Self-assembly of silver (I) metallomacrocycles using ...€¦ · S2 Table of Contents S2 1. 1H NMR Spectra of synthesized compounds.S4 1H NMR (d 6-acetone, 300K) of 2a. S4 1H NMR

S1

Supporting information

Self-assembly of silver (I)

metallomacrocycles using unsupported 1,4-

substituted-1,2,3-triazole “Click” ligands.

Martin L.Gower and James D Crowley*.

Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand

[email protected]

Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2010

S2

Table of Contents S2

1. 1H NMR Spectra of synthesized compounds. S4 1H NMR (d6-acetone, 300K) of 2a. S4

1H NMR (d6-acetone, 300K) of 2b. S5

1H NMR (d6-acetone, 300K) of 3a. S6



Figure 1. Partial 1H NMR spectra (300 MHz, d6-acetone, 300 K) of a) Ligand 2a, b)

[Ag2(2a)2](SbF6)2, 4a. S8


Figure 2. Partial 1H NMR spectra (300 MHz, d6-acetone, 300 K) of a) Ligand 2b, b)

[Ag2(2b)2](SbF6)2. S9



[Ag2(3a)2](SbF6)2, 5a. S10

1H NMR (d6-acetone, 300K) of [Ag2(5b)2](SbF6)2. S11


[Ag2(3b)2](SbF6)2, 5b. S11

2. SPARTAN CPK models of the silver(I) complexes. S12

Figure 5. Space Filling (CPK, left) and tube (right) molecular models of the trimeric 3:3

complex formed between 2a and Ag(SbF6). S12

Figure 6. Space Filling (CPK, left) and tube (right) molecular models showing the complex

formed if Ag(I) binding to the ligands (3a and 3b) was through the N2 nitrogen of the

triazole. S12


S3

3. HR-ESMS Spectra of the silver complexes. S13

Figure 7. HR-ESMS (CH3CN) of [Ag2(2a)2](SbF6)2, 4a. S13

Figure 8. Observed and Calculated isotopic distributions for the

[Ag2(2a)2](SbF6)+ ion. S14

Figure 9. HR-ESMS (CH3CN) of [Ag2(2b)2](SbF6)2, 4b. S15


[Ag2(2b)2](SbF6)2+ ion. S16

Figure 11. HR-ESMS (CH3CN) of [Ag2(3a)2](SbF6)2, 5a. S17


[Ag2(3a)2](SbF6)2+ ion. S18

Figure 13. HR-ESMS (CH3CN) of [Ag2(3b)2](SbF6)2, 5b. S19


[Ag2(3b)2](SbF6)2+ ion. S20

4. X-ray Crystallographic Data S21

Figure 15. ORTEP (top) and space filling (bottom) views of the [2a2Ag2]2+ cation. S21

Figure 16. Two views of [(2a)2Ag2](SbF6)2 (3a) showing the close contacts between the

SbF6- anions and the Ag(I) ions. S22

Figure 17. Two views of the extended structure of [(2a)2Ag2](SbF6)2 (3a). a) a ball and stick

diagram and b) a space filing diagram. S22

Figure 18. ORTEP (top) and space filling (bottom) views of the [(2b)4Ag2]2+ cation. S23

Figure 19. Two views of the extended structure of [(2b)2Ag2](SbF6)2 (3b). a) a ball and stick


Figure 20. An ORTEP diagram of the [(3b)4Ag2]2+ cation. S24

Figure 21. Two views of the complete cationic unit of [(3b)2Ag2](SbF6)2 (5b). a) a ball and

stick diagram and b) a space filing diagram. S25

Figure 22. Two views of the extended structure of [(3b)2Ag2](SbF6)2 (5b). a) a ball and stick


4.1 X-Ray data collection and refinement for 5b (acetone). S26

Table 1 Crystal data and structure refinement for 5b (acetone). S26

Figure 23. An ORTEP diagram of [(3b)4Ag2]2+ cation from the of the crystal structure 5b

(acetone) S27

5. References. S27


S4

1. 1H NMR spectra of synthesized compounds.

