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Novel double-decker phthalocyaninato terbium(III) single molecule magnets

with stabilised redox states

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Published on 24 July 2012 on http://pubs.rsc.org | doi:10.1039/C2DT31171B

Mathieu Gonidec,a,b David B. Amabilinoa and Jaume Veciana*a,b

Received 31st May 2012, Accepted 24th July 2012
DOI: 10.1039/c2dt31171b

Double-decker phthalocyanine lanthanide complexes are single molecule magnets (SMMs) presenting a
thermally activated magnetic relaxation with relatively high effective barriers. For this reason they are
potential candidates as components for data storage and spintronic devices. One of the disadvantages of
these compounds is their redox instability: they are oxidized or reduced in the presence of mild oxidizing
and reducing agents. To solve this issue, we designed, prepared and characterized new double-decker
phthalocyanine based SMMs bearing electron withdrawing groups and therefore presenting an increased
redox stability. In the present article, the synthesis and characterization of these novel compounds is
presented and we demonstrate how the magnetic behavior of the complexes is virtually identical to that of
the parent unsubstituted compounds.

Introduction
Single-molecule magnets (SMMs) were initially foreseen as
compounds which present very interesting properties with potential applications in novel storage devices in which data could be
stored at the single-molecule level.1 For many years, in order to
reach this goal, the science of SMMs has essentially been
focused on deciphering their quantum characteristics29 and
trying to produce novel systems with improved properties1016 so
as to obtain compounds presenting magnetic pseudo-bistability
at reasonably high temperatures. It was not until recently that
they were actually incorporated as active units in hybrid
materials,1727 in order to assert their use as molecular components for spintronic devices. In doing so, the redox instability
of some SMMs was soon detected as a challenge. In particular,
it was shown that Mn12 complexes could undergo reduction on
the Au(111) surface28 and that a similar situation could occur
while depositing terbium double-decker phthalocyanine complexes on Cu(111).17 One of the best candidates for spintronic
applications are lanthanide double-decker phthalocyanine complexes, which present the highest anisotropy barrier of magnetization reversal to date for SMMs.9,16,2931 However, as a result
of their low redox potentials,32,33 double-decker lanthanide complexes are often inadvertently reduced or oxidized and are also
very sensitive to both acids and bases. In order to solve these

Institut de Cincia de Materials de Barcelona (ICMAB-CSIC), 08193

Bellaterra, Spain. E-mail: vecianaj@icmab.es
b
Networking Center on Bioengineering, Biomaterials and Nanomedicine
(CIBER-BBN), 08193 Bellaterra, Spain
Electronic supplementary information (ESI) available: Additional
characterization for [TBA][3ac]: LDI-TOF MS spectra, complementary
cyclic voltammetry data, T(T), (T), T(), ColeCole plots and magnetization hysteresis plots at 7 K. Magnetization hysteresis plot at several
eld sweeping rates for [TBA][3a]. See DOI: 10.1039/c2dt31171b

This journal is The Royal Society of Chemistry 2012

problems, and in the framework of a research program aimed at

checking the robustness of the magnetic behavior of doubledecker complexes as a consequence of different substitution patterns, we designed a series of novel compounds with characteristics which would give them an improved redox stability.
Electroactive substituents were thus introduced on the outer part
of the skeleton of the double-decker lanthanide complexes, with
the effect of stabilizing the negative charge of the anionic state
of the compounds, which resulted in a strong shift of approximately 0.7 V of their rst oxidation potentials. In the present
article, the synthesis and characterization of these novel doubledecker terbium(III) complexes is presented together with their
SMM behaviour.

Experimental
Materials and methods

All the reagents were used as received from commercial sources.

In particular, dry hexanol and DMF were bought from SigmaAldrich in secure-seal packages. NMR spectra were recorded on
Bruker Avance 250, 360 and 400 MHz spectrometers as
specied. The solvent residual peak was used to calibrate the
spectra with literature reference ppm values.34 UV-visible
absorption spectra were collected on a Varian Cary 5000 spectrometer at one data point every 0.66 nm and measured at a scanning rate of 1200 nmmin1. Infrared spectra were recorded on a
Perkin Elmer Spectrum One Fourier Transform spectrometer in
attenuated total reection (ATR) mode. Mass spectra were
recorded on a Bruker Ultraex LDI-TOF spectrometer. Cyclic
voltammetry studies were carried out using a VersaSTAT 3
potentiostat from Princeton Applied Research. Standard cyclic
voltammetry was carried out using a three-electrode arrangement
in a single compartment cell. A glassy carbon working electrode,
Dalton Trans.

