p-tert-butylthiacalix[4]arene-surpported High-nuclearity {Co 24 M 8 } (M = Mo or W) Nanospheres and the Hybrids with Keggin Polyoxometalates

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1 Supporting Information p-tert-butylthiacalix[4]arene-surpported High-nuclearity {Co 24 M 8 } (M = Mo or W) Nanospheres and the Hybrids with Keggin Polyoxometalates Yanfeng Bi, a,b Shangchao Du a,b and Wuping Liao *a Experimental Section Materials and Measurements: p-tert-butylthiacalix[4]arene (H 4 TC4A) was synthesized by literature method, 1 H 3 PMo 12 O 4 and H 3 PW 12 O 4 was synthesized according to the well-known method, 2 and other reagents were purchased from commercial sources and used as received (Co(CH 3 COO) 2 4H 2 O, >99.5%, Sinopharm Chemiscal Reagent Co., Ltd; Na 2 MoO 4 2H 2 O, >99.5%, Na 2 WO 4 2H 2 O, >99.%, Alfa). All the solvents used were analytical reagents. Mo, W, Co, and S analyses were determined by a HITACHI S-48 Scanning Electron Microscope equipped EDS. TGA measurement is performed on a PYRIS DIAMOND. FT-IR spectra (KBr pellets) were recorded on a Bruker Vertex 7 spectrometer. Magnetic susceptibility measurements for 1-4 were performed on a Quantum Design MPMS XL-5 SQUID system in the temperature range of 2 3 K. Diamagnetic corrections for the sample and sample holder were applied to the data. A CHI 44 Electrochemical Workstation was used for the electrochemical measurements. A conventional three-electrode cell, consisting a 3-modified carbon paste electrode (3-CPE ) or a bare carbon paste electrode as the working electrode, a saturated calomel reference electrode (SCE) and a Pt gauze counter electrode was used. All potentials were measured and reported versus the SCE. All the experiments were conducted at room temperature. Syntheses of 1-4: Purple single crystals of 1/2 were obtained from reaction of the mixture of S1

2 p-tert-butylthiacalix[4]arene (.9g,.13 mmol), Co(CH 3 COO) 2 4H 2 O (.1 g,.4 mmol), Na 2 MoO 4 2H 2 O (.48g,.2 mmol)/na 2 WO 4 2H 2 O (.67g,.2 mmol), CHCl 3 (5 ml), and CH 3 CH 2 OH (5ml) in a 2 ml Teflon-lined autoclave which was kept at 13 C for 3 days and then slowly cooled down to 2 C at about 4 C/h. The crystals were isolated by filtration and then washed with 1:1 ethanol-chloroform. Yield: ca. 28 % for 1 and 25% for 2 with respect to calixarene. The EDS analysis of 1 /2 reveals that the molar ratio of Mo/W: Co: S molar is.55: 1.54:1.51/3.86 :11.56: 11.69, comparable to the expected value (8: 24: 24 = 1: 3 : 3). Black/Red single crystals of 3/4 were obtained from reaction of the mixture of p-tert-butylthiacalix[4]arene (.9g,.13 mmol), Co(CH 3 COO) 2 4H 2 O (.1 g,.4 mmol), H 3 PMo 12 O 4 xh 2 O (ca..1g,.5 mmol)/ H 3 PW 12 O 4 xh 2 O (ca..15g,.5 mmol), CHCl 3 (5 ml), and CH 3 CH 2 OH (5ml) in a 2 ml Teflon-lined autoclave which was kept at 13 C for 3 days and then slowly cooled to 2 C at about 4 C/h. The crystals were isolated by filtration and then washed with 1:1 ethanol-chloroform. Yield: ca. 6 % for 3 and 15% for 4 with respect to calixarene. The EDS analysis of 3 /4 reveals that the molar ratio of Mo/W: Co: S is 6.4 : 7.22 : 7.2/3.86: 4.6 : 4.73, comparable to the expected value (2: 24: 24 = 1: 1.2 : 1.2). MO 4 group may come from the decomposition of H 3 PM 12 O 4. The introduction of Na 2 MoO 4 2H 2 O/Na 2 WO 4 2H 2 O into the feed does result in good yield of 3 and 4 but also leads to the formation of some green (Co 4 (TC4A) 2 ) acicular crystals which is an analogue of Mn 4 (TC4A) 2 reported by D. Luneau and co-workers. 3 However, the green acicular crystals can be washed off by CHCl 3 easily. Chloride anions were unexpectedly found in the four products and the assignment was based on charge balance considerations and the long band distances (ca. 2.7 Å, larger than common Co-O distance). The origin of chlorine atoms may result form the decomposition of chloroform. 4 S2