1H NMR (d6-acetone, 300K) of 2a.


S5

1H NMR (d6-acetone, 300K) of 2b.


S6



S7



S8

4.1 1H NMR spectra of the silver(I) complexes.



silver complex 4a.


S9


Figure 2. Partial 1H NMR spectra (300 MHz, d6-acetone, 300 K) of a) Ligand 2b, b) silver complex 4b.


S10



silver complex 5a.


S11



5b.


S12

2. SPARTAN CPK molecular models of the complexes.

Figure 5. Space Filling (CPK, left) and tube (right) molecular models of the trimeric

3:3 complex formed between 2a and Ag(SbF6). (Spartan ’06 Essential Edition for

Windows, Wavefunction, Irvine, CA)

Figure 6. Space Filling (CPK, left) and tube (right) molecular models showing the

complex formed if Ag(I) binding to the ligands (3a and 3b) was through the N2

nitrogen of the triazole. (Spartan ’06 Essential Edition for Windows, Wavefunction,

Irvine, CA)


S13

344.

0209

579.

1396

920.

9244

1264

.724

114

99.8

333

+MS,

0.3

-1.4

min

#(1

6-81

)

0.0

0.2

0.4

0.6

0.8

1.0

1.26

x10

Inte

ns.

500

1000

1500

2000

2500

m/z

3. HR-ESMS spectra of the silver(I) complexes. Figure 7. HR-ESMS (CH3CN) of [Ag2(2a)2](SbF6)2, 4a: m/z = 344.0209 [Ag(2a)]+ (calc. for

C15H13AgN3 344.0157), 579.1396 [Ag(2a)2]+ (calc. for C30H26AgN6 579.1267), 920.9243

[Ag2(2a)2](SbF6)+ (calc. for C30H26Ag2F6N6Sb 920.9245), 1499.8332 [Ag3(2a)3](SbF6)2+ (calc. for


S14

C45H39Ag3F12N9Sb2 1499.8367).

1495.83331496.8351

1497.8335

1498.8357

1499.8333

1500.8356

1501.8331

1503.8331

1504.8352

1505.83411506.8361

+MS, 0.3-1.4min #(16-81)

1495.83601496.8390

1497.8362

1498.8390

1499.8363

1500.8390

1501.8367

1503.8373

1504.8394

1505.83871506.8401

C 45 H 39 Ag 3 F 12 N 9 Sb 2 ,1495.840.0

0.2

0.4

0.6

0.8

5x10Intens.

0.0

0.2

0.4

0.6

0.8

1.05x10

1492.5 1495.0 1497.5 1500.0 1502.5 1505.0 1507.5 1510.0 m/z

Figure 8. Observed (top) and calculated (bottom) isotopic distribution for the [Ag3(2a)3](SbF6)2+ ion.


S15

Figure 9. HR-ESMS (CH3CN) of [Ag2(2b)2](SbF6)2, 4b: m/z = 449.9775 [Ag(2b)H2O]+ (calc. for

C15H10AgF5N3O 449.9795), 757.0273 [Ag(2b)2]+ (calc. for C30H16AgF10N6 757.0328), 1425.8874

[Ag2(2b)3](SbF6)+ (calc. for C45H24Ag2F21N9Sb 1425.8960), 1769.6885 [Ag3(2b)3](SbF6)+ (calc. for

449.

9774

757.

0308

1080

.408

0

+MS,

0.4

-1.3

min

#(2

4-79

)

0.0

0.2

0.4

0.6

0.8

1.06

x10

Inte

ns.

500

1000

1500

2000

2500

m/z


S16

C45H24Ag3F27N9Sb2 1769.6953).

1765.68921766.6939

1767.6878

1768.6888

1769.6885

1770.6905

1771.6877

1772.6910 1773.6893

1774.6889

1775.69051776.6898

+MS, 0.3-1.6min #(16-95)

1765.69471766.6977

1767.6948

1768.6977

1769.6950

1770.6977

1771.6954

1772.6978 1773.6960

1774.69801775.6973

1776.6987

C 45 H 24 Ag 3 F 27 N 9 Sb 2 ,1765.700

1000

2000

3000

4000

5000

Intens.