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a Pt wire secondary electrode and a silver wire as a pseudo reference electrode were used in the cell. The potentials were then
calibrated with ferrocene as an internal reference. The samples
for magnetometry consisted of gelatine capsules lled with
powder samples (about 15 mg of the sample was used for each
measurement). Ac-magnetic susceptibility measurements were
done on a Quantum Design PPMS magnetometer and for magnetization hysteresis, the sample was mounted on a Vibrating
Sample Magnetometer (VSM).
N-Pentadecyl-4,5-dichlorophthalimide (1a). 4,5-Dichlorophthalic acid (10 mmol, 2.35 g, 1.0 eq.), pentadecylamine (16 mmol,
3.6 g, 1.6 eq.) and N,N-dimethylaminopyridine (DMAP,
1.47 mmol, 0.18 g, 0.15 eq.) were dissolved in CH2Cl2 (10 mL)
in a round bottom ask under nitrogen. The ask was cooled to
0 C and dicyclohexylcarbodiimide (DCC, 22 mmol, 4.5 g,
2.2 eq.) was added. The resulting mixture was stirred at 0 C for
15 min and then at room temperature for 12 h. The precipitated
urea was then ltered off and washed thoroughly with CH2Cl2.
The combined organic phases were evaporated on a rotary
evaporator and the obtained solids were puried by silica gel
column chromatography using CH2Cl2 as an eluent, affording
N-pentadecyl-4,5-dichlorophthalimide as a white solid (2.5 g,
59%). MS m/z found: 425.3 (M); Calcd for C23H33Cl2NO2:
426.4. 1H NMR (360 MHz, CDCl3): 7.91 (ArH, s, 2 H), 3.66
(NCH2, t, J = 7.3 Hz, 2 H), 1.59 (NCH2CH2, m, 2 H),
1.24 ((CH2)12CH3, m, 24 H), 0.87 (CH3, t, J = 7.0 Hz, 3 H)
ppm. 13C NMR (63 MHz, CDCl3): 166.4, 138.7, 131.3, 125.3,
38.5, 31.9, 29.7, 29.6, 29.5, 29.4, 29.3, 29.1, 28.4, 26.8, 22.7,
14.1 ppm. FT-IR: 3100 (w), 2947 (m), 2918 (s), 2850 (s),
1775 (m), 1758 (w), 1688 (s), 1614 (w), 1603 (w), 1470 (m),
1434 (m), 1384 (s), 1350 (s), 1343 (m), 1331 (m), 1310 (m),
1269 (w), 1225 (w), 1191 (m), 1159 (w), 1140 (m), 1103 (m),
1080 (w), 1061 (w), 1041 (m), 1009 (m), 979 (w), 851 (w),
933 (w), 906 (m), 892 (w), 853 (m), 790 (w), 759 (w), 743 (s),
736 (s), 707 (s) cm1.
N-Propyl-4,5-dichlorophthalimide (1b). DMAP (0.23 g,
1.9 mmol, 0.15 eq.) and 4,5-dichlorophthalic acid (3.0 g,
13 mmol, 1.0 eq.) were dissolved in CH2Cl2 (30 mL) in a round
bottom ask under argon. The resulting suspension was cooled
to 0 C and DCC (7.9 g, 38 mmol, 3.0 eq.) and propylamine
(0.83 g, 14 mmol, 1.1 eq.) were added. The mixture was stirred
at 0 C for 15 minutes and stirred at room temperature for 2
days. The precipitated urea was then ltered off and washed
thoroughly with CH2Cl2. The organic layer was then evaporated
under vacuum and the residue was puried by silica gel column
chromatography using CH2Cl2 as an eluent, affording the title
compound (2.05 g, 62%) as a white powder. 1H NMR
(360 MHz, CDCl3): 7.90 (ArH, s, 2 H), 3.63 (NCH2,
t, J = 7.3 Hz, 2 H), 1.69 (NCH2CH2, m, 2 H), 0.93 (CH3,
t, J = 7.4 Hz, 3 H) ppm. 13C NMR (91 MHz, CDCl3): 166.6,
138.9, 131.4, 125.4, 40.2, 21.9, 11.4 ppm. FT-IR: 3095 (w),
3028 (w), 2971 (m), 2939 (w), 2877 (w), 1770 (m), 1741 (w),
1715 (s), 1695 (s), 1619 (m), 1604 (m), 1461 (m), 1448 (m),
1440 (m), 1382 (s), 1361 (s), 1346 (s), 1311 (s), 1192 (m),
1177 (m), 1142 (s), 1103 (m), 1094 (m), 1059 (m), 1044 (s),
956 (w), 919 (w), 896 (w), 885 (w), 854 (s), 790 (s), 750 (s),
737 (s) cm1.
Dalton Trans.

