10264 Inorg. Chem.

2009, 48, 10264–10274

DOI: 10.1021/ic901379d

Building Multistate Redox-Active Architectures Using Metal-Complex

Functionalized Perylene Bis-imides
Gudrun Goretzki,† E. Stephen Davies,† Stephen P. Argent,† John E. Warren,‡ Alexander J. Blake,† and
Neil R. Champness*,†
†
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K., and
‡
Daresbury Laboratory, Synchrotron Radiation Source, Warrington WA4 4AD, U.K.
Received July 14, 2009
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A series of multistate redox-active architectures has been synthesized, structurally characterized, and their optical and
redox properties investigated. Specifically, two redox-active ferrocene or cobalt-dithiolene moieties have been
introduced to the “bay” region of perylene-bisimides. Three of these disubstituted perylene-bisimide species have been
structurally characterized by single crystal X-ray diffraction, confirming the twisted nature of the central perylene core.
The first isomeric pair of disubstituted perylene-bisimide isomers, N,N0 -di-(n-butyl)-1,7-diferrocenyl-perylene-
3,4:9,10-tetracarboxylic acid bisimide (2) and N,N0 -di-(n-butyl)-1,6-diferrocenyl-perylene-3,4:9,10-tetracarboxylic
acid bisimide (3), structurally characterized by single crystal X-ray diffraction are reported and compared. Structural
characterization of the cobalt-dithiolene substituted perylene-bisimide, N,N0 -di-(n-butyl)-1,7-dicyclopentadienyl-
cobalt(II)-dithiolenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (4), reveals the expected twisting of the perylene
core and confirms the ene-dithiolate geometry of the cobalt dithiolene moiety. Cyclic voltammetry measurements,
coupled with spectroelectrochemcial and electron paramagnetic resonance studies, of 1-4, where 1 is N,N0 -di-
(n-butyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide, reveal the two anticipated perylene-
bisimide based reductions. In addition, for the ferrocene substituted compounds, 1-3, a single reversible two-electron
oxidation is seen with only a small degree of communication between the ferrocene groups observed in the 1,6-isomer
where the two ferrocene groups are attached to the same naphthyl moiety. In the case of 4, two reversible reductions
associated with the cobalt-dithiolene moieties are observed, confirming communication across the reduced perylene
core.

Introduction Perylene-bisimides and their derivatives have received a

The design of species for storing information at the great deal of attention because of their remarkable electro-
molecular or submolecular scale represents one of the major chemical and optical properties,3 and they are potentially
challenges for molecular nanoscience.1 Such information attractive targets for molecular species capable of informa-
storage may be achieved in a number of ways but perhaps tion storage. Their properties have been exploited for a
the most readily targeted multistate systems are those that number of applications including n-type semiconductors,4
allow switching between molecular redox states.2 Indeed, if thin film-transistors,5 and in solar cells.6 In addition, the
reversible switching is possible in such systems it may be extended aromatic structure of the perylene core coupled
possible to develop molecular units capable of adopting a with extensive scope for derivatization makes them attractive
number of different states that can be probed by a variety
of techniques. In particular, by appropriate choice of com-
::
ponent, redox states can be assessed by electrochemical, (3) Wurthner, F. Chem. Commun. 2004, 1564–1579.
(4) (a) Struijk, C. W.; Sieval, A. B.; Dakhorst, J. E. J.; Van Dijk, M.;
magnetic, electron paramagnetic resonance (EPR), or spectr- Kimkes, P.; Koehorst, R. B. M.; Donker, H.; Schaafsma, T. J.; Picken, S. J.;
oscopic methods. ::
Van de Craats, A. M.; Warman, J. M.; Zuilhof, H.; Sudholter, E. J. R. J. Am.
Chem. Soc. 2000, 122, 11057–11066. (b) Dimitrakopoulos, C. D.; Malenfant,
*To whom correspondence should be addressed. E-mail: neil.champness@ P. R. L. Adv. Mater. 2002, 14, 99–117. (c) Langhals, H. Heterocycles 1995, 40,
nottingham.ac.uk. Phone: þ44 115 951 3505. Fax þ44 115 9513563. 477. (d) Yoo, B.; Jung, T.; Basu, D.; Dodabalapur, A.; Jones, B. A.; Faccetti, A.;
(1) Joachim, C.; Gimzewski, J. K.; Aviram, A. Nature 2000, 408, 541–548. Wasielewski,::M. R.; Marks, T. J. Appl. Phys. Lett. 2006, 88, 082104.
Pease, A. R.; Jeppesen, J. O.; Stoddart, J. F.; Luo, Y.; Collier, C. P.; Heath, J. R. (5) (a) Wurthner, F. Angew. Chem., Int. Ed. 2001, 40, 1037–1039. (b) Jones,
Acc. Chem. Res. 2001, 34, 433–444. Service, R. F. Science 2001, 293, 782–785. B. A.; Facchetti, A.; Wasielewski, M. R.; Marks, T. J. Adv. Funct. Mater. 2008,
(2) Ruben, M.; Breuning, E.; Gisselbrecht, J. P.; Lehn, J.-M. Angew. 18, 1329–1339.
::
Chem., Int. Ed. 2000, 39, 4139–4142. Ruben, M.; Lehn, J.-M.; Muller, P. Chem. (6) Ferrere, S.; Zaban, A.; Gregg, B. A. J. Phys. Chem. B 1997, 101, 4490–
Soc. Rev. 2006, 35, 1056–1067. 4493.