0

2000

4000

6000

1764 1766 1768 1770 1772 1774 1776 m/z

Figure 10. Observed (top) and calculated (bottom) isotopic distribution for the [Ag3(2b)3](SbF6)2+ ion.


S17

Figure 11. HR-ESMS (CH3CN) of [Ag2(3a)2](SbF6)2, 5a: m/z = 501.0789 [Ag(3a)]+ (calc. for

C24H20N6Ag 501.0797), 893.2551 [Ag(3a)2]+ (calc. for C48H40AgN6 893.2543), 1235.0454

352.

0102

501.

0793

893.

2557

1235

.045

416

29.2

186

+MS,

0.0

-0.2

min

#(2

-14)

0.00

0.25

0.50

0.75

1.00

1.25

6x1

0In

tens

.

500

1000

1500

2000

2500

m/z


S18

[Ag2(3a)2](SbF6)+ (calc. for C48H40N12Ag2SbF6 1235.0540), 1629.2186 [Ag2(3a)3](SbF6)+ (calc. for

C72H60N18Ag2SbF6 1629.2293).

1233.0445

1234.0470

1235.0454

1236.0476

1237.0451

1238.0475

1239.0461

1240.0486

1241.0497

+MS, 0.1-0.3min #(3-17)

1233.0538

1234.0566

1235.0540

1236.0566

1237.0545

1238.0568

1239.0557

1240.0573

1241.0597

C 48 H 40 Ag 2 F 6 N 12 Sb 1 ,1233.050.0

0.2

0.4

0.6

0.8

1.0

5x10Intens.

0.0

0.2

0.4

0.6

0.8

1.0

1.25x10

1228 1230 1232 1234 1236 1238 1240 1242 1244 1246 1248 m/z Figure 12. Observed (top) and calculated (bottom) isotopic distribution for the [Ag2(3a)2](SbF6)+ ion.


S19

Figure 13. HR-ESMS (CH3CN) of [Ag2(3b)2](SbF6)2, 5b: m/z = 678.9967 [Ag(3b)]+ (calc. for

C24H10AgF10N6 678.9858), 1253.0809 [Ag(3b)2]+ (calc. for C48H20AgF20N12 1253.0662), 1594.8573

517.

2929

678.

9823

822.

8536

1253

.059

6

1825

.139

8

+MS,

0.8

-2.3

min

#(4

5-13

5)

0.0

0.5

1.0

1.55

x10

Inte

ns.

500

1000

1500

2000

2500

m/z


S20

[Ag2(3b)2](SbF6)+ (calc. for C48H20Ag2F26N12Sb 1594.8655), 1825.1623 [Ag(3b)3]+ (calc. for

C72H30AgF30N18 1825.1469).

1592.8581

1593.8595

1594.8573

1595.8597

1596.8573

1597.8600

1598.8585

1599.8576

+MS, 0.4-2.0min #(26-121)

1592.8653

1593.8682

1594.8655

1595.8682

1596.8660

1597.8683

1598.8672

1599.8688

1600.8712

C 48 H 20 Ag 2 F 26 N 12 Sb 1 ,1592.870

500

1000

1500

2000

2500

Intens.

0

1000

2000

3000

1588 1590 1592 1594 1596 1598 1600 1602 1604 m/z

Figure 14. Observed (top) and calculated (bottom) isotopic distribution for the [Ag2(3b)2](SbF6)+ ion.


S21

7. X-ray data for the silver (I) complexes.

Figure 15. ORTEP (top) and space filling (bottom) views of the [(2a)2Ag2]2+ cation. The SbF6

- anions

are omitted for clarity.


S22

Figure 16. Two views of [(2a)2Ag2](SbF6)2 (3a) showing the close contacts between the SbF6

- anions

and the Ag(I) ions. a) a ball and stick diagram and b) a space filing diagram.

Figure 17. Two views of the extended structure of [(2a)2Ag2](SbF6)2 (3a). a) a ball and stick diagram

and b) a space filing diagram. The SbF6- anions are omitted for clarity.