(S)-N-methyl( phenyl)methyl-4,5-dichlorophthalimide (1c).

4,5-Dichlorophthalic acid (10 mmol, 2.3 g, 1.0 eq.), DMAP

(1.5 mmol, 0.18 g, 0.15 eq.) and (S)-1-phenylethylamine
(11 mmol, 1.3 g, 1.1 eq.) were dissolved in CH2Cl2 (10 mL) in a
round bottom ask under nitrogen. The ask was cooled to 0 C
and DCC (30 mmol, 6.2 g, 3.0 eq.) was added. The resulting
mixture was stirred at 0 C for 15 min and then at room temperature for 12 h. The precipitated urea was then ltered off and
washed thoroughly with CH2Cl2. The combined organic phases
were evaporated on a rotary evaporator and the obtained solids
were puried by silica gel column chromatography using
CH2Cl2 as an eluent, affording (S)-N-methyl( phenyl)methyl-4,5dichlorophthalimide as a white solid (2.2 g, 69%). 1H NMR
(400 MHz, CDCl3): 7.87 (ClArH, s, 2 H), 7.457.55 (NCH
(CH3)ArH, m, 2 H), 7.257.35 (NCH(CH3)ArH, m,
3 H), 5.54 (NCH(CH3), q, J = 7.3 Hz, 1 H), 1.91 (NCH
(CH3), d, J = 7.3 Hz, 3 H) ppm. 13C NMR (63 MHz, CDCl3):
166.3, 139.9, 139.0, 131.2, 128.7, 128.0, 127.5, 125.4, 50.3,
2
17.5 ppm. []25
g1. FT-IR: 3465 (w),
546 = 3.75 deg cm
6094 (w), 3069 (w), 3022 (w), 2985 (w), 2945 (w), 2119 (w),
1771 (m), 1718 (s), 1705 (s), 1614 (m), 1586 (m), 1493 (m),
1456 (m), 1387 (s), 1379 (s), 1354 (s), 1347 (s), 1287 (m),
1214 (m), 1191 (m), 1154 (s), 1138 (m), 1103 (m), 1093 (m),
1050 (m), 1029 (m), 996 (w), 977 (w), 948 (w), 903 (m),
896 (m), 792 (m), 771 (m), 760 (s), 750 (s), 699 (s) cm1.
N-Pentadecyl-4,5-dicyanophthalimide (2a). N-Pentadecyl-4,5dichlorophthalimide (2.3 mmol, 1.0 g, 1.0 eq.), Pd(PPh3)4
(0.47 mmol, 0.54 g, 0.20 eq.) and zinc(II) cyanide (2.8 mmol,
0.33 g, 1.2 eq.) were introduced into a round-bottomed ask
under argon. Dry DMF (4.7 mL) was added and the mixture was
gently stirred at 120 C over 2 h. After this time, concentrated
ammonia was added (30 mL) and the solid residues were
ltered, dried and directly puried by silica gel column chromatography using toluene as an eluent, affording the title compound (0.51 g, 54%) as a white crystalline solid. MS m/z found:
407.4 (M); Calcd for C25H33N3O2: 407.6. 1H NMR (360 MHz,
CDCl3): 8.25 (ArH, s, 2 H), 3.74 (NCH2, t, J = 7.2 Hz,
2 H), 1.69 (NCH2CH2, m, 2 H), 1.25 ((CH2)12CH3, m,
24 H), 0.88 (CH2CH3, t, J = 6.9 Hz, 3 H) ppm. 13C NMR
(63 MHz, CDCl3): 164.8, 135.5, 127.9, 121.3, 114.2, 39.1, 31.9,
29.7, 29.6, 29.5, 29.4, 29.3, 29.0, 28.3, 26.8, 22.7, 14.1 ppm.
FT-IR: 3111 (w), 3050 (w), 2962 (w), 2918 (s), 2850 (s), 2240 (w),
1868 (w), 1781 (m), 1717 (s), 1705 (s), 1623 (w), 1470 (m),
1440 (w), 1416 (w), 1397 (s), 1370 (m), 1358 (m), 1331 (m),
1283 (w), 1271 (w), 1250 (w), 1227 (w), 1205 (w), 1186 (w),
1166 (w), 1151 (w), 1088 (s), 1027 (w), 1003 (w), 970 (w),
961 (w), 939 (m), 888 (w), 849 (w), 814 (w), 788 (m), 768 (w),
745 (s), 719 (s) cm1.
N-Propyl-4,5-dicyanophthalimide (2b). N-Propyl-4,5-dichlorophthalimide (1.9 mmol, 0.50 g, 1.0 eq.), Pd(PPh3)4
(0.39 mmol, 0.45 g, 0.20 eq.) and zinc(II) cyanide (2.3 mmol,
0.27 g, 1.2 eq.) were introduced into a round-bottomed ask
under argon. Dry DMF (3.2 mL) was added and the mixture was
gently stirred at 120 C over 2 h. After this time, concentrated
ammonia was added (30 mL) and the solid residues were
ltered, dried and directly puried by silica gel column
chromatography using CH2Cl2 as an eluent, affording the title
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compound (0.27 g, 58%) as a white crystalline solid. 1H NMR

