Supporting Information

© Wiley-VCH 2007

69451 Weinheim, Germany

0

******************************************************************************

Directed assembly of cluster-based supramolecules into one-dimensional

coordination polymers

**************************************************************

Index 1. Materials and general procedures……………………………………………………………………….……......1

2. X-ray Structure Determinations…………………………………………………………………………..….…...2

3. Supporting Tables……………..…………………………………………………………………………..….……3

Table S1. Crystal data and structure refinement for 1………………………..…………………………..….….3

Table S2. Selected bond lengths (Å) and angles (°) for 1……………………………………………...………….4

Table S3. Crystal data and structure refinement for 2………………………..………………………...……….5

Table S4. Selected bond lengths (Å) and angles (°) for 2……………………………………………………...….6

4. Supporting Figures.…………..……………………………………………………………………………...….....7

Figure S1. IR spectra of 1………………...………………………………………………………………………..7

Figure S2. IR spectra of 2………………...………………………………………………………………….…….7

Figure S3. TGA plot for 1…………...……………………………………………………………………………..8

Figure S4. TGA plot for 2…………...…………………………………………………………………………......8

Figure S5. Powder X-ray diffraction patterns of 1……………………………………………………………....9

Figure S6. Powder X-ray diffraction patterns of 2……………………………………………………………....9

Figure S7. Comparison of powder patterns of 2 after 950°..……………………………………………………10

Figure S8. Temperature dependence of magnetic susceptibily of 1…………………….……………………...10

Figure S9. Temperature dependence of magnetic susceptibily of 2. …………………...……………………...11

1

1. Materials and general procedures.

All of the chemicals were obtained from commercial sources and used without further purification. Elemental

analyses were carried out by the Elemental Analysis Lab of Atlantic Microlab, Inc. Thermogravimetric analyses

were performed with about 14mg sample under a flow of argon or air (40 mL/min) at a ramp rate of 5 °C/min, using

a Perkin-Elmer Pyris 1 TGA system. Infrared spectra were recorded as KBr pellets on a Mattson Infinity System

FTIR spectrometer The magnetic susceptibility data were obtained with a SQUID (superconducting quantum

interference device, MPMS, Quantum Design) magnetometer in a gelatin capsule. The data obtained have been

corrected for the diamagnetic moments of the gelatin capsule.

X-ray powder diffraction data was collected at room temperature using a BRUKER P4 general-purpose four-circle

X-ray diffractometer modified with a GADDS/Hi-Star detector positioned 20cm from the sample. The goniometer

was controlled using the GADDS software suite.[1] The sample was mounted on tape and data was recorded in

transmission mode. The system employed a graphite monochromator and a Cu Ka (λ = 1.54184Å) fine-focus sealed

tube operated at 1.2 kW power (40 kV, 30 mA). Four frames were measured at 2θ = 15, 25, 40 and 55° with

exposure times of 240 seconds/frame. The data was reduced by area integration methods to produce a single powder

diffraction pattern for each frame. Individual powder diffraction patterns were merged and analyzed with the

program EVA to produce a single one-dimensional pattern.[2]

[1] GADDS V4.1.14 “General Area Detector Diffraction System Program for Instrument Control and Data

Collection” BRUKER AXS Inc., 5465 East Cheryl Parkway, Madison, WI 53711-5373 USA

[2] EVA V8.0 “Graphics Program for 2-dimensional Data evaluation and Presentation” BRUKER AXS Inc., 5465

East Cheryl Parkway, Madison, WI 53711-5373 USA.

2

2. X-ray Structure Determinations.

A full hemisphere of diffracted intensities (omega scan width of 0.30°) was measured using graphite-monochromated

MoKα radiation on a Bruker SMART APEX CCD Single Crystal Diffraction System. X-rays were provided by a fine-

focus sealed x-ray tube operated at 50kV and 30mA. Lattice constants were determined with the Bruker SMART

software package (SMART version 5.628 and SAINT version 6.36a, Bruker AXS Inc., Madison, Wisconsin, USA.).

Intensity data were measured at 193(2) K and analysis of them showed negligible decay during data collection. Data

were corrected for absorption effects using the multi-scan technique (SADABS). The structure was solved using

"Direct Methods" techniques and all calculations were performed using the SHELXTL (Version 6.12) interactive

software package (Bruker (2001). Bruker AXS Inc., Madison, Wisconsin, USA).

