Synthesis and spectroscopic properties of porphyrin derivatives of C60

Article abstract of DOI:10.1080/15421401003726907

Chemical synthesis of two C60 fullerene derivatives: with porphyrin (C ₆₀-H₂P) and of the iodide salt of Zn porphyrin (C ₆₀-H₂P)⁺I- is described. Both compounds are soluble in several organic solvents, with a larger solubility observed for C60-H2P. Thin films obtained by solution drawing or by spinning techniques from C₆₀-H₂P solution in organic solvents or dissolved in a polymer matrix show a peculiar granular structure with regular submicron size particles. Their size of is a little smaller in polymer matrix. The solution UV-Vis absorption spectra exhibit typical bands which can be attributed to porphyrin and to the fullerene. A solvatochromic effect is observed in C ₆₀-H₂P which shows a nonzero first hyperpolarizability , most likely due to the charge transfer between fullerene and porphyrin. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15421401003726907

This article was downloaded by: [University of Connecticut]
On: 11 January 2015, At: 22:14
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Molecular Crystals and Liquid Crystals
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gmcl20
Synthesis and Spectroscopic Properties
of Porphyrin Derivatives of C60
M. Prato a , C. Soombar a , E. Vazquez a , J. Niziol b , E. Gondek c , I.
Rau d & F. Kajzar d e
a Dipartimento di Scienze Farmaceutiche , Trieste University , Italy
b AGH University of Science and Technology , Krakow, Poland
c Cracow University of Technology , Krakow, Poland
d Politehnica University of Bucharest , Bucharest, Romania
e UFR Sciences, POMA Laboratory , Angers University , Angers,
France
Published online: 28 May 2010.
To cite this article: M. Prato , C. Soombar , E. Vazquez , J. Niziol , E. Gondek , I. Rau & F. Kajzar
(2010) Synthesis and Spectroscopic Properties of Porphyrin Derivatives of C60, Molecular Crystals and
Liquid Crystals, 521:1, 253-264, DOI: 10.1080/15421401003726907
To link to this article: http://dx.doi.org/10.1080/15421401003726907
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Mol. Cryst. Liq. Cryst., Vol. 521: pp. 253–264, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421401003726907
Synthesis and Spectroscopic Properties
of Porphyrin Derivatives of C60
M. PRATO,1 C. SOOMBAR,1 E. VAZQUEZ,1
J. NIZIOL,2 E. GONDEK,3 I. RAU,4 AND F. KAJZAR4,5
1Dipartimento di Scienze Farmaceutiche, Trieste University, Italy
2AGH University of Science and Technology, Krakow, Poland
3Cracow University of Technology, Krakow, Poland
4Politehnica University of Bucharest, Bucharest, Romania
5UFR Sciences, POMA Laboratory, Angers University, Angers, France
Chemical synthesis of two C60 fullerene derivatives: with porphyrin (C60-H2P) and
of the iodide salt of Zn porphyrin (C60-ZnP)þIꢀ is described. Both compounds are
soluble in several organic solvents, with a larger solubility observed for C60-H2P.
Thin films obtained by solution drawing or by spinning techniques from C60-H2P
solution in organic solvents or dissolved in a polymer matrix show a peculiar
granular structure with regular submicron size particles. Their size of is a little smal-
ler in polymer matrix. The solution UV–Vis absorption spectra exhibit typical bands
which can be attributed to porphyrin and to the fullerene. A solvatochromic effect is
observed in C60-H2P which shows a nonzero first hyperpolarizability b, most likely
due to the charge transfer between fullerene and porphyrin.