3 TGA analyses of 1 and 3 (taken for examples, Fig. S7-8) show that the onset of the solvent loss is at the very beginning of recording and the weight decreases sharply up to 12 C corresponding to the release of the solvent molecules, which indicated the easy lose of solvent molecules even at low temperature. Due to the easy loss of solvent molecules, TGA analyses for 2 and 4, and element analyses for 1-4 were not performed. Preparation of the 3-modified carbon paste electrode and the bare carbon paste electrode: The 3-modified carbon paste electrode was prepared by the following method:.3 g graphite powder and.25g compound 3 were mixed and ground by agate mortar and pestle for approximately 3 min to achieve an even, dry mixture;.2 ml paraffin oil was added and the mixture was stirred with a glass rod; then the homogenized mixture was used to pack 3 mm inner diameter glass tubes to a length of.8 cm. The electrical contact was established with the copper stick, and the surface of the 3-CPE was wiped with weighing paper. The bare carbon paste electrode was prepared by the same procedure as described above except that the modifier was not added. 1 N. Iki, C. Kabuto, T. Fukushima, H. Kumagai, H.Takeya, S. Miyanari, T. Miyashi and S. Miyano, Tetrahedron., 2, 56, H. Wu, J Biol. Chem., 192, 43, C. Desroches, G. Pilet, S. A. Borshch, S. Parola and D. Luneau, Inorg. Chem., 25, 44, Y. F. Bi, G. C. Xu, W. P. Liao, S. C. Du, X. W. Wang, R. P. Deng, H. J. Zhang and S. Gao, Chem. Commun., 2, 46, S3

4 Fig. S1 Representation of the {Co24M8} core and six capping TC4A molecules. Fig. S2 The nanosize {Co4-TC4A} subunit, {PM12O4}, and the cationic [Co24(TC4A)6(MO4)8Cl6]2+ nanosphere. S4

5 Fig. S3 Comparison of the sodalite-like CoII24 with a protrudent MIV8 cube in 1-4 (left) and that with an encapsulated CoIII8 cube in the {Co32} nanosphere reported in ref. 8a (right). Fig. S4 Different contact modes between cationic nanospheres and POMs in 3 (up) and 4 (down). S5

6 Fig. S5 The arrangements and distances between the cationic spherical units and POMs (upper for 3 and bottom for 4). 9 Transmittance(%) compound 1 compound Wavenumber/cm 5-1 Fig. S6 Infrared spectra of compounds 1 and 3. The peaks at 946 and 881cm 1 for 1 are attributed to the ν(mo Od) and ν(mo O Co) vibrations, respectively. The peaks at 66, 965, 884, and 8 cm 1 for 3 are assigned to the ν(p Oa), ν(mo Od), ν(mo Oa), ν(mo Ob Mo), and ν(mo Oc Mo) vibrations, respectively. S6

7 Weightloss (%) Temperature ( o C) Temperature Difference ( o C) Fig. S7 TG and DTA curves for compound 1. The TG curve indicates that solvent molecules are eliminated from the network (calcd %; found %) when the temperature is increased to about 12 o C. Weightloss (%) Temperature ( o C) Temperature Difference ( o C) Fig. S8 TG and DTA curves for compound 3. The TG curve indicates that solvent molecules are eliminated from the network (calcd %; found %) when the temperature is increased to about 12 o C. S7

8 Fig. S9 Cyclic voltammograms of the 3-CPE in the 1M H 2 SO 4 solution at different scan rates (from inner to outer: 2, 4, 6, 8,, 12, 14, 16, 18, 2, 25, 3, 35, 4, 45, 5 mvs 1 ). Insert: The dependence of anodic peak (I, II, III and IV ) and cathodic peak (II, III and IV) current on scan rates. Fig. S Cyclic voltammograms of the 3-CPE in 1 M H 2 SO 4 solution containing.~.7 mm KNO 2 (b-i) and a bare CPE in 1. mm KNO M H 2 SO 4 solution (a). Potentials vs. SCE. Scan rate: 2 mvs 1. Insert: The line dependence of three cathodic peak current on concentration of NO 2 (I = [NO 2 ] for II, I = [NO 2 ] for III, and I = [NO 2 ] for IV). S8