pubs.acs.org/IC Published on Web 10/02/2009 r 2009 American Chemical Society

Article Inorganic Chemistry, Vol. 48, No. 21, 2009 10265
targets for the generation of liquid crystals7 and for surface- bisimide (PBI) core. In particular, a series of molecules has
based self-assembly processes.8 been prepared: 1,7-(CtCFc)2-PBI 1, two isomers of ferroce-
Perylene-bisimides typically display two reversible reduc- nyl (Fc) substituted PBI, 1,7-(Fc)2-PBI 2 and 1,6-(Fc)2-PBI 3,
tion processes3,7,9 accompanied by a variety of color changes10 and a cyclopentadienyl cobalt dithiolene functionalized spe-
and, in some instances, switching of fluorescence proper- cies 1,7-[(cp)Co(II)S2C2H]2-PBI 4 (Scheme 1). Compounds
ties.11 Bearing in mind the rich electrochemical properties of 1-4 are among the first examples of perylenetetracarboxylic
the extensive aromatic perylene-bisimide subunit, it is per- bisimides functionalized with redox active groups. Previous
haps surprising that they have not been developed as com- examples of ferrocene functionalized PBIs,10a,11 in which the
ponents for the burgeoning field of molecules capable of redox active appendages are separated from the perylene core
information storage. However, if chemical derivatization is by a non-conjugated linker, would not be anticipated to, and
considered it becomes more apparent why this is the case. The do not provide direct electrochemical communication to the
most facile synthetic strategy for derivatization of perylene- perylene core.
tetracarboxylic bisimides is via variation in amine appendage
utilized in the initial formation of the imide moiety. Such Experimental Section
functionalization is readily achieved but has limited influence Synthetic Methodology. Perylene-3,4:9,10-tetracarboxylic
upon the electronic and optical properties of the aromatic acid (Aldrich) was used as starting material for the synthesis
perylene core.12 Molecular orbital calculations on such of 1,7-dibromo-perylene-3,4:9,10-tetracarboxylic acid13 and
compounds reveal a node in the highest occupied molecular N,N0 -bis-(n-butyl)-1,7-dibromo-3,4:9,10-perylenetetracarboxylic
orbital (HOMO) at the nitrogen atoms of the two imide bisimide.13 Ethynylferrocene14 and [NBu4][BF4]15 were pre-
functions and this precludes the use of appendages to the pared by literature methods. Ferrocenylboronic acid was pur-
imides for electronic communication pathways. Alterna- chased from Aldrich and used as supplied. All reactions were
tively, derivatization can be achieved in the “bay region” at carried out under an atmosphere of dinitrogen or argon where
noted. Column chromatography was performed on silica gel
the 1, 6, 7, and/or 12 positions of the perylene core. Although (Merck silica gel 60, 0.2-0.5 mm, 50-130 mesh). It is known
synthetically more complex, such reactions have the advan- that the bromination of perylene bis-anhydride affords a mix-
tage that appended functional groups are directly attached to ture of 1,7- and 1,6-isomers, typically is the ratio 80:20.13
the perylene core, a situation which may be anticipated Although the different isomers could be detected via NMR
to facilitate orbital overlap between the appendage and the spectroscopy throughout the synthetic path, separation on the
aromatic core of the molecule, potentially resulting in com- large scale could not be accomplished and, unless otherwise
munication across the molecule. Although a wide variety of stated, the isomeric mixtures were used. 1H NMR (300 MHz)
functionalized perylenetetracarboxylic bisimides is possible, and 13C NMR (75 MHz) were obtained on a Bruker 300 MHz
attachment of appendages to the perylene core in the bay spectrometer. Microanalyses were performed by Stephen Boyer,
London Metropolitan University, London, U.K. MS spectra
region is anticipated to result in twisting of the two naphthyl (MALDI-TOF-MS) were determined on a Voyager-DE-STR
moieties of the perylene core linked at the 13/14 and 17/18 mass spectrometer.
positions.3,10b Although not entirely prohibitive, distortion N,N0 -Di-(n-butyl)-1,7-Di-(trimethylsilylethynylen)perylene-3,
of the perylene core may be anticipated to inhibit commu- 4:9,10-tetracarboxylic Acid Bisimide. N,N0 -di-(n-butyl)-1,7-
nication across this moiety reducing the interaction between dibromoperylene-3,4:9,10-tetracarboxylic acid bisimide13 (3
redox groups on opposing sides of the perylene moiety. mmol) was dissolved in a mixture of dry tetrahydrofuran
We have targeted three related molecular species that (THF, 100 mL) and dry triethylamine (50 mL) in an Ar atmo-
contain redox active metal complex based appendages to sphere. PdCl2(PPh3)2 (84 mg, 0.12 mmol), CuI (29 mg, 0.15
the central N,N0 -di-(n-butyl)-3,4:9,10-tetracarboxylic acid mmol), and ethynyltrimethylsilane (1.66 mL, 12 mmol) were
added, and the reaction mixture was stirred at 80 °C for 4 h,
cooled to room temperature, and poured into 100 mL of cold
(7) Wurthner, F.; Thalacker, C.; Diele, S.; Tschierske, C. Chem.;Eur. J. diluted HCl. The product was extracted with CH2Cl2, and the
2001, 7, 2245–2253. organic layer washed with water until neutral. The crude
(8) (a) Theobald, J. A.; Oxtoby, N. S.; Phillips, M. A.; Champness, N. R.;
product was purified by column chromatography on silica
Beton, P. H. Nature 2003, 424, 1029. (b) Swarbrick, J. C.; Ma, J.; Theobald,
J. A.; Oxtoby, N. S.; O'Shea, J. N.; Champness, N. R.; Beton, P. H. J. Phys. Chem. (CHCl3) to give 1.68 g (89%) of a red powder. 1H NMR
B 2005, 109, 12167. (c) Theobald, J. A.; Oxtoby, N. S.; Champness, N. R.; Beton, (CDCl3): δ = 10.17 (d, 2H, 3J = 8.27); 8.82 (s, 2H); 8.62 (d,
P. H.; Dennis, T. J. S. Langmuir 2005, 21, 2038. (d) Perdig~ao, L. M. A.; Perkins, 2H, 3J = 8.27); 4.25 (t, 4H, NCH2, 3J = 7.5 Hz); 1.78 (m, 4H);
E. W.; Ma, J.; Staniec, P. A.; Rogers, B. L.; Champness, N. R.; Beton, P. H. 1.49 (m, 4H); 1.02 (t, 6H, 3J = 7.3 Hz); 0.41 (s, 18H). 13C NMR
J. Phys. Chem. B 2006, 110, 12539. (e) de Feyter, S.; Miura, A.; Yao, S.; Chen, (CDCl3): δ = 163.18, 162.4288, 138.39, 138.03, 134.23, 133.93,
::
Z.; Wurthner, F.; Jonkheijm, P.; Schenning, A. P. H. J.; Meijer, E. W.; de Schryver, 133.32, 130.40, 130.05, 127.56, 127,29, 123.51, 123.16, 122.0,
F. C. Nano Lett. 2005, 5, 77. (f) Perdigao, L. M. A.; Saywell, A.; Fontes, G. N.; 120.36, 119.80, 106.49, 105.62, 40.51, 30.23, 20.45, 13.95, -0.28.
Staniec, P. A.; Goretzki, G.; Phillips, A. G.; Champness, N. R.; Beton, P. H. Anal. Calcd for C42H42N2O4Si2: C: 72.59 ;H: 6.09; N: 4.03%;
Chem.;Eur. J. 2008, 14, 7600. ::
(9) (a) You, C.; Espindola, P.; Hippius, C.; Heinze, J.; Wurthner, F. Adv. Found: C: 72.70; H: 6.15; N:3.98%. MS (EI): m/z 694.3 (Mþ).
Funct. Mat. 2007, 17, 3764–3772. (b) Ahrens, M. J.; Fuller, M. J.; Wasielewski, N,N0 -Di-(n-butyl)-1,7-diethynylenperylene-3,4:9,10-tetracar-
M. R. Chem. Mater. 2003, 15, 2684–2686. (c) Salbeck, J.; Kunkely, H.; boxylic Acid Bisimide. N,N0 -di-(n-butyl)-1,7-Di-(trimethyl-
Langhals, H.; Saalfrank, R. W.; Daub, J. Chimia 1989, 43, 6–9. (d) Chen, Z.; silylethynylen)perylene-3,4:9,10-tetracarboxylic acid bisimide
::
Debije, M. G.; Debaerdemaeker, T.; Osswald, P.; Wurthner, F. ChemPhysChem 1.39 g (2 mmol) was dissolved in CHCl3 (75 mL) and MeOH
2004, 5, 137–140. :: (20 mL). NaOH (0.72 mmol, 29 mg) was added, and the reaction
(10) (a) You, C.; Wurthner, F. J. Am. Chem. Soc. 2003, 125, 9716–9725.
mixture was stirred at room temperature for 1 h. CHCl3 was
(b) Goretzki, G.; Davies, E. S.; Argent, S. P.; Alsindi, W.; Blake, A. J.; Warren, J.
E.; McMaster, J.; Champness, N. R. J. Org. Chem. 2008, 73, 8808.
(11) (a) Zhang, R.; Wang, Z.; Wu, Y.; Fu, H.; Yao, J. Org. Lett. 2008, 10, :: ::
(13) Wurthner, F.; Stepanenko, V.; Chen, Z.; Saha-Moller, C. R.;
3065–3068. (b) Huang, J.; Wu, Y.; Fu, H.; Zhan, X.; Yao, J.; Barlow, Kocher, N.; Stalke, D. J. Org. Chem. 2004, 69, 7933.
S.; Marder, S. R. J. Phys. Chem. A 2009, 113, 5039–5046. (14) Rosenblum, M.; Brawn, N.; Papenmeier, J.; Applebaum, M. J.
(12) Langhals, H.; Demmig, S.; Huber, H. Spectrochim. Acta 1988, 44A, J. Organomet. Chem. 1966, 6, 173.
1189–1193. (15) Kubas, J. Inorg. Synth. 1990, 28, 68.
10266 Inorganic Chemistry, Vol. 48, No. 21, 2009 Goretzki et al.
Scheme 1. Synthetic Procedures for 1, 4, and 5a

a
(a) Fc-CtCH, Pd(PPh3)2Cl2, CuI, NEt3, toluene, 110 °C, 76%; (b) THF, NEt3, ethynyltrimethylsilane, PdCl2(PPh3)2, CuI, 70°C, 89%; (c) MeOH/
CHCl3, NaOH, 95%; (d) S8, cyclopentadienyl cobalt(I) dicarbonyl, toluene, 110°C, 63%. A mixture of both 1,7- and 1,6-Br2-PBI was used in reactions
(a) and (b) with any residual 1,6-isomers removed during purification procedures.

