1

Supplementary Informations

Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing.

Christophe Bucher†*, Charles H. Devillers†, Jean-Claude Moutet†*, Jacques Pécaut‡, Guy Royal†, Eric Saint-Aman†, Fabrice Thomas§,

†Laboratoire d’Electrochimie Organique et de Photochimie Rédox, UMR CNRS 5630, Institut de Chimie Moléculaire de Grenoble, FR CNRS 2607, Université Joseph Fourier, BP 53, 38041 Grenoble Cédex 9, France Fax: 0476514267; Tel: 0476514481; E-mail: christophe.bucher@ujf-grenoble.fr ‡ DRMFC/CEA/SCIB, Laboratoire de Chimie de Coordination, 17 rue des Martyrs, 38054 Grenoble Cédex 9. § Laboratoire de Chimie Biomimétique, LEDSS, UMR CNRS 5616, Université Joseph Fourier Grenoble 1, BP 53, 38041 Grenoble Cédex 9, France -Table 1. Crystal data and structure refinement for struc. 1 p.2

-Table 2. Crystal data and structure refinement for struc. 2 p.3

-Table 3. Crystal data and structure refinement for struc. 4 p.4

-Table 4. Crystal data and structure refinement for struc. 5 p.5

-NMR Characterization of 1.( 400MHz, CDCl3) p.6 A1:1H / B1:Cosy / C1: HMQC -NMR Characterization of 2.( 400MHz, CDCl3) p.9 A2:1H / B2:Cosy / C2: HMQC -NMR Characterization of 3.( 400MHz, CDCl3) p.12 A3:1H / B3:Cosy / C3: HMQC -NMR Characterization of 4.( 250MHz, CDCl3) p.15 -Characterization of 1, 2, 3, 4, 5 using UV visible spectrocopy p.16 -Spectrophotometric titration of 4 with TBABr and TEAF p. 17 -Electrochemical sensing of TEAF. Detail of the CV and DPV curves p.18

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Table 1. Crystal data and structure refinement for struc. 1

Empirical formula C40 H46 Fe N4 O Formula weight 654.66 Temperature 298(2) K Wavelength 0.71073 A Crystal system Triclinic Space group P-1 Unit cell dimensions a = 7.7327(15) A alpha = 108.78(3) deg. b = 13.530(3) A beta = 91.96(3) deg. c = 17.245(3) A gamma = 91.09(3) deg. Volume, Z 1706.3(6) A^3, 2 Density (calculated) 1.274 Mg/m^3 Absorption coefficient 0.479 mm^-1 F(000) 696 Crystal size 0.50 x 0.20 x 0.20 mm Theta range for data collection 2.32 to 28.76 deg. Limiting indices -10<=h<=10, -17<=k<=17, -18<=l<=23 Reflections collected 10819 Independent reflections 7633 [R(int) = 0.0176] Absorption correction None Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 7633 / 0 / 415 Goodness-of-fit on F^2 1.053 Final R indices [I>2sigma(I)] R1 = 0.0493, wR2 = 0.1277 R indices (all data) R1 = 0.0676, wR2 = 0.1390 Largest diff. peak and hole 0.477 and -0.287 e.A^-3

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Table 2. Crystal data and structure refinement for struc 2

Empirical formula C46 H42 Cl6 Fe2 N4 Formula weight 975.24 Temperature 298(2) K Wavelength 0.71073 A Crystal system Monoclinic Space group P2(1) Unit cell dimensions a = 12.671(3) A alpha = 90 deg. b = 11.944(2) A beta = 112.22(3) deg.

