnetization for.

14 This journal is The Royal Society of Chemistry 0 M / N B koe 0 koe 0 koe 0 koe 50 koe 60 koe 70 koe HT - / koe K - Fig. S5. Plot of reduced magnetization measurement of randomly oriented powder sample of. ' / cm mol Hz 0 Hz 00 Hz 500 Hz khz.5 khz T / K Fig. S6. Temperature dependence of the in-phase AC magnetic susceptibilities of in a zero applied static field and with a 5 Oe oscillating field.

15 This journal is The Royal Society of Chemistry ' / cm mol T / K '' / cm mol - '' / cm mol Hz 0 Hz 00 Hz 500 Hz khz.5 khz T / K / Hz.8 K K Fig. S7. Temperature dependence of the AC magnetic susceptibilities of in koe applied static field and with a 5 Oe oscillating field.

16 Appendix: The model for fitting the magnetic properties of complex by Kambe method. K Mn Mn Mn Mn ( ( ( ( ( ( ( ( ] [( ( ] [( ( ( ( ( ( ( ] [( ] ( [( ( Ĥ B A T B A T T T i i where B A T B A, E(S T,S A,S B = S T (S T + + ( S A (S A + + ( S B (S B + S S A, S B 0 0 S A, S B S T S A = 0 S B = 0, S T = 0 S B =, S T = S A = S B = 0, S T = S B =, S T = 0,, S B =, S T = S A = S B = 0, S T = S B =, S T =,, S B =, S T = 0,,,, S A = S B = 0, S T = S B =, S T =,, S B =, S T =,,,,5 S B =, S T = S A = S B = 0, S T = S B =, S T =,,5 S B =, S T =,,,5,6 S B =, S T =,,,,5,6,7 Electronic Supplementary Material (ESI for Dalton Transactions This journal is The Royal Society of Chemistry 0

17 This journal is The Royal Society of Chemistry 0 S B =, S T,, S B =, S T = 0,,,,,5,6 S B =, S T = = S B =, S T =,,,,5 S B =, S T = 0,,,,,5,6,7,8 S B =, S T,, S B =, S T =,,,,5,6,7 = S B =, S T =,,,5,6 S B =, S T,,5 = (S T, S A, S B S T (S T + S A (S A + S B (S B + E(S T,S A,S B E calc (cm - (0, 0, (, 0, (, 0, (, 0, (, 0, (,, (0,, (,, (,, 6. (,, (,, (,, (,, (,, (,, (,, (,, (5,, (,, (,, (,, (,, (0,, (,, (,, (,, (,, (,, (,, (,, (,, (5,, (,, (,,

18 This journal is The Royal Society of Chemistry 0 (,, (5,, (6,, (,, (,, (,, (,, (,, (,, (,, (,, (5,, (0,, (,, (,, (,, (,, (5,, (6,, (,, (,, (,, (,, (5,, (6,, (7,, (,, (,, (,, (5,, (,, (,, (,, (5,, (6,, (,, (,, (,, (,, (5,, (6,, (7,, (0,,