added to dissolve the product completely, and the NaOH re- bisimide 1a was prepared in an analogous fashion to 1 but using
moved by filtration. Precipitation with methanol yielded the N,N0 -di-(n-octyl)-1,7-dibromoperylene-3,4:9,10-tetracarboxy-
product in quantitative yield and pure enough to be used in the lic acid bisimide as a starting material. 1a 1H NMR (CDCl3):
next step without further purification. Acquisition of a 13C NMR δ = 10.16 (d, 2H, 3J = 6.3 Hz); 8.84 (s, 2H); 8.73 (d, 2H, 3J = 6.3
spectrum was precluded by the poor solubility of the compound. Hz), 4.72 (s, 4H, Fc), 4.49 (s, 4H, Fc), 4.35 (s, 10H, Fc), 4.28
1
H NMR (CDCl3): δ = 10.22 (d, 2H, 3J = 8.10 Hz); 8.95 (s, 2H); (t, 4H, 3J = 7.5 Hz), 1.79 (m, 4H), 1.48 (m, 20H), 0.91 (t, 6H,
8.82 (d, 2H, 3J = 8.10 Hz); 4.29 (t, 4H, 3J = 7.5 Hz); 3.94 (s, 2H); 3
J = 7.3 Hz).
1.76 (m, 4H); 1.49 (m, 4H), 1.01 (t, 6H, 3J = 7.3 Hz). Anal. Calcd N,N0 -Di-(n-butyl)-1,7-diferrocenyl-perylene-3,4:9,10-tetracar-
for C36H26N2O4: C: 78.53; H: 4.76; N: 5.09%. Found: C:78.60; H: boxylic Acid Bisimide 2 and N,N0 -Di-(n-butyl)-1,6-diferrocenyl-
4.83; N: 4.98%. MS (MALDI-TOF): m/z 550.2 (Mþ). perylene-3,4:9,10-tetracarboxylic Acid Bisimide 3. N,N0 -Bis-(n-
N,N0 -Di-(n-butyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10- butyl)-1,7-dibromo-3,4:9,10-perylenetetracarboxylic bisimide13
tetracarboxylic Acid Bisimide 1. N,N0 -Di-(n-butyl)-1,7-dibro- (mixture of isomers, 297 mg, 0.45 mmol), ferrocenylboronic acid
moperylene-3,4:9,10-tetracarboxylic acid bisimide13 (0.66 g, (310 mg, 1.35 mmol), CsF (274 mg, 1.8 mmol), Ag2O (232 mg,
1 mmol) was dissolved in a mixture of dry toluene (100 mL) 1 mmol), and Pd(PPh3)4 (26 mg, 0.022 mmol) were dissolved in
and dry triethylamine (50 mL) in an Ar atmosphere. PdCl2- dry THF (70 mL) and the solution degassed. After stirring at
(PPh3)2 (70 mg, 0.1 mmol), CuI (22 mg, 0.11 mmol), and 80 °C for 24 h the solvent was removed under reduced pressure,
ethynylferrocene14 (0.46 g, 2.2 mmol) were added, and the and the residue subjected to column chromatography on silica
reaction mixture was stirred at 70 °C for 8 h. Following cooling with CH2Cl2 to yield the desired product as a red powder in 35%
to room temperature, the product was extracted with CH2Cl2 yield. The 1,7- (2) and 1,6- (3) were separated on a smaller scale
and filtered through a small silica pad. The crude product by column chromatography using CH2Cl2 as eluent on silica.
was purified by recrystallization from CHCl3 and MeOH to give 2: 1H NMR (CDCl3): δ = 9.02 (s, 2H), 8.16 (d, 2H, 3J = 8.17
0.70 g (76%) of a red powder. Hz), 7.82 (d, 2H, 3J = 8.17 Hz), 4.55 (dd, 8H, FcH), 4.22 (m,
1
H NMR (CDCl3): δ = 10.13 (d, 2H, 3J = 7.74); 8.81 (s, 2H); 14H, NCH2-butyl þ FcH), 1.76 (m, 4H), 1.48 (m, 4H), 1.01 (t,
8.72 (d, 2H, 3J = 7.74), 4.72 (s, 4H, Fc), 4.5 (s, 4H, Fc), 4.36 6H, 3J = 7.5 Hz), 13C NMR (CDCl3): δ = 163.87, 163.73,
(s, 10H, Fc), 4.26 (t, 4H, 3J = 7.5 Hz), 1.78 (m, 4H), 1.48 (m, 138.54, 136.42, 134.24, 133.29, 129.1, 128.67, 128.52, 126.99,
4H), 1.04 (t, 6H, 3J = 7.3 Hz). 13C NMR (CDCl3): δ = 163.39, 121.52, 120.52, 89.61, 70.58, 70.33, 70.25, 40.55, 30.38, 20.56,
163.11, 137.40, 134.23, 132.97, 129.83, 127.69, 127.20, 126.50, 13.98. Anal. Calcd for C52H42N2O4Fe2: C: 71.74; H: 4.86; N:
122.77, 121.82, 120.78, 100.75, 88.13, 71.93, 70.42, 70.30, 63.66, 3.21%. Found: C: 71.75; H: 4.77; N: 3.18%. MS (MALDI-
40.48, 30.98, 30.26, 20.46, 13.94. We were unable to obtain TOF): m/z 870.2 (Mþ).
meaningful CHN data because of incomplete combustion of 1. 3: 1H NMR (CDCl3): δ = 9.13 (s, 2H), 8.23 (d, 2H, 3J = 8.08
MS (MALDI-TOF): m/z 918.2 (Mþ). N,N0 -Di-(n-octyl)-1, Hz), 7.87 (d, 2H, 3J = 8.08 Hz), 4.49 þ 4.40 (dt, 4H each), 4.27
7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid (t, 4H, 3J = 7.5 Hz), 4.17 (s, 10H), 1.81, (m, 2H)), 1.72 (m, 2H),
Article Inorganic Chemistry, Vol. 48, No. 21, 2009 10267
1.46 (m, 4H), 1.04 (t, 3H, 3J = 7.3 Hz). 13C NMR (CDCl3): δ = Crystal data for 2: C52H42Fe2N2O4. Monoclinic, space group
163.91, 163.72, 138.53, 136.44, 134.32 133.36, 129.11, 128.72, C2, a = 30.9591(9), b = 15.4042(3), c = 21.1507(6) Å, β =
128.55, 127.03, 121.53 120.55, 89.51, 70.49, 70.25, 70.21, 40.49, 117.241(2)°, V = 8968.0(4) Å3, Z = 8, Dcalc = 1.290 g cm-3,
30.34, 20.52 13.94; MS (MALDI-TOF): m/z 870.2 (Mþ). μ = 0.693 mm-1, F(000) = 3616. A total of 50313 reflections
N,N0 -Di-(n-butyl)-1,7-dicyclopentadienyl-cobalt(II)-dithiolenyl- were collected, of which 19403 were unique, with Rint = 0.046.
perylene-3,4:9,10-tetracarboxylic Acid Bisimide 4. A mixture of Final R1 (wR2) = 0.0966 (0.269) with GOF = 1.03. Flack
N,N0 -di-(n-butyl)-1,7-diethynylenperylene-3,4:9,10-tetracarboxy- parameter = 0.16(2).
lic acid bisimide (55 mg, 0.1 mmol), cyclopentadienyl cobalt(I) Crystal data for 3: C52H42Fe2N2O4. Triclinic, space group P1,
dicarbonyl (39 mg, 0.216 mmol) and sulfur (13 mg, 0.41 mmol) a = 12.614(3), b = 12.629(3), c = 13.098(3) Å, R = 83.014(3)°,
in degassed toluene (30 mL) was stirred under reflux for 30 h. β = 73.770(3)°, γ = 81.552(3)°, V = 1974.5(9) Å3, Z = 2,
The solvent was removed under reduced pressure and the Dcalc = 1.464 g cm-3, μ = 0.787 mm-1, F(000) = 904. A total of
residue purified by column chromatography (CH2Cl2) to yield 12789 reflections were collected, of which 5588 were unique, with
the product as a dark blue in 63% yield. Rint = 0.065. Final R1 (wR2) = 0.0693 (0.195) with GOF = 1.00.
1
H NMR (CDCl3): δ = 1H NMR (CDCl3): δ = 8.77 (s, 2H, Crystal data for 4: C46H36Co2N2O4S4 3 1.5(C7H8). Triclinic,
thiane), 8.64 (s, 2H), 7.95 (d, 2H, 3J = 8.18 Hz), 7.08 (d, 2H, space group P1, a = 13.2568(6), b = 13.7187(6), c =
3
J = 8.18 Hz), 5.48 (s, 10H, Cp-H), 4.18 (t, 4H, 3J = 7.5 Hz), 14.9131(7) Å, R = 95.129(1)°, β = 108.214(1)°, γ = 108.376(1)°,
1.72, (m, 4H)), 1.43 (m, 4H), 0.99 (t, 6H, 3J = 7.3 Hz); 13C NMR V = 2391.2(2) Å3, Z = 2, Dcalc = 1.479 g cm-3, μ = 0.920 mm-1,
(CDCl3): δ = 163.57, 163.30, 157.77, 140.09, 137.64, 135.89, F(000) = 1102. A total of 27294 reflections were collected, of