(360 MHz, CDCl3): 8.26 (ArH, s, 2 H), 3.72 (NCH2, t, J =
7.4 Hz, 2 H), 1.73 (CH2CH3, m, 2 H), 0.96 (CH3, t, J =
7.3 Hz, 3 H) ppm. 13C NMR (91 MHz, CDCl3): 164.7, 135.3,
127.8, 121.2, 114.0, 40.7, 21.7, 11.2 ppm. FT-IR: 3117 (w),
3055 (w), 2970 (w), 2940 (w), 2881 (w), 2238 (w), 1779 (m),
1709 (s), 1623 (w), 1544 (w), 1458 (w), 1439 (m), 1418 (m),
1396 (s), 1383 (s), 1363 (s), 1348 (s), 1320 (s), 1242 (w), 1179
(m), 1148 (w), 1098 (w), 1080 (s), 1017 (m), 924 (m), 915 (m),
893 (m), 861 (m), 792 (m), 767 (m), 740 (s), 699 (w) cm1.

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(S)-N-methyl( phenyl)methyl-4,5-dicyanophthalimide (2c).

(S)-N-Methyl(phenyl)methyl-4,5-dichlorophthalimide (3.1 mmol,

1.0 g, 1.0 eq.), Pd(PPh3)4 (0.62 mmol, 0.72 g, 0.20 eq.) and
zinc(II) cyanide (3.7 mmol, 0.44 g, 1.2 eq.) were introduced into
a round-bottomed ask under argon. Dry DMF (6.2 mL) was
added and the mixture was gently stirred at 120 C over 2 h.
After this time, concentrated ammonia was added (30 mL) and
the solid residues were ltered, dried and directly puried by
silica gel column chromatography using toluene as an eluent,
affording the title compound (0.68 g, 72%) as a white crystalline
solid. 1H NMR (250 MHz, CDCl3): 8.21 (NCArH, s, 2 H),
7.47.55 (NCH(CH3)ArH, m, 2 H), 7.277.40 (NCH
(CH3)ArH, m, 3 H), 5.58 (NCH(CH3), q, J = 7.2 Hz,
1 H), 1.94 (NCH(CH3), d, J = 7.2 Hz, 3 H) ppm. 13C NMR
(63 MHz, CDCl3): 164.6, 139.0, 135.3, 128.9, 128.5, 128.0,
127.6, 121.2, 114.2, 51.2, 17.4 ppm. FT-IR: 3121 (w), 3062 (w),
2922 (w), 2243 (w), 1779 (m), 1713 (s), 1494 (w), 1457 (w),
1416 (w), 1389 (m), 1362 (s), 1318 (s), 1239 (w), 1214 (w),
1161 (m), 1113 (w), 1096 (m), 1072 (m), 1023 (w), 1003 (w),
993 (w), 920 (m), 904 (s), 849 (w), 805 (m), 771 (m), 741 (s),
2 1
723 (m), 701 (s) cm1. []25
546 = 0.26 deg cm g .

1436 (m), 1404 (m), 1386 (m), 1358 (s), 1215 (m), 115 (s),
1066 (s), 911 (m), 813 (w), 786 (w), 735 (s), 660 (m) cm1.
[TBA][Bis(N,N,N,N-tetrapropyl-29H,31H-2,3,9,10,16,17,23,24phthalocyaninatotetradicarboximide) terbium( III )] ([TBA][3b]). N-Propyl-4,5-dicyanophthalimide (0.42 mmol, 0.10 g,