Keywords Aggregation; fullerene C60; Guterman model; nanoparticles; porphyrine;
zinc porphyrin
Introduction
The discovery of a stable carbon aggregate composed of 60 carbon atoms [1],
forming a truncated icosahedral structure of a diameter of 1 nm (C60), resembling
a regular golf ball in shape and later another one made of 70 carbon atoms (C70),
gave rise to a very important research on synthesis of these materials [2,3] studies
of their properties and applications. These new classes of materials are commonly
called fullerenes, as their chemical structures, particularly that of C60, show some
resemblance with the geodesic dome designed by the American architect Richard
Buckminster Fuller for the world industrial exhibition in 1967 in Montreal, Canada.
Very rapidly it was shown that these materials exhibit exceptional physico-chemical
properties. For example C60 can be doped inside and outside the cage. Doping
outside the cage with alkali ions gives a superconducting material [4].
Address correspondence to F. Kajzar, UFR Sciences, POMA Laboratory, Angers
University, 2 bd Lavoisier, Angers 49045, France. Tel.: þ40213154193; Fax: þ40213154193;
E-mail: frkajzar@yahoo.com
253

254
M. Prato et al.
The p electron conjugation, leading to electron delocalization and as conse-
quence, enhanced second hyperpolarizability c attracted a lot of interest for
these new materials for application in photonics, and particularly in nonlinear optics
[5–9]. Another argument in favor of fullerenes is the absence of low energy CꢀH
and OꢀH vibrations, present in organic polymers, whose harmonics absorb in the
telecommunications window, the wavelength length range of targeted applications
of organic NLO materials. Indeed, as it was shown by Kafafi et al., the C60 material
is perfectly transparent in near IR.
C60 may act as an electron accepting or electron donating molecule. It is a very
useful property for practical applications. In particular it was used by Okada-Shudo
et al. [10] in fabrication of artificial intramolecular charge transfer structures for
second order NLO. This property of C60 is also used in photosensitizing organic
materials, particularly for obtaining photorefractive properties [11] and for medical
applications [12].
Another stable carbon aggregates were discovered later on, particularly the
nanotubes [13,14] which exhibit very interesting properties and actually find a lot
of practical applications [15]. Actually the whole family of these materials, including
nanotubes, are known under the name of fullerenes.
However one of the most important problem encountered with C60 was the poor
solubility of this molecule. Therefore a lot of chemical synthesis work was done in
=
functionalizing it, using the active C C bond. Also functionalizing fullerene with
another molecule may bring another, interesting properties to the new compounds.
In this paper we describe the chemical synthesis of the C60-porphyrin complexes
and their spectroscopic properties. Porphyrin is one of the most studied and interest-
ing molecule. The porphyrin ring is the basic part of chlorophyll with magnesium as
central atom, present in all vegetables and leafs and playing a fundamental role in
photosynthesis, i.e., transformation of CO2 and water into glucose and oxygen.
Similarly important role in living organisms play heme, in which the central atom
is iron. Heme molecule is an important constituent of hemoglobin. Because of a
strong absorption in the visible and the photosensitizing property porphyrin is also
considered as a good candidate for solar energy conversion [16–18]. We have chosen
two porphyrins, one with zinc as central atom and the second one with hydrogen
(cf. Schemes 1 and 2).
Chemical Synthesis
The chemical routes for obtaining both compounds are shown in Scheme 1 (C60-H2P)
and in Scheme 2 (C60-ZnP).
Synthetic Part
Aldehyde b and all other reagents and solvents were obtained from Fluka, Sigma-
Aldrich and J. T. Baker, and used without further purification. Mass spectra were
taken with the PESCIEX API 1 (MS-ES) spectrometers. Infrared spectra were
recorded on a Jasco FTIR-200 spectrometer using KBr powder (DRIFT system).
1H-NMR spectra were recorded on a Jeol (400 MHz) and on a Varian Gemini-200
(200 MHz) at room temperature in CDCl3. 13C-NMR spectra were recorded on a
Varian Gemini-200 (50 MHz) at room temperature in CDCl3. Chemical shifts are

Porphyrin Derivatives of C60
255
Scheme 1. Sequence of chemical reaction leading to synthesis of C60-H2P molecule.
given in parts per million (d) relative to TMS. UV=Vis absorption spectra were
recorded with a Perkin-Elmer Lambda 20 UV=Vis spectrophotometer.
