Triaryl-substituted pyrrolo-p-phenylene-linked porphyrin-fullerene dyads: Expanding the structural diversity of photoactive materials

Article abstract of DOI:10.1016/j.tet.2018.04.084

A protocol for the synthesis of pyrrolo-p-phenylene-linked porphyrin-fullerene dyads suitable as photoactive materials was developed. The sequence of aziridination – aziridine ring opening – 1,3-dipolar cycloaddition reactions enabled us to provide structural variability both to the porphyrin core and to pyrrole linker, which facilitates designing the electronic structure and morphological parameters of the dyads. The key porphyrin building blocks, nitro-porphyrins, were synthesized by a stochastic cyclocondensation of arenecarbaldehydes with p-nitrophenyl(dipyrrolyl)methane.

Full text of DOI:10.1016/j.tet.2018.04.084

Accepted Manuscript
Triaryl-substituted pyrrolo-p-phenylene-linked porphyrin-fullerene dyads: Expanding
the structural diversity of photoactive materials
Artem A. Strelnikov, Dmitriy V. Androsov, Alexander S. Konev, Daniil A. Lukyanov,
Alexander F. Khlebnikov, Alexey V. Povolotskiy, Kaoru Yamanouchi
PII:
S0040-4020(18)30489-7
10.1016/j.tet.2018.04.084
TET 29499
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 6 March 2018
Revised Date: 24 April 2018
Accepted Date: 25 April 2018
Please cite this article as: Strelnikov AA, Androsov DV, Konev AS, Lukyanov DA, Khlebnikov AF,
Povolotskiy AV, Yamanouchi K, Triaryl-substituted pyrrolo-p-phenylene-linked porphyrin-fullerene
dyads: Expanding the structural diversity of photoactive materials, Tetrahedron (2018), doi: 10.1016/
j.tet.2018.04.084.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Triaryl-substituted pyrrolo-p-phenylene-linked porphyrin-fullerene dyads: expanding the
structural diversity of photoactive materials
Artem A. Strelnikov,1 Dmitriy V. Androsov,1 Alexander S. Konev,1* Daniil A. Lukyanov1, Alexander F.
Khlebnikov1, Alexey V. Povolotskiy1, Kaoru Yamanouchi2
1Institute of Chemistry, Saint Petersburg State University, Universitetskii pr. 26, Petrodvorets, 198504, St.
Petersburg, Russia.
2Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo
113-0033, Japan.
*Alexander S. Konev - e-mail: a.konev@spbu.ru, corresponding author.
Abstract
A protocol for the synthesis of pyrrolo-p-phenylene-linked porphyrin-fullerene dyads suitable as
photoactive materials was developed. The sequence of aziridination – aziridine ring opening – 1,3-dipolar
cycloaddition reactions enabled us to provide structural variability both to the porphyrin core and to
pyrrole linker, which facilitates designing the electronic structure and morphological parameters of the
dyads. The key porphyrin building blocks, nitro-porphyrins, were synthesized by a stochastic
cyclocondensation of arenecarbaldehydes with p-nitrophenyl(dipyrrolyl)methane.
Keywords: dipolar cycloaddition; aziridines; donor-acceptor conjugates; fullerenes; porphyrins
Introduction
Porphyrin-fullerene dyads can form a charge separated (CS) state through the intramolecular electron
transfer processes upon photoexcitation,[1-4] and have been considered as promising candidates for the
materials for photovoltaic[5,6] or photo-redox-catalytic applications.[6-8] Recently, Buldum and Reneker
predicted that a rigid p-phenylene linked donor-acceptor dyad should secure dual-channel film
morphology favoring the charge transport after the initial step of the charge separation.[9] In our recent
work, we demonstrated a photovoltaic activity of a similar p-phenylene linked porphyrin-fullerene dyad
1aa which exhibited the photocurrent of up to 4 µA·cm-2.[10]
The performance of the photovoltaic devices based on compounds of this class of dyads should depend on
the electronic and morphological parameters on the molecular level. The most straightforward route for
1

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the tuning the electronic structure of the porphyrin-fullerene dyad is to vary the substituents at the
porphyrin core, which should affect the Gibbs free energy for the charge recombination and the electronic
coupling between the donor and acceptor moieties, both of which are the important parameters in Marcus
theory of charge transfer. Within the class of the dyads, the simplest representative of which is compound
1aa, the morphology of the photoactive films made from such porphyrin-fullerene dyads is expected to be
varied by the changes in the alkyl chains in the ester fragments because of the associated changes in the
intermolecular interactions between the dyads as well as in their steric sizes.