8.0 eq.) was introduced into a dry Schlenk tube under argon.
The Schlenk was degassed and was purged with argon three
times. Dry hexanol (0.8 ml) was added with a syringe followed
by DBU (0.21 mmol, 31 l, 4.0 eq.) and after stirring for
5 minutes under argon, Tb(acac)3[H2O]3 (52 mol, 27 mg,
1.0 eq.) was added as one aliquot together with a catalytic
amount of potassium acetate. The mixture was then heated in a
sand bath to reux at 165 C for 15 h. After that time, a large
excess of tetrabutylammonium acetate was added and the
mixture was precipitated by the addition of methanol and
ltered. The obtained solid was puried by silica gel column
chromatography using CH2Cl2THFAcOH (66 : 33 : 1) as an
eluent. Some metal free phthalocyanine was eluted rst together
with an unidentied impurity. A deep dark blue band was then
eluted with THFAcOH (99 : 1) and was characterized as the
anionic form of [TBA][3b]. The obtained fraction was then
puried by repeated size exclusion chromatography on a BioBeads-SX1 medium using CH2Cl2 as an eluent, affording
the title compound (31 mg, 26%) as a dark purple powder.
MS m/z found: 2074.3 (M3b); Calcd for C104H72N24O16Tb:
2072.8. UV-vis (log()): 359 (5.1), 434 (4.5), 539 (4.1),
582 (4.4), 644 (5.2), 724 (5.0) nm. FT-IR: 2964 (w), 2935 (w),
2875 (w), 1760 (s), 1699 (s), 1482 (w), 1456 (w), 1436 (m),
1404 (s), 1379 (s), 1359 (s), 1345 (s), 1215 (s), 1147 (w),
1111 (s), 1073 (m), 1054 (s), 1002 (m), 976 (m), 955 (m),
907 (m), 889 (m), 842 (w), 814 (w), 785 (w), 733 (s), 699 (m),
659 (m) cm1.

[TBA][Bis(N,N,N,N-tetrapentadecyl-29H,31H-2,3,9,10,16,17,23,24-phthalocyaninatotetradicarboximide) terbium(III)] ([TBA][3a]). N-Pentadecyl-4,5-dicyanophthalimide (0.17 mmol, 70 mg,

[TBA][Bis(N,N,N,N-tetra((S)-methyl(phenyl)methyl)-29H,31H2,3,9,10,16,17,23,24-Phthalocyaninatotetradicarboximide)
terbium(III)]
([TBA][3c]). (S)-N-Methyl( phenyl)methyl-4,5-

8.0 eq.) was introduced into a dry Schlenk tube under argon.
The Schlenk was degassed and was purged with argon 3 times.
Dry hexanol (0.5 ml) was added with a syringe followed by
1,8-diazabicycloundec-7-ene (DBU, 86 mol, 13 mg, 4.0 eq.)
and after stirring for 5 minutes under argon Tb(OAc)3[H2O]6
(0.027 mmol, 12 mg, 1.0 eq.) was added as one aliquot. The
mixture was then warmed in a sand bath to reux at 160 C for
14 h. After that time, a large excess of tetrabutylammonium
acetate was added and the mixture was dried under vacuum to
remove the hexanol. The obtained waxy solid was puried by
silica gel column chromatography using chloroformAcOH
(99 : 1) as an eluent. Two thin bands were eluted containing the
metal free phthalocyanine and an unidentied impurity, respectively. The deep dark blue band remaining at the top of the
column was then eluted with THF and was characterized as
[TBA][3a]. The obtained fraction was puried by repeated size
exclusion chromatography on a BioBeads-SX1 medium using
toluene as an eluent, affording the title compound (27 mg, 37%)
as a waxy green-blue material. MS m/z found: 3419.7 (M3a);
Calcd for C200H264N24O16Tb: 3419.3. UV-vis (log()): 359
(5.0), 434 (4.5), 541 (3.9), 582 (4.3), 644 (5.2), 724 (5.0) nm.
FT-IR: 2921 (s), 2851 (s), 1767 (s), 1705 (s), 1465 (m),

dicyanophthalimide (0.60 mmol, 0.18 g, 8.0 eq.) was introduced

into a dry Schlenk tube under argon. The Schlenk was degassed
and was purged with argon 3 times. Dry hexanol (1.1 ml) was
added with a syringe followed by DBU (0.30 mmol, 45 l,
4.0 eq.) and after stirring for 5 min under argon, Tb(acac)3
[H2O]3 (75 mol, 38 mg, 1.0 eq.) was added as one aliquot
together with a catalytic amount of potassium acetate. The
mixture was then heated in a sand bath to reux at 165 C for
15 h. After that time, a large excess of tetrabutylammonium
acetate was added and the mixture was precipitated by the
addition of methanol and ltered. The obtained solid was
puried by silica gel column chromatography using CH2Cl2
THFAcOH (66 : 33 : 1) as an eluent. Some metal free phthalocyanine was eluted rst together with an unidentied impurity. A
deep dark blue band was then eluted with THFAcOH (99 : 1)
and was characterized as the anionic form of [TBA][3c]. The
obtained fraction was then puried by repeated size exclusion
chromatography on a BioBeads-SX1 medium using CH2Cl2 as
an eluent, affording the title compound (56 mg, 30%) as a shiny
dark purple powder. MS m/z Found: 2570.1 (M3c); Calcd for
C144H88N24O16Tb: 2569.3. UV-vis (log()): 362 (5.1), 434 (4.5),
553 (4.3), 587 (4.4), 647 (5.1), 721 (5.1) nm. FT-IR: 2964 (w),