The N-(3,6-dioxaoctan-1-ammonium trifluoroacetate)-fulleropyrrolidine 3 was
prepared according to reported procedures in the literature [19]. The porphyrin 1
was prepared using the Lindsey conditions reported in the literature [20,21], The
aldehyde a [22], the porphyrin c [23] and the salt 5 [24] were prepared according
to the literature.
Porphyrin (1). To a solution of pyrrole (0.56 mL, 0.008 mol) with the aldehyde a
(1.31 g, 0.006 mol) and the aldehyde b (0.33 g, 0.002 mol) in 800 mL of chloroform

256
M. Prato et al.
Scheme 2. Sequence of chemical reaction leading to synthesis of C60-ZnP molecule.
was added the BF3 ꢁ OEt2 acid catalyst (0.83 mL of a 3.2 M solution in chloroform).
The reaction mixture was stirred at room temperature under N2 for 1 h. Then (1.48 g,
0.006 mol) of the oxidant p-chloranil was added, and the mixture was stirred under
reflux for 1 h more. After cooling to room temperature the acidic solution was
neutralized by addition of triethylamine (0.37 mL) and the solvent was evaporated.
The product was purified by column chromatography (pure hexane following by
CH2Cl2=hexane 1:1) to afford the compound 1 as a violet solid.
1: C70H80N4O2 (MW 1009.4), yield: 21% (420 mg, 0.42 mmol). Analytical data
were identical with the reported data [25].

Porphyrin Derivatives of C60
257
Porphyrin (2). A solution of 1 (240 mg, 0.238 mmol) and of KOH (272 mg,
4.76 mmol) in THF=water (25=10 mL) was stirred under reflux for 5 days. The
violet organic phase was decanted from the colourless aqueous phase, and the
THF was evaporated. The residue was dissolved in dichloromethane and washed 2
times with a saturated solution of NH4Cl and with distilled water. The organic
phase was dried over Na2SO4 and the solvent was evaporated under vacuum. The
crude residue was purified by column chromatography (pure CH2Cl2 following by
EtOAc=MeOH 9:1) to afford the compound 2 as a violet solid.
2: C69H78N4O2 (MW 995.4), yield: 88% (210 mg, 0.211 mmol). Analytical data
were identical with the reported data [26].
C60-H2P (4). The fullerene derivative 3 (52 mg, 0.054 mmol) was dispersed in 6 mL of
dichloromethane with 17 mL (0.113 mmol) of triethylamine and the mixture was stirred
at room temperature for 30 minutes. The porphyrin derivative 2 (45 mg, 0.045 mmol)
was dissolved in 12 mL of dichloromethane with the 1-Hydroxybenzotriazole
hydrate HOBT (13 mg, 0.090 mmol) and the N0-(3-Dimethylaminopropyl)-N-
ethylcarbodiimid Hydrochloride EDC (18 mg, 0.090 mmol). The mixture was then
stirred at room temperature under N2 for 30 min. Then the solution of 3 with NEt3
was added to the solution of porphyrin 2 with HOBT=EDC and the reaction
mixture was stirred overnight at room temperature. The solvent was evaporated and
the crude residue was purified by column chromatography (Toluene=EtOAc 2:3).
The brown purple solid was dissolved in dichloromethane and precipitated by
addition of methanol to afford the desired compound 4.