9 Fig. S11 Cyclic voltammograms of the 1-CPE in the 1M H 2 SO 4 solution at different scan rates (from inner to outer: 6, 8,, 12, 14, 16, 18, 2, 25, 3, 35, 4, 45, 5 mvs 1 ). 5 M / Nβ M / Nβ H / koe T = 2 K H / koe Figure S12. Field-dependencies of magnetization of 1 at 2 K. S9

10 M / Nβ M / Nβ H / koe -5 T = 2 K H / koe Figure S13. Field-dependencies of magnetization of 2 at 2 K. M / Nβ M / Nβ H / koe T = 2 K H / koe Figure S14. Field-dependencies of magnetization of 3 at 2 K. S

11 M / Nβ M / Nβ H / koe T = 2 K H / koe Figure S15. Field-dependencies of magnetization of 4 at 2 K. S11

12 Table S1. Selected bond distances (Å) and angles (º) for 1 and Co(1)-O(1) 1.991(4) 1.993(5) Co(2)-O(1) 1.993(4) 1.995(5) Co(1)-O(1)# (4) 1.993(5) Co(2)-O(1)# (4) 1.995(5) Co(1)-O(3) 2.73(7) 2.52(8) Co(2)-O(4) 2.7(5) 2.65(7) Co(1)-O(3)#4 2.73(7) 2.52(8) Co(2)-O(4) #7 2.7(5) 2.65(7) Co(1)-S(1) 2.462(2) 2.477(3) Co(2)- S(2) 2.463(2) 2.479(3) Co(1)-Cl(1) 2.742(2) 2.747(5) Co(2)- Cl(1) 2.721(2) 2.732(1) Co(3)-O(2) 1.995(5) 1.994(5) Mo(1)-O(3) 1.799(9) 1.835(9) Co(3)-O(2)# (5) 1.995(5) Mo(1)-O(4) 1.89(5) 1.814(6) Co(3)-O(4) 2.64(5) 2.59(6) Mo(1)-O(4) #8 1.89(5) 1.814(6) Co(3)-O(4)#7 2.64(5) 2.59(6) Mo(1)-O(5) 1.681(9) 1.78(1) Co(3)-S(3) 2.459(2) 2.481(3) Co(3)-Cl(2) 2.728(3) 2.53(3) Co(1)-O(1)-Co(2) (19) 115.4(2) Co(1)-O(3)-Co(1)#4.83(229) 2.1(4) Co(2)-O(4)-Co(3).5(2) 1.2(2) Co(3)-O(2)-Co(3)# (3) 115.3(3) Co(1)-Cl(1)-Co(1)# (32) (4) Co(1)-Cl(1)-Co(2) (2) 75.94(1) Co(3)-Cl(2)-Co(3)# (3) 84.55(5) Co(3)-Cl(2)-Co(3)# (32) 144.2(44) Mo(1)-O(3)-Co(1) 128.9(3) 128.4(4) Mo(1)-O(3)-Co(1)# (3) 128.4(4) Mo(1)-O(4)-Co(2) 129.2(3) 128.4(4) Mo(1)-O(4)-Co(3) 129.(3) 129.1(3) #1, -y,x,z; #2, -x,-y,z; #3, y,-x,z; #4, y,x,-z; #5, -x,y,-z; #6, x,y,-z; #7, -x,y,z; #8, y,x,z. S12