134.99, 134.49, 131.96, 130.08, 129.41, 128.86, 127.76, 121.76, which 14145 were unique, with Rint = 0.048. Final R1 (wR2) =
121.65, 79.79, 40.32, 30.26, 20.40, 13.90. Anal. Calcd for 0.0538 (0.161) with GOF = 1.04.
C40H40N4O6: C: 59.61; H: 3.91; N: 3.01%;. Found: C: 59.53; Crystallographic data have been deposited with the Cam-
H: 3.86; N: 2.94%; MS (MALDI-TOF): m/z 926 (Mþ). bridge Crystallographic Data Centre as supplementary publica-
Single Crystal X-ray Diffraction Studies. Single crystal X-ray tions CCDC 731962-731964 for complexes 2-4, respectively.
data for 2 were collected on an Enraf-Nonius KappaCCD area Electrochemical and Spectroelectrochemical Measurements.
detector diffractometer (rotating anode, graphite Mo-KR radia- CH2Cl2 (Fisher) was freshly distilled from calcium hydride
tion λ = 0.71073 Å) or, for 3 and 4, on a Bruker SMART under an atmosphere of dinitrogen. Ferrocene (Aldrich) was
APEXII CCD area detector diffractometer at Station 9.8 of the used as received. Cyclic voltammetric and coulometric studies
Daresbury Laboratory Synchrotron Radiation Source (λ = were carried out using an Autolab PGSTAT20 potentiostat.
0.6911 Å).16 The crystals were cooled using an Oxford Cryo- Standard cyclic voltammetry was carried out under an atmo-
systems cryostat.17 The structures were solved by direct sphere of argon using a three-electrode arrangement in a single
methods using SHELXS97;18 subsequent full-matrix least- compartment cell. A glassy carbon working electrode, a Pt wire
squares refinement employed SHELXL97.18 All hydro- secondary electrode, and a saturated calomel reference elec-
gen atoms were placed in geometrically calculated positions trode, chemically isolated from the test solution via a bridge tube
and thereafter refined using a riding model with Uiso(H) = containing electrolyte solution and fitted with a porous Vycor
1.2Ueq(C). All non-hydrogen atoms were refined with anisotro- frit, were used in the cell. The solutions were 10-3 M in test
pic displacement parameters. For 2 the crystal was found to be compound and 0.4 M in [NBu4][BF4] as supporting electrolyte.
non-merohedrally twinned by 180° rotation about the [-203] Redox potentials are quoted versus the ferrocenium-ferrocene
reciprocal lattice direction: the twin fraction refined to 0.346(3). couple used as an internal reference.19 Compensation for inter-
Geometric restraints were applied to the bond lengths of the nal resistance was not applied.
imide portions of one of the two molecules found in the Bulk electrolysis experiments, at a controlled potential, were
asymmetric unit, (Fe3/Fe4 C1B-C64B). Geometric restraints carried out using a two-compartment cell. The Pt/Rh gauze
basket working electrode was separated from the wound Pt/Rh
were applied to the 1,2 and 1,3 bond lengths of all four butyl
gauze secondary electrode by a glass frit. A saturated calomel
chains. All non-hydrogen atoms were refined anisotropically
reference electrode was bridged to the test solution through a
with appropriate restraints (SIMU, DELU)18 applied to all
Vycor frit orientated at the center of the working electrode. The
displacement parameters. Small electron density peaks near
working electrode compartment was fitted with a magnetic
the bay regions of molecule B (Fe3/Fe4 C1B-C64B) may be a stirrer bar, and the test solution was stirred rapidly during
result of minor conformational disorder, occupational disorder electrolysis.
with the brominated starting material, or handling of the Solutions were 0.4 M in [NBu4][BF4] as supporting electrolyte
twinning. For 3, disorder of the butyl chains was modeled as and 10-3 M in test compound and were prepared using Schlenk
two orientations each with occupancy of 0.5 as determined by line techniques. Electrolyzed solutions were transferred to
refinement before fixing in each case. The butyl chains num- quartz tubes, via steel canula, for analysis by EPR spectroscopy.
bered C51-C540 were modeled isotropically after anisotropic EPR spectra were recorded on a Bruker EMX spectrometry and
refinement became unstable. Appropriate restraints were ap- simulated using WINEPR SimFonia (Shareware version 1.25,
plied to the geometry and displacement parameters of the butyl ::
Bruker Analytische Messtechnik GmbH).
chains. For 4 atom S44 was found to be disordered over two The UV/vis spectroelectrochemical experiments were carried
positions, occupancy summed to unity using a free variable, with out in an optically transparent electrochemical (OTE) cell
appropriate similarity restraints applied to the bond lengths (modified quartz cuvette, optical path length 0.5 mm).20 A
between S44 or S440 and the adjacent carbon atom. Also for 4, a three-electrode configuration, consisting of a Pt/Rh gauze
C6H5Me solvent molecule was found to be disordered over a working electrode, a Pt wire secondary electrode (in a fritted
crystallographic inversion center with further positional disor- PTFE sleeve) and a saturated calomel electrode, chemically
der, indicated by the Fourier map, which could not be modeled. isolated from the test solution via a bridge tube containing
Appropriate restraints were applied to the geometry and dis- electrolyte solution and terminated in a porous frit, was used in
placement parameters of this C6H5Me molecule.
(19) Gagne, R. R.; Koval, C. A.; Lisensky, G. C. Inorg. Chem. 1980, 19,
(16) Cernik, R. J.; Clegg, W.; Catlow, C. R. A.; Bushnell-Wye, G.; 2854.
Flaherty, J. V.; Greaves, N.; Burrows, I.; Taylor, D. J.; Hamichi, M. (20) Macgregor, S. A.; McInnes, E.; Sorbie, R. J.; Yellowlees, L. J.
J. Synchrotron Radiat. 1997, 4, 279–286. Molecular Electrochemistry of Inorganic, Bioinorganic and Organometallic
(17) Cosier, J.; Glazer, A. M. J. Appl. Crystallogr. 1986, 19, 105. Compounds; Pombeiro A. J. L., McCleverty, J. A., Eds.; Kluwer Academic
(18) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112–122. Publishers: Norwell, MA, 1993; p 503.
10268 Inorganic Chemistry, Vol. 48, No. 21, 2009 Goretzki et al.
Scheme 2. Synthetic Procedures for 2 and 3a