4: C137H94N6O3 (MW 1872.3), yield: 89% (74 mg, 0.040 mmol). 1H-NMR
400 MHz (CDCl3): d 8.81 (t, J ¼ 5.2 Hz, 2H, Hb1), 8.77 (t, J ¼ 5.2 Hz, 6H, Hb2),
8.43 (d, J ¼ 8.2 Hz, 2H, Hm), 8.32 (d, J ¼ 8.2 Hz, 2H, Ho), 8.04 (d, J ¼ 1.7 Hz, 2H,
0
00
0
Ho ), 7.92 (d, J ¼ 1.7 Hz, 4H, Ho ), 7.80 (t, J ¼ 1.7 Hz, 1H, Hp ), 7.74 (t, J ¼ 1.7 Hz,
00
2H, Hp ), 7.38 (bs, 1H, NH-CO), 4.05 (t, J ¼ 6.6 Hz, 2H), 3.95 (s, 4H, Hpyrr), 3.88
(m, 8H), 3.29 (t, J ¼ 6.6 Hz, 2H), 1.56 (s, 18H, tBu0), 1.47 (s, 36H, tBu00), ꢀ3.00
(bs, 2H, NHporph). 13C-NMR 200 MHz (CDCl3): d 167.6; 153.1; 148.6; 146.3;
145.9; 144.9; 144.6; 144.1; 143.8; 143.4; 142.8; 141.2; 141.1; 140.5; 140.1; 139.9;
138.1; 134.8; 134.3; 134.0; 131.4; 129.6; 128.9; 128.2; 125.4; 121.9; 121.5; 120.9;
117.8; 70.5; 70.1; 69.7; 69.4; 68.4; 54.6; 39.8; 35.1; 31.9; 29.7. ES-MS (Tetrahydro-
furan): m=z ¼ 1873 [M þ Hþ]. FT-IR: cmꢀ1 3917, 2951, 2875, 2710, 2351, 1788,
1676, 1600, 1473, 1360, 1263, 1128, 985, 918, 812, 737, 542.
Amino Ester (6). The salt 5 (180 mg, 0.332 mmol) was dispersed in 6 mL of
dichloromethane with 115 mL (84 mg, 0.831 mmol.) of triethylamine and the
mixture was stirred at room temperature for 30 minutes. The porphyrin derivative
c (200 mg, 0.277 mmol) was dissolved in 12 mL of dichloromethane with the
1-Hydroxybenzotriazole hydrate HOBT (61 mg, 0.553 mmol) and the N0-(3-
Dimethylaminopropyl)-N-ethylcarbodiimid Hydrochloride EDC (106mg, 0.553
mmol). The mixture was then stirred at room temperature under N2 for 30 min.
Then the solution of 5 with NEt3 was added to the solution of porphyrin c with
HOBT=EDC and the reaction mixture was stirred overnight at room temperature.
The solvent was evaporated and the crude residue was purified by column
chromatography (CH2Cl2=EtOAc 1:9) to afford compound 6 as a violet solid.
1
6: C68H56N6O7Zn (MW 1134.60), yield: 40% (150 mg, 0.133 mmol). H-NMR
200 MHz (CDCl3): d 8.96–8.88 (m, 6H), 8.86–8.80 (m, 2H), 8.27–8.13 (m, 8H),

258
M. Prato et al.
7.95–7.82 (m, 2H), 7.81–7.66 (m, 9H), 7.32–7.01 (m, 10H), 6.93 (t, J ¼ 5.0 Hz, 1H),
5.01, 4.97 (s, 2H), 4.95, 4.87 (s, 2H), 4.08, 4.04 (s, 2H), 3.61–3.34 (m, 12H).
13C-NMR 50 MHz (CDCl3): d 169.68, 166.95, 155.93, 155.65, 150.28, 150.21,
150.17, 149.66, 146.32, 146.21, 142.93, 136.19, 136.02, 135.16, 134.51, 132.56,
132.22, 132.10, 131.59, 128.49, 128.30, 128.08, 127.88, 127.77, 127.62, 127.51,
126.59, 124.92, 121.36, 121.22, 119.52, 70.21, 70.06, 69.80, 67.48, 67.36, 66.82,
50.22, 50.25, 48.12, 47.83, 39.41. ES-MS (Methanol): m=z ¼ 1070 (M-Zn), 1074
(MHþ-Zn). FT-IR: cmꢀ1 3634, 3336, 3055, 2879, 1748, 1703, 1479, 1195, 998, 750,
707, 477.