13 Table S2. Selected bond distances (Å) and angles (º) for compound 3 Co(1)-O(1) 1.971(4) Co(2)-O(1) 1.977(4) Co(1)-O(1)# (4) Co(2)-O(2) 1.976(4) Co(1)-O(6)#3 2.88(5) Co(2)-O(4) 2.9(4) Co(1)-O(6)#4 2.88(5) Co(2)-O(5) #3 2.85(4) Co(1)-S(1) 2.485(3) Co(2)- S(2) 2.494(16) Co(1)-Cl(1) (28) Co(2)- Cl(1) 2.6(14) Co(3)-O(2)# (4) Co(4)-O(3) 1.98(4) Co(3)-O(6) 2.78(5) Co(4)-O(3)# (4) Co(3)-O(6)#5 2.78(5) Co(4)-O(4) 2.82(5) Co(3)-O(2) 1.986(4) Co(4)-O(5)#3 2.87(5) Co(3)-S(3) 2.497(3) Co(4)-S(4) (16) Co(3)-Cl(1) 2.774(3) Co(4)-Cl(2) 2.684(2) Mo(1)-O(4) 1.746(4) Mo(1)-O(6) 1.741(5) Mo(1)-O(5) 1.748(5) Mo(1)-O(7) 1.645(7) Co(1)-O(1)-Co(2) 114.3(2) Co(1)-Cl(1)-Co(2) (16) Co(1)-Cl(1)-Co(3) 122.2(2) Co(2)-O(2)-Co(3) 114.1(2) Co(2)-O(4)-Co(4).47(19) Co(2)- Cl(1)-Co(2)# () Co(3)-O(6)-Co(1)#1 99.9(2) Co(3)-Cl(1)-Co(2) (16) Co(4)-O(3)-Co(4)# (18) Co(4)-Cl(2)-Co(4)# (22) Co(4)-Cl(2)-Co(4)# (22) Mo(1)-O(4)-Co(2) 13.9(3) Mo(1)-O(4)-Co(4) 128.2(2) Mo(1)-O(5)-Co(2)# (2) Mo(1)-O(5)-Co(4)# (2) Mo(1)-O(6)-Co(1)# (3) Mo(1)-O(6)-Co(3) 13.(2) 1, 1-y,1+x,z; 2, -x,2-y,z; 3, -1+y,1-x,z; 4, -1+y,1-x,2-z; 5, x,y,2-z. S13

14 Table S3. Selected bond distances (Å) and angles (º) for compound 4 Co(1)-O(21) 2.111(5) Co(2)-O(26)#1 2.3(6) Co(1)-O(4) 1.991(5) Co(2)-O(23) 2.83(5) Co(1)-S(1) 2.496(3) Co(2)-S(2) 2.463(3) Co(1)-O(19) 2.88(5) Co(2)-O(2) 1.977(5) Co(1)-O(1) 1.982(5) Co(2)-O(1) 1.99(6) Co(1)-Cl(1) 2.272(1) Co(2)-Cl(1) 2.739(3) Co(3)-O(13) 2.92(6) Co(4)-O(15) 2.97(6) Co(3)-O(25)#1 2.92(7) Co(4)-O(3) 1.991(4) Co(3)-S(3) 2.457(2) Co(4)-S(4) 2.466(3) Co(3)-O(3) 1.969(6) Co(4)-O(4) 1.997(6) Co(3)-O(2) 1.976(6) Co(4)-O(17) 2.63(5) Co(3)-Cl(1) 2.727(3) Co(4)-Cl(1) 2.715(2) Co(5)-O(8) 1.976(4) Co(6)-O(22)#1 2.1(6) Co(5)-O(5) 1.994(6) Co(6)-O(14) 2.78(5) Co(5)-S(5) 2.464(3) Co(6)-S(6) 2.473(2) Co(5)-O(17) 2.123(6) Co(6)-O(1) 1.993(7) Co(5)-O(15) 2.81(4) Co(6)-O(6) 1.969(5) Co(5)-Cl(2) 2.737(3) Co(6)-Cl(2) 2.77(3) Co(7)-O(26) 2.75(5) Co(8)-O(8) 1.968(5) Co(7)-O(6) 1.971(5) Co(8)-O(7) 1.984(7) Co(7)-S(7) 2.437(2) Co(8)-S(8) 2.471(2) Co(7)-O(7) 2.1(6) Co(8)-O(18) 2.3(6) Co(7)-O(23)# (6) Co(8)-O(27) 2.88(6) Co(7)-Cl(2) 2.744(3) Co(8)-Cl(2) 2.73(2) Co(9)-O(18) 2.77(5) Co()-O(9) 1.969(6) Co(9)-O(27) 2.95(7) Co()-O(25) 2.79(6) Co(9)-S(9) 2.457(2) Co()-S() 2.46(2) Co(9)-O(12) 1.99(7) Co()-O(13)#1 2.9(6) Co(9)-O(9) 1.985(5) Co()-O() 1.98(6) Co(9)-Cl(3) 2.719(2) Co()-Cl(3) 2.741(3) Co(11)-O(11) 1.999(7) Co(12)-O(11) 1.994(5) S14