In the present study, we focus on the series of porphyrin-fullerene dyads 1 bearing various substituents in
p-position of meso-phenyl rings (Scheme 1), including strong π-donor (CH3O), weak σ-donor (CH3), π-
donor and σ-acceptor (Br) along with strong σ-acceptor (CF3), and alkyl groups of various lengths in the
ester fragments containing ethyl, n-butyl, n-hexyl and n-octyl groups, and develop our synthetic
methodology for the preparation of pyrrolo-p-phenylene-linked porphyrin-fullerene dyads so that the
structural parameters responsible for the perturbation of the electronic structure of the dyad as well as for
the morphology of the film composed of the dyads can be manipulated. In the course of the exploration of
the synthetic routes, we found that nitro-porphyrins are convenient building blocks to incorporate variable
aryl groups into the porphyrin-fullerene dyads.
Scheme 1. Synthetic target: the library of photoactive porphyrin-fullerene dyads 1.
2

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Results and discussion
Taking into account the theoretical work of Buldum and our experimental results on the photocurrent
induced by dyad 1aa, we selected the co-axial orientation of the donor and acceptor fragments
(tetraarylporphyrin and pyrrolofullerene respectively) to be the key structural parameter to be achieved in
the synthesis of a photoactive donor-acceptor dyad. This can be implemented by constructing the
pyrrolidine ring of the pyrrolofullerene fragment via 1,3-dipolar cycloaddition of suitable azomethine-
ylides across [6,6]-double bond of fullerene C60, which is known as Prato reaction.[11]
Azomethine-ylides are usually highly reactive intermediates, which cannot be isolated in most cases and
need to be generated in situ. In Prato reaction, azomethine-ylides are commonly generated by (i)
condensation of α-amino acids with aldehydes or ketones;[12] (ii) prototropic isomerization of imines[13]
and (iii) electrocyclic ring-opening of aziridines.[14] Among these methods, the last approach suits best our
synthetic goal. The potential advantages of the aziridine-based method for azomethine-ylide generation
include stereospecificity of the ylide formation, the easy synthetic route towards the ylide precursor and
the simplicity of introducing structural variations in the target dyads, as can be seen from the
retrosynthetic disconnection of the target class of compounds down to commercial chemicals (Scheme 1).
The main synthetic problems to be solved for practical implementation of this route include the synthesis
of unsymmetric A3B-type porphyrin synthetic block, the construction of the aziridine ring bearing various
alkoxycarbonyl groups and the verification of applicability of the synthesized set of porphyrinylaziridines
in Prato reaction with fullerene C60.
First, the variability of the alkoxycarbonyl groups in the key step of the dyad synthesis, in which the 1,3-
cycloaddition of azomethine ylides across C=C bond of C60, was tested on a model reaction series of
fullerene C60 with dialkyl N-(p-methoxyphehyl)aziridine dicarboxylates 2.
Aziridines 2 were obtained (Scheme 2) by condensation of p-methoxyaniline with alkylglyoxylate 3,
accessible by oxidative cleavage of dialkyl tartrates with periodic acid, followed by BF3-catalyzed
aziridination with alkyl diazoacetate 4, accessible from alkyl glycinate. The reaction proceeded smoothly
for various combinations of alkyl substituents in the starting imine and the diazocompound yielding
mixtures of cis- and trans-aziridines 2 in 79 – 99% yield (Table 1). In accord with the previous reports on
aziridination reactions,[15] cis-aziridines were the major products with the ratio of cis/trans aziridines in
the range between 5:1 and 12:1.