Amino Acid (7). Equivalent amounts of boron tribromide (1.13 mL, 12 mmol) and
trifluoroacetic acid (0.92 mL, 12 mmol) were mixed at 0ꢂC in dichloromethane
(15 mL) whereupon a precipitate was formed. The mixture was evaporated to
dryness under reduced pressure. The residue was dissolved in trifluoroacetic acid
(5 mL) and this solution was added directly to a solution of the amino ester 6
(240 mg, 0.2 mmol) in trifluoroacetic acid (10 mL) and stirred for 1 hour at room
temperature. The solvent was evaporated and the boron compounds were
removed by repeated evaporation with MeOH, yielding a green solid after
precipitation with diethyl ether.
7: C53H44N6O5Zn (MW 910.34), yield: 99% (180 mg, 0.2 mmol). 1H-NMR
200 MHz (CD3OD): d 8.87–8.73 (m, 8H), 8.32 (d, J ¼ 8.2 Hz, 2H), 8.25–8.09 (m,
8H), 7.79–7.66 (m, 9H), 3.99–3.67 (m, 8H), 3.65–3.54 (m, 4H), 3.47 (t, J ¼ 5.2 Hz,
2H). 13C-NMR 50 MHz (CD3OD): d 168.52, 166.94, 149.53, 149.47, 149.39,
148.87, 146.53, 142.76, 133.76, 133.62, 132.44, 130,80, 130.60, 130.10, 127.62,
126.46, 125.50, 124.43, 120.22, 120.04, 118.30, 69.48, 69.42, 69.37, 69.30, 68.87,
67.90, 64.97, 64.91, 38.98, 38.53. ES-MS (Methanol): m=z ¼ 867 (MNaþ-Zn). FT-IR:
cmꢀ1 3555, 3062, 1677, 1549, 1485, 1430, 1196, 1136, 802, 713, 450. UV=Vis
(CH2Cl2): kmax ¼ 349, 418, 435, 514, 550, 593, 651.
C60-ZnP (8). A solution of amino acid 7 (51 mg, 0.056 mmol) in methanol (2 ml)
was added to a mixture of C60 (128 mg, 0.177 mmol) and paraformaldehyde
(118 mg, 3.9 mmol) in toluene (180 mL). The mixture was heated under reflux of
toluene for 1 hour and 45 minutes. After evaporation of solvent, the crude
material was purified by flash chromatography (toluene followed by toluene=
AcOEt 8:2). The brown solid was dissolved in dichloromethane and precipitated
by ethyl ether to afford compound 8.
1
8: C113H44N6O3Zn (MW 1598.99), yield: 33% (30 mg, 0.019 mmol). H-NMR
200 MHz (CDCl3): d 8.90–8.69 (m, 8H), 8.31–7.97 (m, 10H), 7.81–7.63 (m, 9H),
7.21 (bs, 1H), 4.44 (s, 4H), 4.06–3.47 (m, 10H), 3.37–3.18 (m, 2H). ES-MS (Tetra-
hydrofurane=Methanol): m=z ¼ 1537 (masse without Zn) 1600 (MHþ). FT-IR:
cmꢀ1 3301, 3052, 2923, 2792, 1659, 1485, 1342, 1114, 999, 757, 443. UV=Vis
(CH2Cl2): kmax ¼ 512, 550, 590, 663.
(C60-ZnP)þIꢀ (9). A mixture of fulleropirrolidine 8 (30 mg, 0,019 mmol) and
methyl iodide (4 mL, 64.25 mmol) was stirred at 80ꢂC for 24 hours. After this time
the methyl iodide in excess was remove by evaporation, the solid residue was
washed with toluene, dissolved in dichloromethane and precipitated by ethyl ether
to obtain compound 9.