S23

Figure 18. ORTEP (top) and space filling (bottom) views of the [(2b)4Ag2]2+ cation. The SbF6

-

anions are omitted for clarity.


S24

Figure 19. Two views of the extended structure of [(2b)2Ag2](SbF6)2 (3b). a) a ball and stick diagram


Figure 20. An ORTEP diagram of the [(3b)4Ag2]2+ cation. The SbF6- anions and Et2O ligands have

been omitted for clarity.


S25

Figure 21. Two views of the complete cationic unit of [(3b)2Ag2](SbF6)2 (5b). a) a ball and stick

diagram and b) a space filing diagram. The SbF6- anions are omitted for clarity.

Figure 22. Two views of the extended structure of [(3b)2Ag2](SbF6)2 (5b). a) a ball and stick diagram



S26

4.1 X-Ray data collection and refinement for 5b (acetone).

X-Ray data for 5b (acetone) was recorded with a Bruker APEX II CCD

diffractometer at 89(2) K using Mo Kα radiation (λ = 0.71073 Ǻ). The structure was

solved by direct methods using SIR97,1 with the resulting Fourier maps revealing the

location of all non-hydrogen atoms of the core metallomacrocycle unit. Following the

location of the core atoms of 5b (acetone) in the F map there was still residual

electron density present near the silver atoms of the structure. This was modelled as

coordinated acetone. However, these acetone molecules are badly disordered.

Disappointingly, this disorder could not be satisfactorily resolved; as such there is

residual electron density around the coordinated acetone molecules within the

structure. One of the pentafluorobenzyl groups displayed large thermal parameters

potentially due to further disorder, as such it was restrained using ISOR and SIMU

commands in SHELXL-972. Weighted full matrix refinement on F2 was carried out

using SHELXL-972 with all non-hydrogen atoms being refined anisotropically, while

the disordered acetone molecules were refined isotropically. The hydrogen atoms

were included in calculated positions and were refined as riding atoms with individual

(or group, if appropriate) isotropic displacement parameters.

The ORTEP3 diagrams have been drawn with 50% probability ellipsoids. Crystal

data and collection parameters are given in Table 1.

Table 1 Crystal data and structure refinement for 5b (acetone).

Identification code 5b (acetone) CCDC 751439

Empirical formula C33H28O3F16AgSbN6

Formula weight 1090.23

Temperature 89(2)

Crystal system Monoclinic

Space group P21/n

a/Å, b/Å, c/Å 19.902(4), 9.080(2), 23.168(5)

α/°, β/°, γ/°, 90, 113.594(1), 90

Volume/Å3 3836.7(14)

Z 4

ρcalcmg/mm3 1.887


S27

m/mm-1 1.336

F(000) 2136

Crystal size 0.58 × 0.28 × 0.07

Theta range for data collection1.14 to 24.59°

Index ranges -23 ≤ h ≤ 23, -10 ≤ k ≤ 10, -27 ≤ l ≤ 27

Reflections collected 72868

Independent reflections 6446 [R(int) = 0.062]

Data/restraints/parameters 6446/127/503

Goodness-of-fit on F2 1.078

Final R indexes [I>2σ (I)] R1 = 0.0801, wR2 = 0.206

Final R indexes [all data] R1 = 0.0873, wR2 = 0.2119

Largest diff. peak/hole 3.089/-1.063

Figure 23. An ORTEP diagram of [(3b)4Ag2]2+ cation from the of the crystal structure 5b (acetone).

The SbF6- anions and acetone ligands have been omitted for clarity.

5. References

1. A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori and R. Spagna, J. Appl. Crystallogr., 1999, 32, 115-119.

2. G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr., 2008, A64, 112-122.

3. L. J. Farrugia, J. Appl. Crystallogr., 1997, 30, 565.


Documents

Self-assembly of silver (I) metallomacrocycles using ...€¦ · S2 Table of Contents S2 1. 1H NMR Spectra of synthesized compounds.S4 1H NMR (d 6-acetone, 300K) of 2a. S4 1H NMR