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Fig. 1 Molecular structure of the phthalimide substituted doubledecker tebium(III) complexes [TBA][3ac].

2939 (w), 2875 (w), 1763 (s), 1700 (s), 1482 (m), 1450
1401 (m), 1377 (s), 1334 (s), 1206 (m), 1144 (m), 1111
1092 (m), 1049 (s), 1029 (m), 1013 (m), 906 (s), 854
814 (w), 802 (w), 774 (w), 749 (m), 735 (s), 693
663 (s) cm1.

(m),
(m),
(w),
(s),

Scheme 1 Synthesis of the imide substituted double-decker complexes

[TBA][3ac].

Results and discussion

Design and synthesis

In order to stabilize the negative charge of the anionic doubledecker complexes, cyclic imide derivatives were introduced on
the periphery of the phthalocyanine ligands (Fig. 1). The choice
of the substituents was based on the electron withdrawing capability of the carbonyl groups and the symmetric functionalization
thus obtained, yielding a symmetric molecular structure. Moreover, phthalimides are notoriously stable moieties used as amine
protecting groups.35 While carbonyl substituted phthalocyanines
are known,36 to the best of our knowledge the [TBA][3ac] salts
are the rst reported examples of phthalocyanine double-decker
complexes bearing these substituents, in this case in the form of
an N-substituted phthalimide.
The target double-decker complexes [TBA][3ac] were synthesized in good yields using an original three step pathway
from commercially available dichlorophthalic acid (see
Scheme 1). The dichlorophthalimides 1ac were rst prepared in
yields of approximately 60% by reacting the desired primary
amines with dichlorophthalic acid in conditions similar to those
of the Steglich esterication, that is in the presence of dicyclohexylcarbodiimide (DCC) and N,N-dimethylaminopyridine
(DMAP).37 Subsequently, the chlorides were displaced by cyanides in a tandem catalyzed reaction with zinc cyanide and tetrakis-triphenylphosphine palladium(0),25,38 affording the imide
phthalonitriles 2ac with yields varying from 54 to 72%.
Finally, the salts of the anionic double-decker complexes [TBA][3ac] were prepared by boiling the corresponding phthalonitriles in n-hexanol with the acetylacetonate salts of the terbium(III)
ion in the presence of 1,8-diazabicycloundec-7-ene (DBU)
and a catalytic amount of potassium acetate, in a variation of the
classical conditions performed by De Cian et al.,39 followed by
treatment with an excess amount of tetrabutyl ammonium acetate
([TBA][OAc]).
Dalton Trans.

Fig. 2 Normalized UV-visible absorption spectra of [TBA][3ac] in

dichloromethane solutions at concentrations of 6.9, 8.6 and 7.5
105 M, respectively.

The moderate yields obtained (2637%) could be accounted

for by partial degradation of the imide groups in the harsh reaction conditions necessary to prepare the double-decker complexes, as partially hydrolized fragments were detected in the
crude reaction products by mass spectroscopy and were eliminated during the purication process.

UV-visible spectroscopy

The absorption spectra of the salts [TBA][3ac] (Fig. 2) were

globally quite similar and consistent with their structures, presenting features akin to those of classical anionic double-decker
phthalocyanine lanthanide complexes40 but also exhibiting some
major differences.
While anionic terbium(III) double-decker complexes usually
present an intense Q band at 623 nm with a shoulder at around
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Fig. 3 Absorption spectral changes upon the heterogeneous oxidation

of the anionic form [TBA][3a] in a dichloromethane solution containing
a small crystal of iron(III) perchlorate.