a
(a) FcB(OH)2, Pd(PPh3)4, AgO, CsF, toluene, 110 °C, 65% (1,7 isomer), 12% (1,6 isomer).

Figure 1. Views of the single crystal structures of compounds 2 (a) and 3 (b) illustrating the twisted arrangement of the perylene core in both the 1,7- and 1,6-isomers
of this compound. Displacement ellipsoids are drawn at the 50% probability level. In the case of (a) only one of a pair of independent molecules is shown.

the cell. The potential at the working electrode was controlled by ratio which it has not proven possible to separate.13 The
a Sycopel Scientific Ltd. DD10 M potentiostat. The UV/vis 1,7-isomer is always the major product from the bromi-
spectra were recorded on a Perkin-Elmer Lambda 16 spectro- nation of perylene-3,4:9,10-tetracarboxylic acid and as
photometer. The cavity was purged with dinitrogen, and tem- a result the same isomer is also the major product
perature control at the sample was achieved by flowing cooled
dinitrogen across the surface of the cell. from substitution reactions using the “as synthesised”
N,N0 -bis-(n-alkyl)-dibromo-3,4:9,10-perylenetetracarbo-
Results and Discussion xylic bisimide. Thus in this study it was found that only in
the case of di-Fc substituted compounds (2 and 3) did the
Synthesis. Compounds 1-5 were prepared as outlined isolation of the minor 1,6 isomer (3) prove possible. For 1
in Scheme 1 (1, 4, 5) and Scheme 2 (2, 3), exploiting and 4 the 1,7 isomers could be isolated but unfortunately
Sonagashira coupling in the case of 1, 4, and 5 to we were unable to separate pure samples of the corre-
introduce acetylenyl functionality to the perylene, repla-
sponding 1,6 isomers. Compound 5 was prepared by
cing bromo substituents. For the synthesis of 4, following
utilizing a Sonagashira coupling of phenylacetylene with
the initial introduction of acetylenyl substituents to the
Br2-PBI and provided a useful comparison to the other
perylene core, reaction with S8 and cyclopentadienyl-
compounds in terms of the redox behavior.
cobalt(I) dicarbonyl affords compound 4 in good yield.
Single Crystal X-ray Diffraction Structural Studies.
Compounds 2 and 3 (Scheme 2) were prepared by the
Single crystals of compounds 2-4 were grown by vapor
direct Suzuki coupling of Fc[B(OH)2] in the presence of
Pd(PPh3)4, AgO, and CsF in C6H5Me.21 diffusion of C6H5Me (2, 4) or n-hexane (3) into CHCl3
In the case of compounds 2 and 3 the 1,7 (2) and less solutions of the respective compounds and X-ray diffrac-
commonly studied 1,6 (3) isomers were successfully iso- tion data collected allowing determination of the con-
lated by column chromatography. Preparation of the formational arrangement of the molecules in the solid-
dibromo-substituted PBI, N,N0 -bis-(n-alkyl)-dibromo- state (see Figure 1 for views of compounds 2 and 3 and
3,4:9,10-perylenetetracarboxylic bisimide, yields a mix- Table 1 for selected bond lengths and angles). The single
ture of both 1,7- and 1,6- isomers in an estimated 80:20 crystal structures of 2 and 3 represent the first examples of
a structurally characterized pair of 1,6- and 1,7-isomers
(21) Qiu, W.; Chen, S.; Sun, X.; Liu, Y.; Zhu, D. Org. Lett. 2006, 8, 5. of perylene-bisimides. Both 2 and 3 adopt Fe-C bond
Article Inorganic Chemistry, Vol. 48, No. 21, 2009 10269
Table 1. Selected Bond Lengths (Å), Angles, and Torsion Angles (deg) for 2, 3, and 4

2
Fe1-C31A 2.045(6) Fe2-C41A 2.033(5)
Fe1-C32A 2.045(5) Fe2-C42A 2.047(5)
Fe1-C33A 2.042(6) Fe2-C43A 2.049(5)
Fe1-C34A 2.039(5) Fe2-C44A 2.034(6)
Fe1-C35A 2.042(6) Fe2-C45A 2.024(5)
Fe1-C36A 2.053(6) Fe2-C46A 2.037(6)
Fe1-C37A 2.056(6) Fe2-C47A 2.056(7)
Fe1-C38A 2.049(6) Fe2-C48A 2.058(7)
Fe1-C39A 2.043(5) Fe2-C49A 2.040(6)
Fe1-C40A 2.044(6) Fe2-C50A 2.028(5)
Fe-C(31A-35A) ave. 2.043 Fe-C(41A-45A) ave. 2.037
Fe-C(36A-40A) ave. 2.049 Fe-C(46A-50A) ave. 2.044
C13A-C14A 1.477(8) C17A-C18A 1.482(9)

C12A-C13A-C14A-C1A -15.8(11) C14A-C1A-C31A-C35A 135.5(7)

C6A-C17A-C18A-C7A -18.5(10) C18A-C7A-C41A-C45A 132.8(6)

Fe3-C31B 2.058(6) Fe4-C41B 2.048(7)

Fe3-C32B 2.071(6) Fe4-C42B 2.022(5)
Fe3-C33B 2.058(6) Fe4-C43B 2.010(6)
Fe3-C34B 2.038(6) Fe4-C44B 2.029(6)
Fe3-C35B 2.039(6) Fe4-C45B 2.054(6)
Fe3-C36B 2.056(7) Fe4-C46B 2.037(6)
Fe3-C37B 2.064(8) Fe4-C47B 2.036(6)
Fe3-C38B 2.076(8) Fe4-C48B 2.045(7)
Fe3-C39B 2.075(6) Fe4-C49B 2.050(7)
Fe3-C40B 2.062(8) Fe4-C50B 2.044(5)
Fe-C(31B-35B) ave. 2.053 Fe-C(41B-45B) ave. 2.032
Fe-C(36B-40B) ave. 2.066 Fe-C(46B-50B) ave. 2.042
C13B-C14B 1.501(11) C17B-C18B 1.512(12)

C12B-C13B-C14B-C1B -17.9(13) C14B-C1B-C31B-C35B 143.9(8)

C6B-C17B-C18B-C7B -17.3(13) C18B-C7B-C41B-C45B 132.9(8)
3
Fe1-C31 2.036(6) Fe2-C41 2.063(6)
Fe1-C32 2.051(6) Fe2-C42 2.052(7)
Fe1-C33 2.047(6) Fe2-C43 2.048(7)
Fe1-C34 2.051(7) Fe2-C44 2.028(7)
Fe1-C35 2.024(6) Fe2-C45 2.029(7)
Fe1-C36 2.038(7) Fe2-C46 2.063(8)
Fe1-C37 2.046(8) Fe2-C47 2.027(8)
Fe1-C38 2.055(8) Fe2-C48 2.041(8)
Fe1-C39 2.040(8) Fe2-C49 2.030(8)
Fe1-C40 2.040(7) Fe2-C50 2.047(8)
Fe-C(31-35) ave. 2.042 Fe-C(41-45) ave. 2.044
Fe-C(36-40) ave. 2.044 Fe-C(46-50) ave. 2.042
C13-C14 1.466(8) C17-C18 1.461(9)

C12-C13-C14-C1 -19.6(10) C14-C1-C31-C35 -46.9(9)

C6-C17-C18-C7 -23.4(9) C17-C6-C41-C45 -42.6(10)
4
Co1-S32 2.1167(8) Co2-S42 2.1096(7)
Co1-S34 2.1132(8) Co2-S44 2.1116(11)
Co1-C35 2.052(4) Co2-C45 2.047(3)
Co1-C36 2.046(4) Co2-C46 2.048(3)
Co1-C37 2.045(3) Co2-C47 2.047(4)
Co1-C38 2.055(3) Co2-C48 2.024(4)
Co1-C39 2.049(3) Co2-C49 2.026(3)
S42-C41 1.722(3) S32-C31 1.719(2)
S44-C43 1.706(3) S34-C33 1.706(3)
C41-C43 1.363(4) C31-C33 1.369(4)
C13-C14 1.466(3) C17-C18 1.471(3)
Co1-Cpa 1.660 Co2-Cpa 1.651
S32-Co1-S34 91.67(3) S42-Co2-S44 91.62(3)

C12-C13-C14-C1 -21.7(4) C14-C1-C31-C33 -47.9(4)

C6-C17-C18-C7 -15.3(4) C18-C7-C41-C43 128.7(3)
a
Distance between the cobalt cation and the centroid of the Cp ring.