A summary of crystal data and structure refinement for 1 is provided in Table S1. An irregular crystal was selected

and attached to quartz fibers for single crystal X-ray analysis. The integration of the data using a triclinic cell

yielded a total of 22276 reflections to a maximum θ angle of 27.50°, of which 11313 were independent (Rint =

3.95%), and 9111 (80.54%) were greater than 2σ(F2). The structure was solved and refined in the space group P-1

(No. 2), with Z = 1. All nonhydrogen atoms were refined anistropically. Hydrogen atoms on C atoms are generated

and refined isotropically. No attempt was made to locate the hydrogen atoms on the solvent molecules. The final

anisotropic full-matrix least-squares refinement on F2 with 604 variables converged to R1 = 6.70% for observed data

and wR2 = 16.29% for all data. The largest residual peak on the final difference electron density synthesis was

1.425e-/Å3 (0.81 Å from Nb3) and the largest hole was –1.207e-/Å3 (0.44Å from Mn1).

A summary of crystal data and structure refinement for 2 is provided in Table S3. The integration of the data using a

triclinic cell yielded a total of 21319 reflections to a maximum θ angle of 27.50°, of which 10815 were independent

(Rint = 5.77%), and 7343 (67.89%) were greater than 2σ(F2). The structure was solved and refined in the space group

P-1 (No. 2), with Z = 1. All nonhydrogen atoms except the coordinated methanol molecule and all the uncoordinated

water molecules were refined anistropically. Hydrogen atoms on C atoms are generated and refined isotropically. No

attempt was made to locate the hydrogen atoms on the disordered solvent molecules. The final anisotropic full-

matrix least-squares refinement on F2 with 558 variables converged to R1 = 5.99% for observed data and wR2 =

13.00% for all data. The maximum residual peak and hole on the final difference fourier map corresponded to

0.967e-/Å3 (0.75Å from O14) and –0.704e-/Å3 (0.92Å from Nb3), respectively.

3

3. Supporting Tables.

Table S1. Crystal data and structure refinement for 1. Empirical formula C86H90Cl12Mn4N16Nb6O10 Crystal appearance Dark-brown, irregular Formula weight 2710.36 Temperature 193(2) K Crystal system Triclinic space group P-1 Unit cell dimensions A (Å) 12.904(2) B (Å) 14.024(2) C (Å) 14.101(2) α (°) 100.340(2) β (°) 91.070(2) γ (°) 94.313(2) Volume(Å3) / Z 2502.0(7)/ 1 Diffractometer Siemens Smart CCD λ(Mo Kα),Å 0.71073 Calculated density 1.799 Mg/m3 Absorption coefficient 1.530 mm-1 F(000) 1348 Crystal size 0.18 x 0.09x 0.08 mm Theta range for data collection 3.76 to 27.50° Limiting indices -16≤h≤16, -18≤k≤18, -18≤l≤18 Reflections collected / unique 22276 / 11313 R(int) 0.0395 Completeness to theta = 27.50 98.4 % Absorption correction Multi-scan Max. and min. transmission 1.000000 and 0.774252 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 9111/ 311 / 604 Goodness-of-fit on F2 1.132 Final R indices [I>2sigma(I)] R1 = 0.0670, wR2 = 0.1544 R indices (all data) R1 = 0.0843, wR2 = 0.1629 Max/mean shift in final cycle 0.001/0.000 Largest diff. peak and hole 1.425 and -1.207 e. Å3 *R= ∑(||Fo|-|Fc||) / ∑ |Fo| , **wR = {∑w [(F2

