Supplementary Material for Dalton Transactions
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Supplementary Information
Synthesis of 4
To macrocyclic amide 2S1 (170 mg, 0.672 mmol) was added ethanol (2 cm3) and the solution buffered to pH
9 (using Merck VWR 9.2 buffer solution, 2 cm3) and CuCl2 (89.5 mg, 0.665 mol) added. The reaction
mixture was then heated at reflux for 18 h. The solvent was removed under reduced pressure and the resultant
blue solid recrystallised from hot ethanol to yield 4 as blue crystals suitable for single crystal X-ray
diffraction (84.4 mg, 33%); m.p. 172-174oC; max/cm-1 1664 (C=O); max/nm 271 (6348), 360 (1215), 580
(105), 714 (120); m/z (ES) 743.4 (4%, 2M-Cl+), 353.1 (50, M-Cl+); (HRMS Found: (M-Cl+) 353.1293
C14H29ClCuN3O requires 353.1290).
X-Ray Crystallography
The intensity data were collected using an Enraf-Nonius Kappa CCD area detector on an Enraf Nonius
FR591 rotating anode generator at 120 (2) K. Graphite monochromated MoK radiation ( = 0.71073 Å)
was used with  and  to fill the Ewald sphere. Data collection, cell refinement and data reduction were
carried out using the DENZOS2 and COLLECTS3 packages. Preliminary absorption correction was carried
out by multiple scans using SORTAV.S4 The structures were solved by the heavy-atom method using the
programs SHELXS-97,S5 and DIRDIFS6 and refined anisotropically (non-hydrogen atoms) by full-matrix
least-squares on F2 using SHELXL-97.S5 The H-atom positions were calculated geometrically and refined
with a riding model. Data were corrected for absorption using an isotropic non-hydrogen model with the
programme XABS2.S7 The program ORTEP-3,S8 was used for graphical representations and WINGXS9 was
used to prepare material for publication for all structures.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
0.7
0.6
0.5
Absorbance
0.4
0
20
40
60
80
100
0.3
0.2
0.1
0
180
280
380
480
580
680
780
880
980
1080
1180
-0.1
-0.2
Wavelength (nm)
Fig. S1 UV-visible spectra of 4 in ethanol at room temperature recorded after various times (given in legend
in minutes)
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
3
2.5
0
10
25
35
45
65
85
105
165
185
215
245
275
335
395
12h
24h
Absorbance
2
1.5
1
0.5
0
180
280
380
480
580
680
780
880
980
1080
1180
-0.5
Wavelength (nm)
Fig. S2 Time dependent UV-visible spectra of 4 after refluxing in ethanol (0-395 mins, 12 h and 24 h)
Cyclic Voltammetry
Cyclic voltammetry was performed using an EG and G Princeton Applied Research Versastat II with Pt
working and counter electrodes and an Ag reference electrode. All data were collected in dry degassed DCM
solutions with nBu4NCl as the supporting electrolyte using EG and G Model 270/250 Research
Electrochemistry Software 4.40. All potentials are referenced relative to Fc/Fc+ at E0 = 0 V.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
E (mV)
-2100
-1900
-1700
-1500
-1300
-1100
-900
-700
-500
200 mV/s
100 mV/s
50 mV/s
25 mV/s
Fig. S3 Cyclic Voltammagrams of cathodic sweeps of 4 in DCM with nBu4NCl as the supporting electrolyte
referenced to Fc/Fc+.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
E (mV)
-2000
-1800
-1600
-1400
-1200
-1000
-800
-600
15 mV/s
10 mV/s
Fig S4 Cyclic votammetry in DCM with nBu4NCl as supporting electrolyte at slow scan rates
EPR Spectroscopy
X-band spectra (ca. 9.4 GHz) were measured on an EMX hybrid spectrometer and K-band (ca. 24.0 GHz) Qband (ca. 34.0 GHz) spectra on an ESP300 spectrometer. The magnetic fields were calibrated with a Bruker
ER035M Gaussmeter and the microwave frequencies measured with an EIP588C microwave counter.
