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Eur. J. Org. Chem. 2006 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 · ISSN 1434–193X

SUPPORTING INFORMATION

Title: Pseudorotaxanes and Rotaxanes Formed by Viologen Derivatives Author(s): Adam B. Braunschweig, Célia M. Ronconi, Ja-Young Han, Fabio Aricó, Stuart J. Cantrill, J. Fraser Stoddart,* Saeed I. Khan, Andrew J. P. White, David J. Williams Ref. No.: O200500947

Table of Contents General Methods………………………………………………………….…….S3 Mass Spectroscopic Data……………………………………………….……....S4 1H NMR Spectrum of 7·2PF6……..…………………………………...….……S7 13C NMR Spectrum of 7·2PF6……..…………………………………………...S8 1H NMR Spectrum of 8·2PF6……..……………………………………………S9 13C NMR Spectrum of 8·2PF6……..…………………………………………...S10 VT 1H NMR of DB24C8⊂6·2PF6…………………………………………...…S11 VT 1H NMR of Dp24C8⊂6·2PF6…………………………………………...…S12 VT 1H NMR ofBMP25C8⊂6·2PF6……………………..…………………...…S13 Van’t Hoff Plots…………………………………………………………...……S14 ITC of DB24C8⊂1-H·PF6…………………………………………………...…S15 ITC of DP24C8⊂1-H·PF6…………………………………………………...…S16 ITC of BMP25C8⊂1-H·PF6………………….……………………………...…S17 ITC of DB24C8⊂5·2PF6……………..……………………………………...…S18 ITC of DP24C8⊂5·2PF6……………..……………………………………...…S19 ITC of BMP25C8⊂5·2PF6……………..………………….………………...…S20 Solid-state structural data for DP24C8⊂6·2PF6……………………………..S21 Solid-state structural data for 6·2PF6……………….………………………..S22

S2

General Procedures. All reagents and solvents were used as received unless otherwise

stated. The dibenzylammonum salts 1-H·PF6,1 2-H·PF6,2 3-H·PF6,3 and 4-H·PF6,4 as well

as the crown ethers DP24C85 and BMP25C85 were synthesized as previously reported.

DB24C8 was purchased from a commercial supplier. Dibenzyl-4,4'-bipyridinium

bis(hexafluorophosphate),6 (5·PF6); bis(4''-methylbenzyl)-4,4'-bipyridinium

bis(hexafluorophosphate),6 (8·PF6). Reactions were monitored by TLC using aluminum

sheets precoated with silica gel 60F (Merck 5554). Column chromatography was carried

out using silica gel 60F (Merck 40-60 µm, 230-240 mesh). Melting points are

uncorrected. 1H NMR and 13C NMR Spectra were recorded at 500 MHz and the chemical

shifts reported are referenced to the residual solvent peak. 19F NMR Spectra were

recorded at 400 MHz. Fast atom bombardment mass spectra (FAB-MS) were obtained

using a Kr primary atom beam, in conjunction with a m-nitrobenzyl alcohol matrix.

Electrospray ionization mass spectra (ESI-MS) were performed using commercially

available instrumentation.

General Procedure for Preparing Samples for Determining Values of Ka by the

Single-Point Method. Solutions for NMR spectroscopic analysis were prepared as

follows: To a small vial were added appropriate amounts of guest and crown ether (host);

a known volume of CD3CN was then added to yield the desired final concentrations of

the two components. After careful mixing, the resulting solution was transferred to an

NMR tube and analyzed immediately. Solutions were discarded after use. This procedure

was repeated to prepare samples using the crown ethers BP24C8 and DB24C8. Values

of Ka were calculated using the single-point technique.7

S3

General Procedure for Determining Ka Values by Isothermal Titration Calorimetry

(ITC). ITC runs were carried out as follows: solutions (1.5 mM) of the crown ethers

(hosts) in MeCN were also prepared in volumetric glassware. Solutions (20 mM) of

guests in MeCN were prepared in volumetric glassware. The host solutions were added

to the cell of the calorimeter and the cell was warmed up to 298 K. In aliquots of 5-7

µLs, the guests were added into the sample cell with 200 s increments between additions

of aliquots. Fits to determine thermodynamic parameters were carried out using software

provided by Microcal LLC.8

References and Notes

(1) Ashton, P. R.; Chrystal, E. J. T.; Glink, P. T.; Menzer, S.; Schiavo, C.; Spencer,

N.; Stoddart, J. F.; Tasker, P. A.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1996, 2,

709–728.