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Unsymmetrically substituted trans-aziridines trans-2ab, trans-6ac and trans-2ad showed expectable AB
3
pattern at 3.44 ppm for the aziridine protons with JHH coupling constant of 2 Hz, typical for trans-
aziridines.[16] The corresponding AB signal for cis-aziridines cis-2ab, cis-2ac, cis-2ad was reduced to a
singlet shifted to the stronger field (3.0 ppm). Configuration of these aziridines and of symmetrically
3
13
substituted aziridines 2aa, 2bb, 2cc and 2dd was confirmed by observing the JHH coupling of the C-
3
satellite signals. Cis-aziridines are characterized by JHH of 6-7 Hz,[17] while trans-aziridines show lesser
value of 0-2 Hz (Table 1).
Scheme 2. Synthesis of pyrrolofullerenes.
Table 1. Reaction yields and selected NMR data for aziridines 2.
R1
R2
Yield of
Yield of
3JHH, Hz
3JHH, Hz
trans-2
δ H2(3), ppm
cis-2
δ H2(3), ppm
trans-2
3.44
2
cis-2, %
trans-2, % cis-2
6a
3.04
0a
[18]
Et
Et
Et
Et
Et
86
13
14
12
6
2aa
2ab
2ac
2ad
2bb
2cc
2dd
Bu 77
Hex 78
Oct 73
6.7a
6.7a
6.7a
6.7a
6.6a
6a
3.00
2.4
3.43, 3.44
3.43, 3.44
3.43, 3.44
3.43
3.03
3.03
3.03
3.02
3.04
2.4
2.3
2.4a
2.4a
0a
Bu Bu 82
Hex Hex 86
Oct Oct 81
17
10
13
3.45
[18]
3.44
aFor 13C satellite signals.
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Table 2. Reaction yields and selected NMR data for fulleropyrrolidines 5.
R1
R2
Trans
Cis
5
δ H2(5), δ C2(5), δ C3(4)
,
δ H2(5), δ C2(5), δ C3(4)
,
Yield,
%
Yield,
%
ppm
6.51
6.50
ppm
74.7
74.6,
74.9
74.6,
74.9
74.6,
74.9
74.8
ppm
71.2
ppm
-
ppm
-
ppm
-
[18]
Et
Et
Et
47
-
5aa
Bu 49
Hex 57
Oct 38
71.2,
71.23
48
5.69,
5.72
5.70,
5.72
5.70,
5.72
77.9,
78.2
77.9,
78.1
77.9,
78.1
78.2
71.4,
71.44
5ab
5ac
5ad
5bb
Et
Et
6.50,
6.51
6.50
71.21, 59
71.24
71.38,
71.43
71.40,
71.44
71.4
71.22, 42
71.24
Bu Bu 57
71.3
25
6.51
6.51
6.52
5.71
5.71
5.72
Hex Hex 50
Oct Oct 41
74.8
74.8
71.2
71.2
58
31
78.1
78.1
71.4
71.4
5cc
[18]
5dd
Aziridines 2 were reacted with fullerene C60 to give pyrrolofullerenes 5 (Scheme 2) in 25 – 59% yield
(Table 2). The solubility of the resulting adducts increased dramatically when either one or both ethyl
groups in 5aa were changed for longer alkyl chains: n-butyl, n-hexyl or n-octyl. The reaction of aziridines
2 with C60 proceeded stereospecifically, with cis-aziridines giving only trans-adducts, and trans-
aziridines – cis-adducts.
The configuration of the pyrrolofullerenes was established based on the chemical shift of the pyrrolidine
1
HC2(5) proton in H NMR spectra. The signal of this proton is shifted towards weak field for trans-
pyrrolofullerenes as compared to cis-pyrrolofullerenes[18] (6.5 and 5.7 ppm respectively). For
unsymmetrically substituted pyrrolofullerenes 5ab, 5ac and 5ad, the signals of the pair of non-equivalent
pyrrolidine protons H2 and H5 could be discerned as two singlets both for cis-isomers (5.69 and 5.71 ppm)
and trans-isomers (6.50 and 6.51), except compound trans-5ab, where the corresponding signals
coalesced into a single singlet (6.5 ppm) of double integral intensity. We attribute this to the strong
deshielding effect of the carbonyl group in the case of trans-isomers, which masks the small differences in
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chemical surrounding of these protons. The non-equivalence of the CH fragments in the pyrrolidine ring
13
can be seen in C NMR spectra of this pyrrolofullerene, where a pair of signals for C2(5) carbons was
observed (74.6 and 74.9 ppm for trans-isomers) along with two more signals for C3(4) carbons (71.20,
71.23) (Table 2). The attribution of signals for C2(5) and C3(4) carbons was based on the correlation cross-
1
peaks observed in H-13C HSQC spectrum of cis-5ab between the pyrrolidine protons signals at 5.7 ppm
1
and the C2(5) carbons signals at 78 ppm due to the JC-H heterocoupling constant combined with the
observation of the intensive correlation cross-peaks in 1H-13C HMBC spectrum of cis-5ab between the
pyrrolidine protons signals at 5.7 ppm and the C3(4) carbons signals at 71.4 ppm, which was due to the 3JC-
H vicinal heterocoupling constant (Scheme 3).