Modulation frequencies of 100 KHz were used. EPR simulations were performed using in-house software.S10
From the value of D (ZFS), it is possible to calculate the distance between the two copper atoms, R, using the
perturbation theory by Boyd et al.S11 However it is necessary to assume that D is due entirely to dipole-dipole
interaction between the two copper(II) atoms and the symmetry arrangements of the two metals are limited
where the two dipoles are identical sites of orthorhombic symmetry and the g and D tensor principal axes are
all parallel. Considering these limitations, it has been possible to calculate the range of distances R, from the
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
expression of diagonal elements of D tensor,S10 where l, m, n are the direction cosines between the principal
axes of the g tensors.
z
Dxx = gxx2e2(1-3l2)/R3
Dyy = gyy2e2(1-3m2)/R3
Dzz = gzz2e2(1-3n2)/R3
z
R
n
Orientation of the g
tensors principal axes.
y
x
m
x
l
y
The medium value calculated is 4.8 Å (the values are between 3.9 and 5.9 Å), which is in agreement with the
small value of D, suggesting that in frozen solutions of 4 the two copper centres are ligand-bridged, the more
likely candidate is chloride.
Date: 14.08.1903 Time: 15:22
Filename:
C:\MYDOCU~1\JOANNA\WATKIN~1\1463_q1.spc
[*10^ 3]
10
5
0
-5
-10
-15
-20
-25
10000
10500
11000
11500
12000
[G]
Fig. S5 Powder Q-band (34.0076 GHz) EPR spectrum of 4 at 293 K
12500
13000
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Fig. S6 Fluid solution X-band (9.4471 GHz) EPR spectrum of 4 at 293 K in CH2Cl2/toluene
2250
2500
2750
3000
3250
[G]
3500
3750
4000
Fig.S7a X-band (9.4552 GHz) EPR spectrum of 4 and simulation (---)
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Fig. S7b K-band (24.1795 GHz) EPR spectrum of 4 and simulation (---)
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Supplementary References
S1 J.E.W. Scheuermann, F. Ronketti, M. Motevalli, D.V. Griffiths and M. Watkinson, New J. Chem., 2002,
26, 1054.
S2 DENZO Data collection and processing software: Z. Otwinowski and W. Minor, Methods in
Enzymology, Volume 276: Macromolecular Crystallography, part A, p.307-326, 1997, C.W. Carter, Jr and
R.M. Sweet, Eds., Academic Press.
S3 COLLECT Data collection and processing user interface: Collect: Data collection software, R. Hooft,
Nonius B.V., 1998.
S4 SORTAV absorption correction software package: R.H. Blessing, Acta Crystallogr., Sect. A., 1995, 51, 33
and R.H. Blessing, J. Appl. Cryst., 1997, 30, 421.
S5 G.M. Sheldrick, 1997 SHELX-97. Program for solution and Refinement of Crystal Structures. University
of Göttingen, Germany.
S6 DIRDIF-99 program system. P.T. Beurskens, G. Beurskens, W.P. Bosman, R. de Gelder, S. GarciaGranda, R.O. Gould, R. Israel and J.M.M. Smits, Crystallography Laboratory, University of Nijmegen,
The Netherlands. 1999.
S7 S. Parkin, B. Moezzi and H. Hope, J. Appl. Cryst., 1995, 28, 53.
S8 L.J. Farrugia, ORTEP-3 for Windows. J. Appl. Crystallogr., 1997, 30, 565.
S9 L.J. Farrugia, WinGX- A Windows Program for Crystal Structure Analysis, University of Glasgow,
Glasgow, 1998.
S10 F.E. Mabbs and D. Collison, Electron Paramagnetic Resonance of d Transition Metal Compound,
Elsevier, Amsterdam, 1992.
S11 P.D.W. Boyd, A.D. Toy and T.D. Smith, J. Chem. Soc., Dalton Trans., 1973, 1549.