9: C114H47IN6O3Zn (MW 1740.93), yield: 99% (33 mg, 0.019 mmol). ES-MS
(Tetrahydrofurane=Methanol): m=z ¼ 1611 (Mþ). Both compounds are partly

Porphyrin Derivatives of C60
259
soluble in common organic solvents. C60-H2P is soluble in dioxane at least 22 mg=ml
(not more than 77.2 mg=ml), 1,1,2-trichloroethane, 1,2-dichloroethane, acetone,
chloroform, DMF, DMSO. The iodide salt (C60-ZnP)þIꢀ issoluble in toluene
(at least 21 mg=ml), and slightly in DMF and in dioxane. Insoluble in DMSO,
and in acetonitrile.
Thin Film Formation
Because of poor solubility of the iodide salt, thin film formation ability was tested
only for C60-H2P either in its pristine form or in blend with a polymer (PMMA).
Two techniques were used:
– solution casting
– solution drawing
In all cases thin films of a granular form were obtained, as shown in Figures 1–2.
The size of particles is typically of few hundreds of nanometers. It doesn’t depend
on the solvent used nor on the deposition conditions. A slightly smaller particles
are obtained from C60-H2P dissolved in polymer (PMMA) (cf. Fig. 2). Apparently
this ability to form well defined, regular nanoparticles is a property of this molecule
and a finger print of a strong cohesion within this material, thus a strong interaction
between the molecules. We note here that aggregation of porphyrin molecules was
already reported either at higher solution concentrations [27] or by modifying
environment (pH, polarity, etc.) [28–30]. Similar property can be expected for the
second synthesized molecule, not tested in this study because of the already
mentioned limited solubility.
UV-Vis Spectroscopy
Figure 3 shows absorption spectra of C60-H2P in different solvents. Well defined
contribution of C60 absorption bands at 350 nm are seen as well as the porphyrin
Soret (around 427 nm, except in 1,1,2-trichloroethane where it is red shifted to by
about 30 nm) and four, weaker, Q bands in the wavelength range 500–700 nm [31].
Figure 1. Optical microscope picture of thin film obtained by spin coating of C60-H2P
compound from 1,1,2-trichloroethane solution.

260
M. Prato et al.
Figure 2. Optical microscope picture of thin film obtained by spin coating of C60-H2P
solution in PMMA. Here dioxane was used as solvent.
Although these bands seem to disappear completely in spectrum measured in of
1,1,2-trichloroethane, they are only strongly quenched in this solvent. This con-
clusion arises from Figure 4. The observed absorption spectra are in good agreement
with the Gouterman four orbital model [32] (two HOMO and two LUMO), accord-
ing to which the strong Soret band is due to the singlet – singlet transition between
Figure 3. Optical absorption spectra of C60-H2P measured in solvents of increasing dipole
moments (polarity), dioxane 0.4D (debye), chloroform 1.4D, 1,1,2-trichloroethane 1.7D,
1,2-dichloroethane 1.75D, acetone 2.7D, dimethylformamide (DMF) 3.8, dimethylsulfoxide
(DMSO) 3.9D.

Porphyrin Derivatives of C60
261
Figure 4. Absorption spectra in UV-vis wavelength range measured for C60-H2P compound
in 1,1,2-trichloroethane measured in more concentrated solution then the spectrum shown
in Figure 3.
the lowest (S0) and the highest (S2) states, whereas the weaker Q band arises from
S0 to S1 transition. The observed several absorption bands in Q band are due the
vibronic contributions. In the range 500–650 nm fullerene contributes to the absorp-
tion spectrum of the compound too. Central atom and the side groups influence the
postion of both Soret and Q bands.
Figure 5. Optical absorption spectra of [C60-ZnP]þIꢀ in two solvents: DMF and Dioxan.