c = 15.545(3) A gamma = 90 deg. Volume, Z 2178.1(8) A^3, 2 Density (calculated) 1.487 Mg/m^3 Absorption coefficient 1.073 mm^-1 F(000) 1000 Crystal size 0.50 x 0.20 x 0.20 mm Theta range for data collection 1.42 to 28.90 deg. Limiting indices -16<=h<=13, -15<=k<=14, -17<=l<=20 Reflections collected 13871 Independent reflections 8981 [R(int) = 0.0160] Absorption correction None Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 8981 / 4 / 556 Goodness-of-fit on F^2 1.061 Final R indices [I>2sigma(I)] R1 = 0.0435, wR2 = 0.1063 R indices (all data) R1 = 0.0525, wR2 = 0.1141 Absolute structure parameter 0.027(14) Largest diff. peak and hole 0.453 and -0.354 e.A^-3

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Table 3. Crystal data and structure refinement for struc 4

Empirical formula C48 H48 Fe2 N4 O Zn Formula weight 873.97 Temperature 223(2) K Wavelength 0.71073 A Crystal system Tetragonal Space group P4(1)2(1)2 Unit cell dimensions a = 10.7004(15) A alpha = 90 deg. b = 10.7004(15) A beta = 90 deg. c = 34.398(7) A gamma = 90 deg. Volume, Z 3938.6(11) A^3, 4 Density (calculated) 1.474 Mg/m^3 Absorption coefficient 1.374 mm^-1 F(000) 1816 Crystal size 0.30 x 0.15 x 0.08 mm Theta range for data collection 1.99 to 28.99 deg. Limiting indices -12<=h<=14, -13<=k<=13, -21<=l<=46 Reflections collected 16132 Independent reflections 4838 [R(int) = 0.0214] Absorption correction None Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 4838 / 0 / 255 Goodness-of-fit on F^2 1.162 Final R indices [I>2sigma(I)] R1 = 0.0312, wR2 = 0.0719 R indices (all data) R1 = 0.0342, wR2 = 0.0727 Absolute structure parameter 0.027(13) Largest diff. peak and hole 0.301 and -0.500 e.A^-3

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Table 4. Crystal data and structure refinement for struc 5.

Empirical formula C45 H40 Cl2 Cu Fe2 N4 Formula weight 882.95 Temperature 293(2) K Wavelength 0.71073 A Crystal system Orthorhombic Space group Pnma Unit cell dimensions a = 14.7414(19) A alpha = 90 deg. b = 18.668(2) A beta = 90 deg. c = 13.5904(17) A gamma = 90 deg. Volume, Z 3740.0(8) A^3, 4 Density (calculated) 1.568 Mg/m^3 Absorption coefficient 1.512 mm^-1 F(000) 1812 Crystal size 0.40 x 0.20 x 0.20 mm Theta range for data collection 1.85 to 29.10 deg. Limiting indices -19<=h<=19, -25<=k<=18, -17<=l<=13 Reflections collected 22287 Independent reflections 4794 [R(int) = 0.0183] Absorption correction None Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 4794 / 2 / 297 Goodness-of-fit on F^2 1.137 Final R indices [I>2sigma(I)] R1 = 0.0393, wR2 = 0.0899 R indices (all data) R1 = 0.0449, wR2 = 0.0926 Largest diff. peak and hole 1.072 and -0.757 e.A^-3

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NMR Characterization of 1.( 400MHz, CDCl3) A1:1H / B1:Cosy / C1: HMQC (A1) 1H spectrum of 1 (CDCl3, 400 MHz).

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(B1) 1H-1H COSY map of 1 (CDCl3, 400 MHz)

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(C1) HMQC map of 1(CDCl3, 400MHz)

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NMR Characterization of 2.( 400MHz, CDCl3) A2:1H / B2:Cosy / C2: HMQC (A2) 1H spectrum of 2 (CDCl3, 400 MHz).

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(B2) 1H-1H COSY map of 2 (CDCl3, 400 MHz)

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(C2) HMQC map of 2(CDCl3, 400MHz)

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NMR Characterization of 3.( 400MHz, CDCl3) A3:1H / B32:Cosy / C3: HMQC (A3) 1H spectrum of 3 (CDCl3, 400 MHz).