(2) Ashton, P. R.; Bartsch, R. A.; Cantrill, S. J.; Hanes, Jr., R. E.; Hickingbottom, S.

K.; Lowe, J. N.; Preece, J. A.; Stoddart, J. F.; Talanov, V. S.; Wang, Z.-H. Tetrahedron

Lett. 1999, 40, 3661–3664.

(3) Cantrill, S. J.; Youn, G. J.; Stoddart, J. F.; Williams, D. J. J. Org. Chem. 2001, 66,

6857–6872.

(4) Ashton, P. R.; Fyfe, M. C. T.; Hickingbottom, S. K.; Stoddart, J. F.; White, A. J.

P.; Williams, D. J. J. Chem. Soc., Perkin Trans. 2 1998, 2117–2128.

S4

(5) Chang, T.; Heiss, A. M.; Cantrill, S. J.; Fyfe, M. C. T.; Pease, A. R.; Rowan, S. J.;

Stoddart, J. F.; White, A. J. P.; Williams, D. J. Org. Lett. 2000, 2, 2947–2950.

(6) Kamogawa, H.; Yamada, H. Bull. Chem. Soc. Jpn. 1991, 64, 3196–3198.

(7) For publications that address the single-point method, see: (a) Stauffer, D. A.;

Barrans, R. E.; Dougherty, D. A. J. Org. Chem. 1990, 55, 2762–2767. (b) Adrian, J.

C.; Wilcox, C. S. J. Am. Chem. Soc. 1991, 113, 678–680. (c) Petti, M. A.; Shepodd, T. J.;

Barans, R. E.; Dougherty, D. A. J. Am. Chem. Soc, 1998, 110, 6825–6840.

(8) Software used to determine fits by ITC was provided by Microcal, LLC,

Northampton, MA, US

S5

S6

1 H N

MR

500

MHz

CD3C

N29

8 K

7 2P

F 6-

S7

13C

NMR

500

MHz

CD3C

N29

8 K

7 2P

F 6-

S8

1 H N

MR

500

MHz

CD3C

N29

8 K

8 2P

F 6-

S9

13C

NMR

500

MHz

CD3C

N29

8 K

8 2P

F 6-

S10

1 H N

MR

/ 500

MHz

CD

3CN

/ 298

K6

2PF 6

-

DB24C8

S11

1 H N

MR

/ 500

MHz

CD

3CN

/ 298

K6

2PF 6

-

DP24C8

S12

1 H N

MR

/ 500

MHz

CD

3CN

/ 298

K6

2PF 6

-

BMP25C8

S13

Van't Hoff Plot for the [2]Pseudorotaxanes (1:1 Complexes) formed in MeCN Solutions at 298 K between DB24C8, BMP25C8 and DP24C8 and the

Dibenzylbipyridinium Thread 6-2PF6

0

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0.003 0.0032 0.0034 0.0036 0.0038 0.004 0.0042 0.0044

1/T

Rln

Ka DB24C8

BMP25C8

DP24C8

S14

S15

S16

S17

S18

S19

S20

The molecular structure of the cationic Ci-symmetric [2]pseudorotaxane DP24C8⊂6⋅2PF6 (30% probability ellipsoids).

S21

Crystal data for 6·2PF6: [C28H26N2O4](PF6)2, M = 744.45, monoclinic, C2/c (no. 15), a = 37.946(3), b = 6.7686(6), c = 12.8205(13) Å, β = 98.348(7)°, V = 3258.0(5) Å3, Z = 4 (C2 symmetry), Dc = 1.518 g cm–3, µ(Mo-Kα) = 0.239 mm–1, T = 293 K, colorless platy prisms; 2427 independent measured reflections, F2 refinement, R1 = 0.052, wR2 = 0.124, 1603 independent observed reflections [|Fo| > 4σ(|Fo|), 2θmax = 47°], 281 parameters. CCDC 264705.

The molecular structure of the cationic C2-symmetric thread 6·2PF6 (30% probability ellipsoids).

S22