262
M. Prato et al.
Figure 6. Comparison of optical absorption spectra of C60-H2P and [C60-ZnP]þI) in dioxane.
As already mentioned, we observe an important red shift of the porphyrin
absorption spectrum between dioxane and 1,1,2-trichloroethane solution. Such a
solvatochromic property is a finger print of nonzero first hyperpolarizability b which
is proportional to the difference of dipolar moments at fundamental and first
allowed excited state [33] and is used to determine this NLO hyperpolarizability
[34]. As both molecules C60 and H2P are centrosymmetric one can reasonably
assume that a charge transfer occurs between them.
Figure 4 shows optical absorption spectra of [C60-ZnP]þIꢀ in two solvents:
DMF and dioxane. The absorption spectrum is very similar to that of C60-H2P
with, similarly, contributions coming from C60 and ZnP. Also the harmonic replicas
are present in the 500–700 nm wavelength range. Because of poor solubility of this
molecule no absorption spectra for solution in 1,1,2-trichloroethane are available.
Also no solvatochromic effect is observed in other solutions using the same solvents
as in the case of C60-H2P. A slight, red shift is visible between absorption spectrum of
[C60-H2P]þ Iꢀ and that of C60-H2P, as displayed in Figure 6.
Conclusions
We have synthesized two new C60 fullerene derivatives: with porphyrin (C60-H2P)
and an iodide salt of Zn porphyrin (C60-ZnP)þIꢀ. First molecule shows better
solubility than the second. Absorption spectra exhibit a strong Soret band and four
Q bands, in agreement with the Gouterman four orbital model. A solvatochromic
effect in C60-H2P is observed, with a red shift of about 30 nm of Soret band between
1,1,2-trichloroethane and several other solvens (dioxane, acetone, chloroform,
DMF, DMSO . . .). This indicates that the molecule exhibit second order NLO
properties. Solution cast thin films of C60-H2P are composed from regular submi-
cron size particles. The size of the particles depends on the environment. When
C60-H2P is dissolved in PMMA their size is reduced.

Porphyrin Derivatives of C60
263
References
[1] Kroto, H. W., Heath, J. R., O’Brien, S. C., Curl, R. F., & Smalley, R. E. (1985). Nature,
318, 162.
[2] Kratschmer, W., Lamb, L. D., Fostiropoulos, K., & Huffman, D. R. (1990). Nature, 347,
354.
[3] Kratschmer, W., Fostiropoulos, K., & Huffman, D. R. (1990). Chem. Phys. Lett.,
170, 167.
[4] Buntar, V. & Weber, H. W. (1996). Supercond. Sci. & Technol., 9(8), 599–615.
[5] Blau, W. J., Byrne, H. J., Cardin, D. J., Dennis, T. J., Hare, J. P., Kroto, H. W., Taylor,
R., & Walton, D. R. M. (1991). Phys. Rev. Lett., 67, 1423.
[6] Kafafi, H., Lindle, J. R., Pong, R. G. S., Bartoli, F. J., Lingg, L. J., & Milliken, J. (1992).
Chem. Phys. Lett., 188, 492.
[7] Kajzar, F., Taliani, C., Danieli, R., Rossini, S., & Zamboni, R. (1994). Chem. Phys. Lett.,
217, 418.
[8] Kajzar, F., Taliani, C., Danieli, R., Rossini, S., & Zamboni, R. (1994). Phys. Rev. Lett.,
217, 418.
[9] Koudoumas, E., Konstantaki, A., Mavromanolakis, S., Couris, S., Fanti, M.,
Zerbetto, F., Kordatos, K., & Prato, M. (2003). Chemistry – A European Journal,
9(7), 1529–1534.
[10] Kajzar, F., Okada-Shudo, Y., Meritt, C., & Kafafi, Z. (2001). Synth. Metals, 117,
189–193.
[11] Kippelen, B. & Peyghambarian, N. (1994). Nature, 371, 497.