19 This journal is The Royal Society of Chemistry 0 (,, (,, (,, (,, (5,, (6,, (7,, (8,, Ng kt Ng A kt B 6 i 6 i ai exp( Ei / kt Ng kt bi exp( Ei / kt E( ST, SA, SB ST ( ST (ST exp[ ] kt E( ST, SA, SB (ST exp[ ] kt M (zj'/ Ng S T =, S T (S T +(S T + = 6 S T =, S T (S T +(S T + = 0 S T =, S T (S T +(S T + = 8 S T =, S T (S T +(S T + = 80 S T = 5, S T (S T +(S T + = 0 S T = 6, S T (S T +(S T + = 56 S T = 7, S T (S T +(S T + = 80 S T = 8, S T (S T +(S T + = A=6exp( /kt+0exp(6 /kt+8exp( /kt+80exp(0 /kt+6exp(/kt+6exp(/kt+ / kt- /kt+0exp(/kt+ /kt+ /kt+6exp(/kt+6 /kt-6 /kt+0exp(/kt+6 /kt- /kt +8exp(/kT+6 /kt+ /kt+0exp(/kt+ /kt-8 /kt+8exp(/kt+ /kt- /kt+80 exp(/kt+ /kt+6 /kt+8exp(/kt+0 /kt-0 /kt+80exp(/kt+0 /kt- /kt+0e xp(/kt+0 /kt+8 /kt+0exp(6/kt+6exp(6/kt+ /kt-6 /kt+0exp(6/kt+ /kt- /kt +8exp(6/kT+ /kt+ /kt+6exp(6/kt+6 /kt-0 /kt+0exp(6/kt+6 /kt-6 /kt+8exp (6/kT+6 /kt+80exp(6/kt+6 /kt+8 /kt+6exp(6/kt+ /kt-6 /kt+0exp(6/kt+ / kt- /kt+8exp(6/kt+ /kt-6 /kt+80exp(6/kt+ /kt+ /kt+0exp(6/kt+ /k T+ /kt+0exp(6/kt+0 /kt-0 /kt+8exp(6/kt+0 /kt- /kt+80exp(6/kt+0 /k T-6 /kt+0exp(6/kt+0 /kt+ /kt+56exp(6/kt+0 /kt+6 /kt+8exp(/kt+0ex p(/kt+ /kt-8 /kt+8exp(/kt+ /kt- /kt+80exp(/kt+ /kt+6 /kt+6exp( /kt+6 /kt-6 /kt+0exp(/kt+6 /kt- /kt+8exp(/kt+6 /kt-6 /kt+80exp(/ kt+6 /kt+ /kt+0exp(/kt+6 /kt+ /kt+6exp(/kt+ /kt- /kt+0exp(/ kt+ /kt-8 /kt+8exp(/kt+ /kt- /kt+80exp(/kt+ /kt- /kt+0exp( /kt+ /kt+6 /kt+56exp(/kt+ /kt+8 /kt+6exp(/kt+0 /kt-0 /kt+0exp (/kt+0 /kt-6 /kt+8exp(/kt+0 /kt-0 /kt+80exp(/kt+0 /kt- /kt+ 0exp(/kT+0 /kt- /kt+56exp(/kt+0 /kt+0 /kt+80exp(/kt+0 /kt+ /k T+80exp(0/kT+8exp(0/kT+ /kt-0 /kt+80exp(0/kt+ /kt- /kt+0exp(0/