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(B3) 1H-1H COSY map of 3 (CDCl3, 400 MHz)

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(C3) HMQC map of 3 (CDCl3, 400MHz)

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NMR Characterization of 4 1H NMR spectrum of 4 (CDCl3, 250 mHz)

4 44 4

10

5

12

4 44 4

10

5

12

MeOH

H2OCHCl3

4 44 4

10

5

12

4 44 4

10

5

12

MeOH4 44 4

10

5

12

4 44 4

10

5

12

MeOH

H2OCHCl3

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UV-Visible features recorded in dichloromethane at 20°C, C = 10-5 M, using a 1 cm cell.

300 400 500 600 700 800

0

10000

20000

30000

40000

50000

60000

2 3 1

ε (M

-1.c

m-1)

wavelength (nm)

300 400 500 600 700 800

0

20000

40000

60000

80000

100000

4 5

ε (M

-1.c

m-1)

wavelength (nm)

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Spectrophotometric titration of 4 with Tetrabutylammonium bromide and Tetraethylammonium fluoride in CH2Cl2 (0.1M tetrabulylammonium perchlorate)

0,0000 0,0005 0,0010 0,0015 0,0020 0,0025

0,0

0,1

0,2

0,3

0,4

0,5

0,6

Equation of the curve fit: Abs-Abs0=(ε2-ε1)(1/2)((L0+S0+(1/K))-((L0+S0+(1/K))2-4L0S0)1/2))

with ε1 and ε2 : extinction coefficients of free 4 and 4 saturated with TBABr, respectively.L0: concentration of 4; S0: concentration of TBABr; K: association constant with fluoride.

Chi2 = 0.00007K 3031.63048 ± 86.53777

Abs - Abs0 at λ = 328 nm as a function of TBABr concentration for 4 (c = 1.10-5 M) in CH2Cl2 0,1 M TBAP, l = 1 cm.

A-A

0 à λ

=328

nm

[TBABr] (mol/L)

0,000 0,001 0,002 0,003 0,004 0,005

0,00

0,05

0,10

0,15

0,20

0,25

0,30

Equation of the curve fit: Abs-Abs0=(ε2-ε1)(1/2)((L0+S0+(1/K))-((L0+S0+(1/K))2-4L0S0)1/2))

with ε1 and ε2 : extinction coefficients of free 4 and 4 saturated with TEAF, respectively.L0: concentration of 4; S0: concentration of TEAF; K: association constant with fluoride.

Chi2 = 0.00008K = 8221.33324±691.182

Abs - Abs0 at λ = 328 nm as a function of TEAF concentration

for 4 (c = 1.10-5 M) in CH2Cl2 0,1 M TBAP, l = 1 cm.

Abs

-Abs

0 at λ

= 3

28 n

m

[TEAF] (mol/L)

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Evolution of the DPV and the CV curves recorded in a CH2Cl2 0,1 M TBAP solution of 4 (5×10-4 M) upon adding increasing amounts of

tetraethylammonium fluoride (TEAF).WE: vitreous carbon ø = 3 mm, Aux: Pt wire, Ref: Ag/AgNO3 10-2 M.

(Vs Ag/AgNO3 10-2M)

(Vs Ag/AgNO3 10-2M)

∆E = 140 mV 44 + 0.94 equivalent of TEAF4 + 1.41 equivalent of TEAF4 + 6.10 equivalent of TEAF4 + 45.48 equivalent of TEAF

44 + 0.94 equivalent of TEAF4 + 1.41 equivalent of TEAF4 + 6.10 equivalent of TEAF4 + 45.48 equivalent of TEAF

After the addition of 2.34 equivalent of TEAF the waves corresponding to the oxydationof the ferrocene in the free complexe and with the fluoride become both irrversible.

44 + 2.34 equivalent of TEAF44 + 2.34 equivalent of TEAF

Increment E = 0.002 VAmplitude = 0.05 VPulseWidth = 0.05 sPulse Period = 0.2 s

scan rate = 0.1 V/s