lengths anticipated for the ferrocenyl units with staggered species, confirming the oxidation state of the ferrocenyl
cyclopentadienyl rings, as opposed to ferrocenium substituents.
10270 Inorganic Chemistry, Vol. 48, No. 21, 2009 Goretzki et al.
As anticipated for disubstituted perylenetetracar-
boxylic bisimides, in each case the molecule adopts a
twisted arrangement of the perylene core (Figure 1)
induced by steric interactions between the substituents
and the hydrogen atom located on the adjacent bay region
position of the perylene ring. Thus, the perylene core can
be considered as two naphthyl moieties linked at the 13/14
and 17/18 positions. Interplanar angles of 22.76/23.63°
(2) or 21.41° (3) are observed between these two naphthyl
subunits. The twisting of the two naphthyl subunits is
accompanied by the internaphthyl C-C bond lengths
being relatively long, 1.477(8)-1.512(12) Å (2) or
1.466(8)/1.461(9) Å (3), in comparison to average CdC
double bond lengths (c.f. 1.41 Å for the average bond
length within each naphthyl unit). The ferrocene moieties
are positioned on opposing sides of the perylene-bisimide
plane such that the cyclopentadienyl group adopts a
twisted arrangement, with an interplanar angle of 41.4°
(or 47.3°), with respect to the naphthyl group to which
each is attached. Figure 2. Views of the single crystal structures of compound 4 illustrat-
The discontinuity in aromaticity across the perylene ing the twisted arrangement of the perylene core. The relative orientations
of the Co-dithiolene moieties in the solid state are also illustrated.
core in these disubstituted species may be anticipated to Displacement ellipsoids are drawn at the 50% probability level.
reduce electronic communication across the central “aro-
matic” scaffold. However, there are noticeable differ- Compound 2 adopts π-π interactions between adja-
ences between some of the molecules. In particular, cent molecules to form pairs of stacked molecules with the
compound 3 represents the first structurally characterized Fc groups oriented such that they protrude from the
example of a 1,6-disubstituted perylenetetracarboxylic opposing faces of the stacked pairs (Figure 3a)
bisimide and has both substituents attached to the same (centroid 3 3 3 centroid separations between nearest-neigh-
naphthyl moiety, thereby reducing the implications of the bor naphthyl aromatic rings 3.70, 3.64, 3.64, 3.73 Å). In
perylene twist such that a clear aromatic pathway bet- contrast to 2, compound 3 adopts an extended stack via
ween the two Fc subunits is maintained in the molecule. the formation of π-π interactions (Figure 3b). Because of
Compound 4 crystallizes as a toluene solvate in the the relative arrangement of the Fc groups in 3, being the
triclinic space group P1. As with 2 and 3, the perylene disubstituted 1,6-isomer, the molecule is non-centrosym-
core is twisted with an interplanar angle of 21.23° metric with one-half of the molecule Fc substituted and
between these two naphthyl subunits and is accom- the other half unsubstituted. The molecules stack such
panied by the observation of relatively long C-C that the unsubstituted ends of the molecule are π-π
bonds between the two naphthyl groups 1.466(3)/ stacked with the unsubstituted end of an adjacent mole-
1.471(3) Å (see Figure 2 for a view of compound 4 and cule interacting via naphthyl moieties forming pairs
Table 1 for selected bond lengths and angles). The of molecules (centroid 3 3 3 centroid separations between
(Cp)Co-dithiolene moieties are positioned on adjacent nearest-neighbor aromatic rings 3.71 Å). These pairs of
sides of the perylene-bisimide plane such that the dithio- molecules also interact through the Fc-substituted ends of
lene group (CoS2C2) adopts a twisted arrangement with each molecule such that the imide moieties of each
an interplanar angle of 47.8° (or 54.7°) with respect to the molecule are stacked with the adjacent imide group
naphthyl group to which each unit is attached. Inspection (centroid 3 3 3 centroid separation 3.55 Å). Thus, through
of the bond lengths and angles of the Co-dithiolene a combination of two different interactions extended
moiety (Table 1) indicates that the formal cobalt(II) stacks are observed in the solid-state structure of 3.
center and dithiolene ligand adopt a geometry similar to In a similar manner to 2, compound 4 also exhibits
that reported for the analogous phenyl substituted dithio- pairs of stacked molecules but with π-π interactions
lene, [CpCo(S2C2(H)Ph)],22 indicating an ene-dithiolate between adjacent imide rings (centroid 3 3 3 centroid se-
arrangement of the dithiolene moiety. paration 3.62 Å). Within each molecule one imide ring
The solid-state structures of perylenetetracarboxylic participates in π-π interactions with another molecule
bisimides have a significant effect on the properties of of 4 while the other imide ring in the molecule forms a
the compounds, leading to conductivity in particular.23 π-π interaction with a guest toluene solvent molecule
Compounds 2-4 all adopt restricted stacked arrange- (centroid 3 3 3 centroid separation 3.57 Å), thereby pre-
ments because of the disubstituted nature of each com- cluding extension of the π-π stack beyond a dimeric unit.
pound, such that the extended stacks observed for Electrochemical Studies. Cyclic voltammetry was used to
unsubstituted perylenetetracarboxylic bisimides10b are assess the redox behavior of compounds 1a-5 and to estab-
not observed. lish the influence of the redox active, ferrocenyl or cobalt-
dithiolene appendages attached to the perylene-bisimide
(22) Periyasamy, G.; Burton, N. A.; Hillier, I. H.; Vinccent, M. A.; Disley, cores. As a result of enhanced solubility the dioctyl
H.; McMaster, J.; Garner, C. D. Faraday Discuss. 2007, 135, 469–488.
(23) Chen, Z.; Stepanenko, V.; Dehm, V.; Prins, P.; Siebbeles, L. D. A.;
derivatized version of 1, N,N0 -di-(n-octyl)-1,7-diethynyl-
:: ferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide
Seibt, J.; Marquetand, P.; Engel, V.; Wurthner, F. Chem.;Eur. J. 2007, 13,
436. 1a, was used for electrochemical, spectroelectrochemical
Article Inorganic Chemistry, Vol. 48, No. 21, 2009 10271

Figure 3. View of the stacking between adjacent molecules observed in the structures of (a) 2, (b) 3, and (c) 4. Note the formation of dimeric pairs in each
case but in the case of 3, 1,6-(Fc)2-PBI, dimeric pairs are in turn stacked to form extended one-dimensional arrays.

and EPR studies. The replacement of n-butyl by n-octyl at the

imide nitrogen is not anticipated to make any difference to the
electrochemical properties of the compound because of the
node in the HOMO at the nitrogen atoms of the two imide
functions.12
Cyclic voltammograms recorded for compounds 1a
and 5 (Figure 4), 2, 3, and 4 (Figure 5) and Table 2 for
pertinent electrochemical data. The reduction processes
of all four compounds follow the same trends reported for
other perylene-bisimide compounds.9 Hence, all the com-
pounds undergo two reversible one-electron reduction
processes based on the perylene core (Figures 4, 5).
Trends in reduction potentials correspond to the electron
withdrawing or donating nature of the group attached to
the perylene-bis-(dicarboximide) framework and, as
demonstrated by 2 and 3, the position of bay-substitution
on the perylene core has only a small effect on these
Figure 4. Cyclic voltammograms recorded for 1a (top) and 5 (bottom)
potentials. For 2 and 3, the ferrocenyl group (σp: -0.15)24 in CH2Cl2 containing [Bu4N][BF4] (0.4 M) at 0.1 V s-1.
donates electron density relative to the acetylene linker
in 1 and 1,7-(CtCPh)2-PBI, prepared as a model complex In the case of the ferrocenyl substituted compounds
(for CCPh σp: þ0.14): as a result, reduction processes 1a-3 the oxidation processes associated with the ferro-
occur at slightly more negative potentials. Given the cenyl groups is of particular interest. The oxidation of 1a
similarity between potentials of the first and second (Figure 4) was determined by coulometry to be a two-
reductions of 1,7-(CtCPh)2-PBI and compound 4, it electron process, and given the nature of the molecule and
would appear that the CpCo(dithiolene) moiety acts as potential of oxidation (perylenes usually oxidize at sig-
an electron withdrawing moiety. nificantly greater potentials,25 unless substituted by