15 Co(11)-O(22) 2.72(5) Co(12)-O(21) 2.89(4) Co(11)-S(11) 2.479(2) Co(12)-S(12) 2.467(3) Co(11)-O(14)# (6) Co(12)-O(19) 2.99(5) Co(11)-O() 1.982(5) Co(12)-O(12) 1.994(5) Co(11)-Cl(3) 2.691(3) Co(12)-Cl(3) 2.761(3) W(1)-O(13) 1.788(5) W(2)-O(17) 1.82(5) W(1)-O(14) 1.783(7) W(2)-O(18) 1.796(6) W(1)-O(15) 1.798(6) W(2)-O(19) 1.82(5) W(1)-O(16) 1.715(7) W(2)-O(2) 1.71(7) W(3)-O(21) 1.796(5) W(4)-O(25) 1.781(5) W(3)-O(22) 1.797(6) W(4)-O(26) 1.791(6) W(3)-O(23) 1.793(5) W(4)-O(27) 1.784(7) W(3)-O(24) 1.712(7) W(4)-O(28) 1.76(6) Co(1)-O(1)-Co(2) 115.4(3) Co(1)-O(4)-Co(4) 116.4(3) Co(1)-O(19)-Co(12) 2.(2) Co(1)-O(21)-Co(12) 1.6(2) Co(1)-Cl(1)-Co(2) (6) Co(1)-Cl(1)-Co(3) (8) Co(1)-Cl(1)-Co(4) 77.12(7) Co(2)-O(2)-Co(3) 117.1(3) Co(2)-O(23)-Co(7)#1 1.1(2) Co(2)-Cl(1)-Co(3) 76.21(7) Co(2)-Cl(1)-Co(4) (8) Co(3)-O(3)-Co(4) 115.8(3) Co(3)-O(13)-Co()#1 1.2(2) Co(3)-Cl(1)-Co(4) (6) Co(4)-O(15)-Co(5) 1.8(2) Co(4)-O(17)-Co(5) 1.5(2) Co(5)-O(5)-Co(6) 116.4(2) Co(5)-O(8)-Co(8) 115.5(3) Co(5)-Cl(2)-Co(6) 77.(8) Co(5)-Cl(2)-Co(7) 121.5(1) Co(5)-Cl(2)-Co(8) (6) Co(6)-O(6)-Co(7) 116.(3) Co(6)-O(14)-Co(11)#1.8(3) Co(6)-Cl(2)-Co(7) (6) Co(6)-Cl(2)-Co(8) (9) Co(7)-O(7)-Co(8) 117.2(2) Co(7)-O(26)-Co(2)#1 2.(2) Co(7)-Cl(2)-Co(8) (8) Co(8)-O(27)-Co(9) 1.1(3) Co(8)-O(18)-Co(9) 1.2(3) Co(9)-O(9)-Co() 117.2(2) Co(9)-O(12)-Co(12) 116.3(3) Co(9)-Cl(3)-Co() (7) Co(9)-Cl(3)-Co(11) 121.8(8) Co(9)-Cl(3)-Co(12) 76.28(7) Co()-O()-Co(11) 115.6(2) S15

16 Co()-O(25)-Co(3)#1 1.5(2) Co()-Cl(3)-Co(11) 76.28(66) Co()-Cl(3)-Co(12) (1) Co(11)-O(11)-Co(12) 116.2(3) Co(11)-O(22)-Co(6)#1 1.6(3) Co(11)-Cl(3)-Co(12) 76.9(7) W(1)-O(13)-Co(3) 128.8(3) W(1)-O(13)-Co()# (4) W(1)-O(14)-Co(11)# (2) W(1)-O(14)-Co(6) 129.4(3) W(1)-O(15)-Co(4) 128.9(2) W(1)-O(15)-Co(5) 128.7(3) W(2)-O(17)-Co(4) 129.(3) W(2)-O(17)-Co(5) 128.1(3) W(2)-O(18)-Co(8) 129.4(2) W(2)-O(18)-Co(9) 128.8(3) W(2)-O(19)-Co(1) 129.6(2) W(2)-O(19)-Co(12) 127.7(3) W(3)-O(21)-Co(12) 127.4(3) W(3)-O(21)-Co(1) 129.6(2) W(3)-O(22)-Co(11) 128.7(3) W(3)-O(22)-Co(6)# (2) W(3)-O(23)-Co(2) 129.8(3) W(3)-O(23)-Co(7)# (3) W(4)-O(25)-Co() 128.3(4) W(4)-O(25)-Co(3)# (4) W(4)-O(26)-Co(7) 127.3(3) W(4)-O(26)-Co(2)#1 13.2(3) W(4)-O(27)-Co(9) 129.8(3) W(4)-O(27)-Co(8) 128.9(3) #1, 1-x,-y,1-z. S16