675 nm,41 the Q band of [TBA][3a] ([TBA][3b] and [TBA][3c],

respectively) is shifted to a higher wavelength and appears as
two resolved bands at 644 (644 and 647, respectively) and 724
(724 and 721, respectively) nm. The characterization of the
anionic redox state was conrmed by adding a small crystal of
iron(III) perchlorate to a dichloromethane solution of compound
[TBA][3a]. The iron perchlorate is insoluble in dichloromethane
and so the oxidation took place slowly and could be monitored
by recording the spectral changes of the solution over time
(Fig. 3). The conversion of the native anionic state [TBA]+[3a]
to its neutral form, 3a0, proceeded with well dened isosbestic
points at 700 and 666 nm and the nal neutral state exhibited an
absorption spectrum consistent with that of neutral doubledecker complexes.40
Notably, two bands appear in the UV-visible and NIR regions
at 467 and 918 nm, respectively, which is a signature of the
-radical ligands present in neutral double-decker complexes.
The main difference between the spectral features of 3a0 and the
unsubstituted complex [Pc2Tb]0 is a small shift of the Q band to
a lower energy (681 nm for 3a0 instead of the usual 667 nm for
previously reported complexes).

Fig. 4 Cyclic voltammograms of 1.0 mM solutions of [TBA][3a]

(top), [TBA][3b] (middle) and [TBA][3c] (bottom) in dichloromethane
containing 0.1 M TBA+PF6.

other redox processes, suggests that the compounds form aggregates in the conditions of the experiment. This hypothesis is also
supported by the fact that the branched phenylethyl substituted
compound [TBA][3c] presents reversible voltammograms for all
the studied redox processes, which can be attributed to the
absence of aggregation due to the bulkiness of its side groups.

Electrochemistry

In order to characterize the redox properties of [TBA][3ac],

cyclic voltammograms were recorded in dichloromethane solutions. For the sake of simplicity, only the data concerning the
two oxidation processes is shown in Fig. 4. For more detailed
information see Fig. S4 to S9 in the ESI. The data conrms that
the compounds present an increased redox stability of the
anionic state under ambient conditions. Indeed, the rst oxidation potentials are found to be around 0.3 V vs. Fc/Fc+ for all
three compounds, which corresponds to a shift of approximately
0.7 V with respect to the unsubstituted Pc2Tb33,42 (the full list of
half-wave potentials is given in Table 1). It is noticeable that for
[TBA][3a] and [TBA][3b], the rst oxidation process is not well
dened and appears as two waves of lower intensity for
[TBA][3a] and as an asymmetrical shape for [TBA][3b]. This
fact, combined with the reversible waves associated with the
This journal is The Royal Society of Chemistry 2012

Magnetic properties

The slow magnetic relaxation of single molecule magnets is

reected in the temperature and frequency dependent maxima in
the ac-magnetic characteristics.1 In the case of [TBA][3ac], the
frequency dependent in-phase and out-of-phase ac-magnetic susceptibilities, M() and M(), were measured at temperatures
ranging from 5 to 55 K. Their temperature dependent counterparts (M(T) and M(T)) were measured at several frequencies
between 111 and 9999 Hz. For the sake of simplicity, only
M() is represented here (Fig. 5) and the rest of the data is provided in the ESI.
The in-phase and out-of-phase components were tted to a
ColeCole model,43 optimizing the parameters so as to t both
Dalton Trans.

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Table 1 Measured oxidation and reduction potentials for [TBA][3ac] in dichloromethane0.1 M TBAPF6, and the reported values for the
unsubstituted compound in the same conditions.32 The potentials are quoted versus Fc/Fc+ which is taken as 0.49 V vs. SCE. The calculated E
values correspond to the potential shifts with respect to Pc2Tb
Compound
[TBA][3a]
[TBA][3b]
[TBA][3c]
[TBA][Pc2Tb]

+0.84
+0.76
+0.78
+0.02

+0.28
+0.28a
+0.31
0.40

Red1

Red2

0.93
0.96
0.93
1.57

1.13
1.19
1.12
1.81

EOx2

EOx1
a

+0.80
+0.74
+0.76

+0.68
+0.68a
+0.71

ERed1

ERed2

+0.64
+0.61
+0.64

+0.68
+0.62
+0.69

These values are approximated since this redox process was poorly dened in the experimental conditions.

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Ox1

Ox2

Fig. 6 Arrhenius plots for [TBA][3a] (top), [TBA][3b] (middle) and

[TBA][3c] (bottom) extracted from the susceptibility plots of ac() and
ac(T). The dotted lines correspond to the linear ts of the thermally activated regimes of all three compounds.
Fig. 5 Frequency dependent plot of the out-of-phase ac-magnetic susceptibility M() plots for [TBA][3a] (top), [TBA][3b] (middle) and
[TBA][3c] (bottom), between 5 and 50 K. The continuous lines are best
ts to a ColeCole model.

sets of data, with = 2:

s T  s

Dalton Trans.