::
(25) Lee, S. K.; Zu, Y.; Herrmann, A.; Geerts, Y.; Mullen, K.; Bard, A. J.
(24) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165–195. J. Am. Chem. Soc. 1999, 121, 3513–3520.
10272 Inorganic Chemistry, Vol. 48, No. 21, 2009 Goretzki et al.
precipitated salt being stripped off the electrode surface.
Evidence for this came from coulometry, where it was
observed that as the oxidation progressed, a dark solid
coated the electrode. Spectroelectrochemistry showed
this process to be chemically reversible; oxidation resulted
in a significant drop in intensity across the spectral range,
corresponding to the oxidation and subsequent loss of
chromophore from solution, while reduction regenerated
the original spectral profile of [1a]0 almost exactly.
Of interest was the difference between the physical
properties, upon oxidation, of 1a (Figure 4) and the
compounds 2 and 3 (Figure 5). While oxidation of 1a
yielded an insoluble product, which reflected in the wave-
form obtained for the cyclic voltammogram (Figure 4 and
Supporting Information), both 2 and 3 appeared to
give soluble products upon oxidation; hence the cyclic
voltammogram comprised a single wave both in the
Figure 5. Cyclic voltammograms recorded for 4 (top), 2 (middle), and 3
(bottom) in CH2Cl2 containing [Bu4N][BF4] (0.4 M) at 0.1 V s-1. forward and reverse cycle of the ferrocenylium/ferrocenyl
couple.
The oxidation of both 2 and 3 was determined, by
Table 2. Electrochemical Data for Disubstituted PBI Derivativesa coulometry and UV/vis spectroelectrochemistry at 243 K,
to be a two-electron, chemically reversible process as-
compound 1st reduction 2nd reduction oxidation ΔE(Fcþ/Fc)
signed as the oxidation of the ferrocenyl groups. The
1a -0.94 (0.07) -1.13 (0.07) (0.07) small positive shift in oxidation potential for both 2 and 3
2 -1.11 (0.07) -1.29 (0.07) þ0.15 (0.07) (0.07)b with respect to unsubstituted ferrocene is consistent with
3 -1.12 (0.07) -1.31 (0.06) þ0.17 (0.09) (0.08)b substitution of one ferrocenyl cyclopentadienyl ring by
4 -0.96 (0.07) -1.12 (0.08)c d (0.07) an electron withdrawing moiety. Only a small variation
5 -0.96 (0.10) -1.13 (0.09) (0.09)
between the potential of oxidation for 2 and 3 was
a
All potentials reported as E1/2 (= (Epa þ Epc)/2) in V vs Fcþ/Fc at observed, with 2 slightly easier to oxidize.
0.1 Vs-1 scan rate and quoted to the nearest 0.01 V. Values in More interestingly the behavior of the oxidation couple
parentheses are ΔE (= Epa - Epc) for the couple at 0.01 Vs-1. b [Fe
(C5Me5)2] (Fc*) used as internal standard: E1/2 Fc*þ/Fc* vs E1/2 Fcþ/Fc
for 2 and 3 with variation in scan rate revealed a small
was -0.52 V by independent calibration under identical conditions. c In degree of communication between the two ferrocenyl
addition two further reduction couples were observed but were too substituents (Figure 5). For 3, the waveshape appeared
closely overlapped to be resolved by cyclic voltammetry; however, these broad with ΔE (= Epa - Epc) values considerably higher
were resolved by square wave voltammetry as peaks at -1.34 and than those of Fc*, bis-(pentamethylcyclopentadie-
-1.44 V (the 1st and 2nd reductions were -0.94 and -1.10 V, respec-
tively by square wave voltammetry). d Oxidation process at Epa 0.65 V nyl)iron(II), used as the internal standard. We interpret
with corresponding reduction at 0.27 V. this broad shape as resulting from the close overlap of two
oxidation processes, one on each ferrocenyl, occurring at
N-donor groups),26,10b this was assigned to the simulta- slightly different potentials: this is a consequence of
neous oxidation of the two ferrocene groups.10a,11 Addi- communication through the naphthalene linker between
tionally, under the conditions of study 1,7-(CtCPh)2- the ferrocene centers, although the absence of two re-
PBI 5 (Figure 4) does not exhibit an oxidation process. solved waves would suggest the extent of this commu-
The unusual form of the cyclic voltammogram was nication to be small. This contrasts with the oxidation
ascribed to oxidation followed by deposition of the behavior of 2 which, at a scan rate of 0.1 V s-1, gave
generated ferrocenium salt on the surface of the working separation between the forward and reverse waves of the
electrode. In the first half-cycle, a single anodic waveform oxidation cycle consistent with that of the internal stan-
was observed for which Ipa was proportional to (scan dard. However, as the scan rate was lowered, ΔE dropped
rate)1/2 (R2 = 0.987). In the second half-cycle, corre- below that of Fc* under identical conditions, such that, at
sponding to the reduction of the electro-generated salt, 0.01 V s-1, the separation was 55 mV, below the value
two waves are observed, the intensities of which are scan expected for a one-electron reversible couple (ca. 70-
rate, and hence time scale, dependent. At faster scan rates, 80 mV as observed for the internal standard) and less than
corresponding to shorter time scales, a process at more that expected for two one-electron reversible couples that
positive potential dominated; this was assigned to the show no communication. This small value of ΔE may
reduction of the ferrocenium salt in solution. result from a genuine two-electron reversible process,
At slower scan rates, a reduction at slightly lower with ΔE larger than the theoretical value of 30 mV. The
potential was more intense and showed significant cur- tentative assignment of this process as two sequential one-
rent variation with scan rate. This was attributed to the electron oxidation processes, that is, an EE process, with
these characteristics would mean that the oxidation,
(26) (a) Lukas, A. S.; Zhao, Y.; Miller, S. E.; Wasielewski, M. R. J. Phys. which occurs on two different groups (but with equivalent
Chem. B 2002, 106, 1299–1306. (b) Zhao, Y.; Wasielewski, M. R. Tetrahedron orbitals) in the molecule results in these groups interact-
Lett. 1999, 40, 7047–7050. (c) Ahrens, M. J.; Tauber, M. J.; Wasielewski, M. R.
J. Org. Chem. 2006, 71, 2107–2114. (d) Tauber, M. J.; Kelley, R. F.; Giaimo,
ing attractively (i.e., ΔEo (= Eox1 - Eox2) > 35.6 mV)
J. M.; Rybtchinski, B.; Wasielewski, M. R. J. Am. Chem. Soc. 2006, 128, 1782– which would require a large structural rearrangement, or
1783. a large solvation effect or ion pairing as a result of the first
Article Inorganic Chemistry, Vol. 48, No. 21, 2009 10273
Table 3. EPR Data for Disubstituted PBI Derivatives 1-5 in Reduced Statesa

compound giso aiso/10-4 cm-1 b

[1a]- 2.004 1.51 (a2H), 0.59 (a2H), 0.55 (a2H), 0.52 (a2N)c
[2]- 2.005 1.23 (a2H), 0.63 (a4H), 0.63 (a2N)d
[3]- 2.005 1.22 (a2H), 0.62 (a4H), 0.58 (a2N)e
[4]- 2.010 f
[4]4- 2.004 f
[5]- 2.003 f
a
In CH2Cl2 containing [nBu4N][BF4] (0.4 M) at 298 K unless stated
otherwise. b Simulation of experimental parameters. c Lorentzian line
shape and 0.35 G line width. d Gaussian line shape and 0.7 G line width.
e
Gaussian line shape and 0.57 G line width. f Unresolved.