o − F2c)] / ∑w [(F 2o ) 2]}0.5

w = [σ2(F2o) + (0.0723P)2+4.0411P] −1 , where P = (F2

o +2 F2c)/3

4

Table S2. Selected bond lengths (Å) and angles (°) for 1. Nb-C 2.266(6)~ 2.273(7) Nb-Cl 2.4538(16)~2.4743(15) Nb-Nb 2.9200(8)~2.9280(8) C≡N 1.128(9)~1.153(8) Mn(1)-O(1) 1.859(5) Mn(2)-O(4) 1.839(5) Mn(1)-O(2) 1.872(5) Mn(2)-O(3) 1.901(4) Mn(1)-N(2) 1.999(6) Mn(2)-N(3) 1.973(6) Mn(1)-N(1) 2.003(6) Mn(2)-N(4) 1.994(6) Mn(1)-O(5) 2.262(6) Mn(2)-N(102) 2.222(6) Mn(1)-N(101) 2.291(6) Mn(2)-O(3)#2 2.363(4) Cl-Nb-Cl1 87.30(6)~89.66(6) Cl-Nb-Cl2 162.70(5)~ 162.92(5) Nb-Nb-Nb3 89.83(2)~ 90.17(2) C-Nb-Cl 79.70(17)~83.13(17) Nb-Nb-Nb4 59.820(19)~60.090(19) Nb-Cl-Nb 72.48(4)~73.19(4) C≡N-Mn 153.2(6)~159.5(6) N≡C-Nb 175.0(6)~178.8(6) O(1)-Mn(1)-O(2) 95.2(2) O(4)-Mn(2)-O(3) 93.1(2) O(1)-Mn(1)-N(2) 173.9(3) O(4)-Mn(2)-N(3) 176.7(3) O(2)-Mn(1)-N(2) 89.7(3) O(3)-Mn(2)-N(3) 89.7(2) O(1)-Mn(1)-N(1) 91.6(2) O(4)-Mn(2)-N(4) 91.4(3) O(2)-Mn(1)-N(1) 173.1(3) O(3)-Mn(2)-N(4) 170.9(2) N(2)-Mn(1)-N(1) 83.5(3) N(3)-Mn(2)-N(4) 85.6(3) O(1)-Mn(1)-O(5) 88.1(2) O(4)-Mn(2)-N(102) 92.7(2) O(2)-Mn(1)-O(5) 91.0(2) O(3)-Mn(2)-N(102) 98.9(2) N(2)-Mn(1)-O(5) 88.1(2) N(3)-Mn(2)-N(102) 88.5(2) N(1)-Mn(1)-O(5) 87.8(3) N(4)-Mn(2)-N(102) 88.8(2) O(1)-Mn(1)-N(101) 90.3(2) O(4)-Mn(2)-O(3)#2 90.17(19) O(2)-Mn(1)-N(101) 96.8(2) O(3)-Mn(2)-O(3)#2 77.13(18) N(2)-Mn(1)-N(101) 92.8(3) N(3)-Mn(2)-O(3)#2 88.77(19) N(1)-Mn(1)-N(101) 84.6(2) N(4)-Mn(2)-O(3)#2 94.9(2) Mn(2)-O(3)-Mn(2)#2 102.87(18) N(102)-Mn(2)-O(3)#2 175.2(2)

Symmetry transformations used to generate equivalent atoms: #1 -x,-y+1,-z #2 -x+1,-y+2,-z

1 The two chlorate atoms act as edge ligands of Nb atoms inside a face. 2 The two chlorate atoms act as edge ligands of Nb atoms inside an equatorial plane. 3 The three Nb atoms are inside an equatorial plane. 4 The three Nb atoms are inside a face.

5

Table S3. Crystal data and structure refinement for 2.

Empirical formula C93H106.50Cl12Mn4N17.50Nb6O18 Crystal appearance red-brown needle-plate Formula weight 2960.08 Temperature 193(2) K Crystal system Triclinic space group P-1 Unit cell dimensions A (Å) 13.1923(16) B (Å) 14.2188(17) C (Å) 16.3598(19) α (°) 97.737(2) β (°) 100.990(2) γ (°) 102.532(2) Volume(Å3) / Z 2890.7(6) / 1 Diffractometer Siemens Smart CCD λ(Mo Kα),Å 0.71073 Calculated density 1.700 Mg/m3 Absorption coefficient 1.337 mm-1 F(000) 1481 Crystal size 0.40 x 0.07 x 0.03 mm θTheta range for data collection 3.83 to 27.50 deg.° Limiting indices -16≤h≤17, -18≤k≤18, -20≤l≤21 Reflections collected / unique 25667 / 13079 R(int) 0.0327 Completeness to theta = 27.50 98.4% Absorption correction Multi-scan Max. and min. transmission 1.000000 and 0.742663 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 10437 / 338 /688 Goodness-of-fit on F2 1.028 Final R indices [I>2sigma(I)] R1 = 0.0435, wR2 = 0.1049 R indices (all data) R1 = 0.0581, wR2 = 0.1130 Max/mean shift in final cycle 0.001/0.000 Largest diff. peak and hole 1.040, -0.929 *R= ∑(||Fo|-|Fc||) / ∑ |Fo| , **wR = {∑w [(F2