[12] Bosi, S., Da Ros, T., Spalluto, G., & Prato, M. (2003). European Journal of Medicinal
Chemistry, 38(11–12), 913–923.
[13] Ijima, S. (1991). Nature, 354, 56.
[14] Ijima, S. & Ichihashi, T. (1993). Nature, 363, 603.
´
[15] (2002). In: Science and Application of Nanotubes, Tomanek, D. & Enbody, R. J. (Eds.),
Kluwer: Paris.
[16] Sacriciftci, N. S., Smilowitz, L., Heeger, A. J., & Wudl, F. (1992). Science, 258, 1474.
[17] Tachibana, Y., Haque, S. A., Mercer, I. P., Durrant, J. T., & Klug, D. R. (2000). J. Phys.
Chem. B, 104, 1198.
[18] Gra¨tzel, M. (2001). Nature, 414, 338.
[19] Kordatos, K., Da Ros, T., Bosi, S., Vazquez, E., Bergamin, M., Cusan, C., Pellarini, F.,
Tomberli, V., Baiti, B., Pantarotto, D., Georgakilas, V., Spalluto, G., & Prato, M. (2001).
J. Org. Chem., 66, 4915.
[20] Lindsey, J. S., Hsu, H. C., & Schreiman, I. C. (1986). Tet. Lett., 27, 4969.
[21] Flamigni, L., Talarico, A. M., Ventura, B., Marconi, G., Sooambar, C., & Solladie, N.
(2004). Eur. J. Inorg. Chem., 2557.
´
[22] Newman, M. S. & Lee, L. F. (1972). J. Org. Chem., 37, 4468.
[23] Matile, S., Berova, N., Nakanishi, K., Novkova, S., Philipova, I., & Blagoev, B. (1995).
J. Am. Chem. Soc., 117, 7021.
[24] Da Ros, T., Bergamin, M., Vazquez, E., Spalluto, G., Baiti, B., Moro, S., Bouturine, A.,
& Prato, M. (2002). Eur. J. Org. Chem., 405.
[25] Tamiaki, H., Suzuki, S., & Maruyama, K. (1993). Bull. Chem. Soc. Jpn., 66(9), 2633.
[26] Luo, C., Guldi, D. M., Imahori, H., Tamaki, K., & Sakata, Y. (2000). J. Am. Chem. Soc.,
122, 6535.
[27] Shelnutt, J. A., Dobry, M. M., & Satterlee, J. D. (1984). J. Phys. Chem., 88, 4980.
[28] Pasternack, R. F., Bustamante, C., Collings, P. J., Giannetto, A., & Gibbs, E. J. (1993).
J. Am. Chem. Soc., 115, 5393.
[29] Inamura, I. & Uchida, K. (1991). Bull. Chem. Soc. Jpn., 64, 2005.
[30] Lina, Jin-Shyong, Chen, Yu-Chying, Chen, Chien-Chon, Diau, Eric Wei-Guang, & Liu,
Tzeng-Feng. (2006). J. Chin. Chem. Soc., 53, 201–208.

264
M. Prato et al.
[31] Milgrom, L. R. (1997). The Colours of Life: An Introduction to the Chemistry of
Porphyrins and Related Compounds, OUP: Oxford; (1997). or The Porphyrins,
Dolphin, D. (Ed.), Academic Press: New York.
[32] Guterman, M., Wagniere, G. H., & Snyder, L. C. (1963). J. Mol. Spectrosc., 11, 108–127.
[33] Page, R. H., Jurich, M. C., Reck, B., Sen, A., Twieg, R. J., Swalen, J. D., Bjorklund,
G. C., & Wilson, C. G. (1990). J. Opt. Soc. Am. B, 7, 1239.
[34] Gonin, D., Noel, C., & Kajzar, F. (1994). EFISH and THG measurements on organic
molecules in solution. Nonl. Optics, 8, 37.