electron transfer step.27 However, we do not discount the

existence of other mechanisms to explain the observed
behavior.
Compound 4 gave a redox process consistent in beha-
vior with the presence of a CpCo(dithiolene) manifold Figure 6. Experimental (bottom) and simulated (top) EPR spectra for
(oxidation at Epa 0.65 V and an associated reduction at electrochemically generated 3- in CH2Cl2 containing [Bu4N][BF4] (0.4 M)
at 291 K.
Epc 0.27 V, vs Fcþ/Fc at 0.1 V s-1);28 this was not further
studied. However, reduction processes observed for 4 are
of considerable interest with a total of four reduction
processes observed (Figure 5). The third and fourth
reductions are unique to 4 and are assigned as two one-
electron reductions on the CpCo(dithiolene) units, the
potentials of which are consistent with literature values.28
Potentials of the third and fourth reductions were re-
solved by square wave voltammetry and show a difference
of about 0.1 V, indicating communication between the
two redox centers. Significant communication between
these centers contrasts with the behavior of 2 and 3 upon
oxidation; hence, communication between the two Co
centers would appear to be facilitated by changes occur-
ring in the perylene framework upon double reduction.
EPR Studies. The electrochemical one-electron reduc-
tion of each compound produced paramagnetic species.
As fluid solutions at ambient temperature, EPR spectro-
scopy gave signals consistent with the generation of the Figure 7. Experimental EPR spectra for electrochemically generated
radical anions, see Table 3. Hyperfine splittings were 44- in CH2Cl2 containing [Bu4N][BF4] (0.4 M) at 77 K.
observed for 1a, 2, and 3 (see Figure 6 and Supporting
Information); each of which was simulated by the coup- nucleus (I = 7/2; see Figure 7), the spectral profile of
ling of the unpaired electron to the nucleus of six hydro- which was very similar to literature reports of other
gen atoms, presumably those of the perylene core, and [CpCo(dithiolene)] moieties.29 However, reproduction
two nitrogen atoms.20 For both 4 and 5, one electron of all the features in the experimental spectrum was not
reduction yielded spectra with no or only poorly defined achieved by simulation using rhombic parameters, a
hyperfine splitting. point noted previously for the EPR spectrum of [Cp-
Two electron reductions of 1a-4 yield the correspond- Co(pyridine-4-yl-ene-1,2-dithiolate)]- recorded at X- and
ing dianionic species, all of which are dark blue. These Q-band frequencies as a frozen glass in tetraethylene
solutions were essentially EPR silent, with only residual glycol at 77 K, and a consequence of the non-coincidence
signals present relative to their monoanion analogues of A and g tensors giving a monoclinic EPR symmetry.30
(3-18%). For 4, further reduction at potentials beyond Spectroelectrochemistry. In situ one- and two-electron
the fourth process regenerated an EPR active species: reductions of 1a-5 were followed by UV/vis/nIR spectro-
upon cooling to 77 K, this species gave a spectrum electrochemistry at an optically transparent electrode.
consistent with an unpaired electron coupled to a Co The one-electron reduced radical anions show major
bands which are red-shifted relative to their parent mo-
(27) Bard, A. J.; Faulkner, L. R. Electrochemical Methods, Fundamentals
lecules, with series of transitions extending into the nIR
and Applications, 2nd ed.; Wiley: New York; pp 505-507. region. The second reduction blue-shifts the spectra with
(28) (a) Ushijima, H.; Kajitani, M.; Smimizu, K.; Sat^o, G. P.; Akiyama, respect to those of the radical anion, with the most intense
T.; Sugimori, A. J. Electroanal. Chem. 1991, 303, 199–209. (b) Kajitani, M.; transitions for 1a (634 nm), 2 (630 nm), 3 (628 nm), and 5
Akiyama, T.; Sugimori, A.; Hirakata, K.; Hoshina, Y.; Satsu, Y.; Sato, G. P.;
Shimizu, K. J. Electroanal. Chem. 1988, 251, 421–428.
(639 nm) all occurring at similar wavelengths, a result
(29) (a) Takayama, C.; Kijitani, M.; Sugiyama, T.; Akiyama, T.; Shimizu,
K.; Sugimori, A. Organometallics 1997, 16, 3498–3503. (b) Hartigan, H. J.;
Seeber, G.; Mount, A. R.; Yellowlees, L. J.; Robertson, N. New J. Chem. 2004, (30) Mabbs, F. E.; Collison, D. Electron Paramagnetic Resonance of d
28, 98–103. Transition Metal Compounds; Elsevier: Amsterdam, 1992; Chapter 7.
10274 Inorganic Chemistry, Vol. 48, No. 21, 2009 Goretzki et al.
reduced 4 has a less broad appearance to the visible
spectral profile and as such is more similar to those of
the dianionic species of 1a, 2, and 3.

Conclusions
A series of difunctionalized perylene-bisimides has been
synthesized, structurally characterized by single crystal X-ray
diffraction methods, and their optical and redox properties
investigated. Compounds 1-4 represent multistate redox-
active architectures with two redox-active ferrocene or co-
balt-dithiolene moieties introduced into the “bay” region of
the perylene-bisimide core. Structural characterization of
2-4 confirms the anticipated twisted nature of the central
perylene core. Compounds 2 and 3 represent the first pair of
disubstituted perylene-bisimide 1,7- and 1,6-isomers with
similar degrees of twisting of the perylene core in both cases,
Figure 8. UV-visible spectra recorded in CH2Cl2 containing 23.2° (ave. for 2) vs 21.41° (3). Structural characterization of
[Bu4N][BF4] (0.4 M) using spectroelectrochemical methods for 1a at 4 also reveals the expected twisting of the perylene core and
273 K. The spectrum of 1a is represented by the solid line, 1a- (dashed confirms the ene-dithiolate geometry of the cobalt dithiolene
line), 1a2- (short dashed line), and the oxidized species 1a2þ (dashed- moiety.
dotted line).
Cyclic voltammetry measurements, coupled with spectro-
electrochemical and EPR studies, of 1a-4, where 1a is
N,N0 -di-(n-octyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10-
tetracarboxylic acid bisimide, reveal the two anticipated
perylene-bisimide based reductions. The ferrocene substi-
tuted compounds 1a-3 also display a single reversible two-
electron oxidation, with only a small degree of communica-
tion between the ferrocene groups observed in the 1,6-isomer
where the two ferrocene groups are attached to the
same naphthyl moiety. In the case of 4 two reversible
reductions associated with the cobalt-dithiolene moieties
are observed, confirming communication across the reduced
perylene core.
These studies reveal that in designing multistate redox-
active architectures using perylene-bisimides the isomeric
arrangement of the redox-active appendages has to be
considered with 1,6-isomers exhibiting a greater tendency
toward communication across the perylene core, facilitated
by a single naphthyl group. However, the introduction of
Figure 9. UV-visible spectra recorded in CH2Cl2 containing [Bu4N]- groups capable of further reductive processes, such as the
[BF4] (0.4 M) using spectroelectrochemical methods for 4 at 273 K. The cobalt-dithiolene moieties, also facilitates communication
spectrum of 4 is represented by the solid line, 4- (dashed line), 42- (short across the perylene subunit, presumably as a result of the
dashed line), and 44- (dashed-dotted line).
reduced nature of the perylene core at the potentials required
for cobalt-dithiolene reduction. In summary, we have suc-
consistent with other bisimide perylene compounds. Re- cessfully prepared multistate redox-active architectures based
presentative UV spectra for the reduced and oxidized upon “bay”-functionalized perylene-bisimides.
states for compound 1a are shown in Figure 8, while
spectra for 2, 3, and 5 and representative spectra revealing Acknowledgment. We would like to gratefully acknowl-
sharp isosbestic points for the oxidative and reductive edge the support of the Engineering and Physical Sciences
transitions of compound 3 are given in the Supporting Research Council (EP/D048761/1) and the EU through
Information, as is a full tabulated list of adsorption the NANOMESH STRP NMP4-CT-2004-013817 for
maxima for all oxidation states of 1a-5. funding. We thank the National Crystallography Service
For 4, the transitions in the visible region appear broad, at the University of Southampton, U.K., for data collec-
at least for the dianionic redox state (Figure 9). This may tion and STFC for access to SRS Station 9.8.
result from the overlap of two strongly absorbing chro-
mophores; those transitions associated with the neutral, Supporting Information Available: Supporting Information
anionic and dianionic bisimide perylene core combined includes additional figures and data for cyclic voltammograms,
with transitions of the [CpCo(dithiolene)] moiety, usually EPR spectra, spectroelectrochemistry and X-ray crystallo-
found at about 580 nm. Reduction of the [CpCo- graphic files (CIF) are available. This material is available free
(dithiolene)] unit depletes this transition; hence, fully of charge via the Internet at http://pubs.acs.org.