1 1 sin=2
1 21 sin=2 zza

T  s

1 cos=2
1 21 sin=2 zza

The tted relaxation times, , together with those extracted

from the temperature dependent plots were used to build the
Arrhenius plots for compounds [TBA][3ac] (Fig. 6). As usually
occurs with double-decker SMMS,29,44 the Arrhenius plots presents two regimes: a linear part at higher temperature, corresponding to a thermally activated Orbach relaxation process, and
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a deviation from the same at lower temperature where tunnelling

is predominant. The observed effective barrier heights for
[TBA][3ac] were found to be obs = 445, 428 and 463 cm1,
respectively, with pre-exponential factors of 01 = 6.35 1011,
1.34 1010 and 2.22 1011, respectively. The values obtained
here are in good agreement with those estimated from the
f-electronic structure of the unsubstituted anionic double-decker
phthalocyanine terbium(III) complex, with the energy difference
between J6 and J5 estimated at about 420 cm1 for
[TBA][Pc2Tb]. The ColeCole plots at 35 K (ESI) show that
[TBA][3ac] presents a single magnetic relaxation process with
a small dispersion of the relaxation rates (1 = 0.750.80).
Overall, the susceptibility data of [TBA][3ac] proves to be very
consistent from one substituent to the other, demonstrating the
robustness of the properties of this new family of complexes
towards subtitution on the imido nitrogen atom, which makes
this system a promising and versatile platform for potential
future applications. Magnetization hysteresis plots were recorded
for all three compounds at 2 and 7 K, at a eld sweeping rate of
1 Tmin1, and for |0H| 5 T. The curves were normalized to
their 5 T values and are plotted in Fig. 7 for |0H| 1 T (the
hystereses curves measured at 2 K are provided in the ESI). As
occurs with previously reported anionic double-decker
SMMs,9,41,45 [TBA][3a], [TBA][3b] and [TBA][3c] present
buttery-shaped hysteresis curves with a narrowing of the loops
for |0H| 0.09 T, which is known to be a result of the quantum
tunnelling of magnetization (QTM) occurring between the eight
low-lying |Jz>|Iz> states of the anionic compounds. As a result
of this phenomenon, the remnant magnetization and coercive
elds are minimal.
It is worth mentioning that the magnetization behavior
does not deviate much from that of the unsubstituted [TBA][Pc2Tb] and that all three compounds present similar features.
Nevertheless, the width of the hystereses close to the zero
eld varies slightly from one compound to another. In particular, [TBA][3b] presents an almost closed hysteresis loop,
which could be the result of slightly more efcient tunnelling in the solid state of this compound with respect to the other
two.

Conclusions
In the present work, the synthesis of a new family of doubledecker phthalocyanine complexes was demonstrated. Their
absorption, electrochemical and magnetic characterization
showed that the oxidation and reduction potentials of the new
compounds all present strong shifts of 0.60.8 V with respect to
complexes with more electron rich phthalocyanine rings, which
provides an unprecedented redox stability to this new family of
molecules. Indeed, while the unsubstituted neutral Pc2Tb can be
easily oxidized and reduced, often not on purpose, by the action
of mild chemical agents, the window of stability for the new
reported compounds spans about 1.2 V and is almost centered on
0 V vs. SCE. Despite this strong shift in redox potentials, we
have shown how the magnetic behaviour of the complexes is
intact, as can be seen in both the ac-magnetic susceptibility data
and the hystereses of magnetization. It is therefore expected that
the new system presented in this article will be a good candidate
This journal is The Royal Society of Chemistry 2012

Fig. 7 Hysteresis of magnetization for [TBA][3a] (top), [TBA][3b]

(middle) and [TBA][3c] (bottom) measured at 2 K and a sweeping rate
of 1 Tmin1.

for future applications in hybrid molecular devices, limiting the

occurrence of charge transfer between the inorganic substrates
and the SMMs.

Acknowledgements
This work has been carried out within the 6th and 7th FPs of the
EU, under contracts MAGMANet (no. 515767), FuMaSSEC
(MEST-CT-2005-020992) and supported by the Spanish projects
EMOCIONA (CTQ2006-06333/BQU), POMAs (CTQ2201019501), the Generalitat de Catalunya AGAUR (2009SGR00516) and the CIBER de Bioingeniera, Biomateriales y Nanomedicina (CIBER-BBN), promoted by ISCIII, Spain. We
warmly thank Amable Bernab (ICMAB-CSIC) for recording
the IR and LDI-TOF spectra and Bernat Bozzo for the PPMS
susceptibility and hysteresis measurements.
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