20 This journal is The Royal Society of Chemistry 0 kt+ /kt+8 /kt+0exp(0/kt+6 /kt-0 /kt+8exp(0/kt+6 /kt- /kt+80exp(0/k T+6 /kt-6 /kt+0exp(0/kt+6 /kt+ /kt+56exp(0/kt+6 /kt+6 /kt+6exp(0/kt + /kt-0 /kt+0exp(0/kt+ /kt-6 /kt+8exp(0/kt+ /kt-0 /kt+80exp(0 /kt+ /kt- /kt+0exp(0/kt+ /kt- /kt+56exp(0/kt+ /kt+0 /kt+80ex p(0/kt+ /kt+ /kt+6exp(0/kt+0 /kt-8 /kt+0exp(0/kt+0 /kt- /kt+8e xp(0/kt+0 /kt-8 /kt+80exp(0/kt+0 /kt-0 /kt+0exp(0/kt+0 /kt-0 /kt +56exp(0/kT+0 /kt+ /kt+80exp(0/kt+0 /kt+6 /kt+exp(0/kt+0 /kt+ /kt B=+exp( /kt+5exp(6 /kt+7exp( /kt+9exp(0 /kt+exp(/kt+exp(/kt+ /kt- /kt+exp(/kt+ /kt- /kt+5exp(/kt+ /kt+ /kt+exp(/kt+6 /kt-6 /kt+5ex p(/kt+6 /kt- /kt+7exp(/kt+6 /kt+ /kt+5exp(/kt+ /kt-8 /kt+7exp(/kt+ /kt- /kt+9exp(/kt+ /kt+6 /kt+7exp(/kt+0 /kt-0 /kt+9exp(/kt+0 /kt- /kt+exp(/kt+0 /kt+8 /kt+5exp(6/kt+exp(6/kt+ /kt-6 /kt+5exp(6/kt+ / kt- /kt+7exp(6/kt+ /kt+ /kt+exp(6/kt+6 /kt- /kt+exp(6/kt+6 /kt-0 /kt +5exp(6/kT+6 /kt-6 /kt+7exp(6/kt+6 /kt+9exp(6/kt+6 /kt+8 /kt+exp(6/kt+ / kt-6 /kt+5exp(6/kt+ /kt- /kt+7exp(6/kt+ /kt-6 /kt+9exp(6/kt+ /kt+ /kt+exp(6/kt+ /kt+ /kt+5exp(6/kt+0 /kt-0 /kt+7exp(6/kt+0 /kt- /kt +9exp(6/kT+0 /kt-6 /kt+exp(6/kt+0 /kt+ /kt+exp(6/kt+0 /kt+6 /kt+7e xp(/kt+5exp(/kt+ /kt-8 /kt+7exp(/kt+ /kt- /kt+9exp(/kt+ /kt+6 /k T+exp(/kT+6 /kt-6 /kt+5exp(/kt+6 /kt- /kt+7exp(/kt+6 /kt-6 /kt+9e xp(/kt+6 /kt+ /kt+exp(/kt+6 /kt+ /kt+exp(/kt+ /kt- /kt+exp( /kt+ /kt- /kt+5exp(/kt+ /kt-8 /kt+7exp(/kt+ /kt- /kt+9exp( /kt+ /kt- /kt+exp(/kt+ /kt+6 /kt+exp(/kt+ /kt+8 /kt+exp( /kt+0 /kt-0 /kt+5exp(/kt+0 /kt-6 /kt+7exp(/kt+0 /kt-0 /kt+9exp(/ kt+0 /kt- /kt+exp(/kt+0 /kt- /kt+exp(/kt+0 /kt+0 /kt+5exp( /kt+0 /kt+ /kt+9exp(0/kt+7exp(0/kt+ /kt-0 /kt+9exp(0/kt+ /kt- /kt +exp(0/kt+ /kt+8 /kt+5exp(0/kt+6 /kt-0 /kt+7exp(0/kt+6 /kt- /kt+9ex p(0/kt+6 /kt-6 /kt+exp(0/kt+6 /kt+ /kt+exp(0/kt+6 /kt+6 /kt+exp(0 /kt+ /kt-0 /kt+5exp(0/kt+ /kt-6 /kt+7exp(0/kt+ /kt-0 /kt+9exp(0/ kt+ /kt- /kt+exp(0/kt+ /kt- /kt+exp(0/kt+ /kt+0 /kt+5exp(0 /kt+ /kt+ /kt+exp(0/kt+0 /kt-0 /kt+exp(0/kt+0 /kt-8 /kt+5exp(0/ kt+0 /kt- /kt+7exp(0/kt+0 /kt-8 /kt+9exp(0/kt+0 /kt-0 /kt+exp(0/ kt+0 /kt-0 /kt+exp(0/kt+0 /kt+ /kt+5exp(0/kt+0 /kt+6 /kt+7exp(0 /kt+0 /kt+ /kt

21 This journal is The Royal Society of Chemistry 0 Section. Supplementary Physical Characterizations Fig. S8. (a TGA curve of. The first weight loss of 6.9 % in the range of 0 ~ C are attributed to the loss of all lattice water molecules and coordinated water molecules (calcd. 7.6%; the second weight loss at ca. 560 C corresponds to loss of the CO - ions; (b TGA curve of. The first weight loss of 6.0 % in the range of 0 ~ C are attributed to the loss of all lattice water molecules and coordinated water molecules (calcd. 7.5%; the second weight loss in the range of 506 ~ 560 C corresponds to loss of the CO - ions. Fig. S9. IR spectrum for showed the characteristic peaks of carbonate at 6 and 65.

22 This journal is The Royal Society of Chemistry 0 Fig. S0. IR spectrum for showed the characteristic peaks of carbonate at 59 and 78. Fig. S. Energy-dispersive X-ray (EDX analysis of the microtube of.