o − F2c)] / ∑w [(F 2o ) 2]}0.5

w = [σ2(F2o) + (0.0598P)2+0.8822 P] −1 , where P = (F2

o +2 F2c)/3

6

Table S4. Selected bond lengths (Å) and angles (°) for 2. Nb-Cl 2.4494(9)~ 2.4772(9) Nb-Nb 2.9255(5)~ 2.9401(5) Nb-C 2.284(4)~2.296(4) N≡C 1.133(5)~1.150(5) Mn(1)-O(1) 1.858(3) Mn(2)-O(4) 1.847(3) Mn(1)-O(2) 1.870(3) Mn(2)-O(3) 1.850(3) Mn(1)-N(1) 1.992(3) Mn(2)-N(4) 1.989(4) Mn(1)-N(2) 1.996(3) Mn(2)-N(3) 1.992(3) Mn(1)-N(101) 2.317(3) Mn(2)-O(5) 2.288(3) Mn(1)-N(5) 2.362(3) Mn(2)-N(102) 2.324(3) Cl-Nb-Cl1 87.22(3)~89.99(3) C-Nb-Cl 79.16(9)~83.77(9) Cl-Nb-Cl2 162.79(3)~163.26(3) Nb-Cl-Nb 72.52(3)~73.60(3) Nb-Nb-Nb3 59.787(12)~60.239(12) Nb-Nb-Nb4 89.860(12)~90.140(12) N≡C-Nb(1) 172.1(3)~176.7(4) C≡N-Mn 150.7(3)~158.9(3) O(1)-Mn(1)-O(2) 94.54(13) O(4)-Mn(2)-O(3) 92.26(13) O(1)-Mn(1)-N(1) 91.87(12) O(4)-Mn(2)-N(4) 175.62(15) O(2)-Mn(1)-N(1) 171.97(13) O(3)-Mn(2)-N(4) 90.60(14) O(1)-Mn(1)-N(2) 175.91(13) O(4)-Mn(2)-N(3) 91.18(14) O(2)-Mn(1)-N(2) 89.49(14) O(3)-Mn(2)-N(3) 176.51(14) N(1)-Mn(1)-N(2) 84.17(13) N(4)-Mn(2)-N(3) 85.93(15) O(1)-Mn(1)-N(101) 93.59(12) O(4)-Mn(2)-O(5) 89.77(13) O(2)-Mn(1)-N(101) 90.56(12) O(3)-Mn(2)-O(5) 91.12(13) N(1)-Mn(1)-N(101) 93.87(12) N(4)-Mn(2)-O(5) 86.85(14) N(2)-Mn(1)-N(101) 85.64(12) N(3)-Mn(2)-O(5) 88.29(14) O(1)-Mn(1)-N(5) 89.45(11) O(4)-Mn(2)-N(102) 93.39(13) O(2)-Mn(1)-N(5) 83.53(12) O(3)-Mn(2)-N(102) 95.63(13) N(1)-Mn(1)-N(5) 91.71(12) N(4)-Mn(2)-N(102) 89.63(14) N(2)-Mn(1)-N(5) 91.73(12) N(3)-Mn(2)-N(102) 84.76(13) N(101)-Mn(1)-N(5) 173.56(12) O(5)-Mn(2)-N(102) 172.42(12)

1 The two chlorate atoms act as edge ligands of Nb atoms inside a face. 2 The two chlorate atoms act as edge ligands of Nb atoms inside an equatorial plane. 3 The three Nb atoms are inside a face. 4 The three Nb atoms are inside an equatorial plane.

7

5. Supporting Figures

Figure S1. IR spectra of 1.

Figure S2. IR spectra of 2.

8

Figure S3. TGA plot for 1 heated from 30 °C to 950 °C at 5 °C /min under a flow of air (40 mL/min).

(b)

Figure S4. TGA plot for 2 heated from 30 °C to 950 °C at 5 °C /min under a flow of air (40 mL/min)

9

Figure S5. Powder X-ray diffraction patterns of 1: pattern simulated from crystal structure in black; observed

pattern at room temperature in red; observed pattern after being heated to 950°C in green; simulated from crystal

structure of MnNb2O6 in blue.

Figure S6. Powder X-ray diffraction patterns of 2: pattern simulated from crystal structure in black; observed

pattern at room temperature in red; observed pattern after being heated to 600°C in green; observed pattern after

being heated to 950°C in blue.

10

Figure S7. Comparison of Powder patterns of 2 after 950°C with that simulated from MnNb2O6 and Mn3O4. ICSD

code for MnNb2O6: 31944; ICSD code for Mn3O4: 30005.

Figure S8. Temperature dependence of magnetic susceptibily of 1. (5-300K at 1000G).

11

Figure S9. Temperature dependence of magnetic susceptibily of 2. (5-300K at 1000G).

For 1, based on the isotropic Heisenberg model Η = -2JS1S2 (S1 = S2 = 2), the van Vleck equation is given as

follows:

)1(3

297531

301452 22

/20/12/6/2

/20/12/6/222

dimer +×+++++

+++×= SS

kTNg

eeeeeeee

kTNg

kTJkTJkTJkTJ

kTJkTJkTJkTJ ββχ

For 2, the equation is given as follows:

)1(3

4 22

+×= SSkT

Ng βχ

χβχ

χ)/'2(1 22NgzjM −

=