Scheme 3. Representation of cross-peaks in 2D NMR spectra of trans-5ab and cis-5ab.
The protocol for construction of an aziridine ring on a porphyrin framework has been reported in our
previous work[10] for compound 1aa. However, a different approach to the synthesis of the key
intermediates, nitro-porphyrins 6b-f, was found to be necessary in the case of dyads bearing substituted
aryl group. To synthesize these porphyrins, a stochastic cyclocondensation of arenecarbaldehydes 7b-f
with p-nitrophenyl(dipyrrolyl)methane (8) was used instead of nitration of the corresponding
unsymmetrical porphyrins (Scheme 4).
Compared to the reaction with p-nitrobenzaldehyde, the application of dipyrromethane 8 reduces the
differences in reactivity of different aldehydes, providing kinetic uniformity, which is important for
successful formation of A3B porphyrinogens in a stochastic cyclocondensation step. Otherwise, when
aldehydes A and B of significantly different reactivity are directly condensed with pyrrole, formation of
A4 or B4 porphyrins prevails. For example, reaction of aldehyde 7f containing extremely electron-rich
2,4,6-trimethoxysubstituted phenyl ring with electron-deficient p-nitrobenzaldehyde (9) and pyrrole gave
mainly symmetric porphyrins 10 and 11 (Scheme 5), whereas the replacement of aldehyde 9 with
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dipyrromethane 8 resulted in the successful synthesis of mixed A3B-type nitro-porphyrin 6f in 12% yield
(Scheme 4).
Scheme 4. Synthesis of target porphyrin-fullerene dyads 1. Reaction conditions: i. 1. Pyrrole, I2, DCM/30
°C, 2. chloranil; ii. 1. Pyrrole, I2, CHCl3/61 °C 2. chloranil; iii. 1. SnCl2/HCl, 2. NH4OH aq.; iv. 1.
RO2CCHO, 2. RO2CCHN2, BF3·OEt2; v. chlorobenzene/100 °C.
O2N
ArCHO
X
6f
+
+
O
N
7f
H
9
1. I2, DCM/30 °C
2. chloranil
NO2
Ar
Ar
N
N
HN
N
H
Ar
N
N
Ar
+
H
N
NH
Ar
Ar
10
11
O2N
Ar = 2,4,6-(CH3O)3-C6H2
trace amounts
Scheme 5. Side-reactions in stochastic condensation of aldehydes 9 and 7f with pyrrole.
[19,20,21]
Nitro-porphyrins 6b-f were reduced to amino-porphyrins 12b-f by SnCl2
in hydrochloric acid.
Alternative reports suggest reduction by NaBH4/Pd/C,[22] or H2/Pd,[23] but tin(II) chloride seems to be the
most common reductant. In our systems, the reduction proceeded smoothly giving the desired amino-
porphyrins in 47-84% yield (Scheme 4) in most cases. However, when strong acceptors like CF3-group
were presented in the tetraphenylporphyrin central core, the reduction proceeded with a low conversion
(yet with good yield, 67% yield of reduction step as estimated for a two-step synthesis of 12c from 6c)
and attempts were made to accelerate it by applying more harsh conditions of elevated temperature. In
this case, the conversion of the starting material was complete but the yield of 12c decreased to 26% and
the reaction was accompanied by chlorination of the p-nitrophenyl group, giving after in situ reduction
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chlorinated amino-porphyrin 13 as a by-product in 29% yield (Scheme 6). No chlorination product was
observed when amino-porphyrin 12c was subjected to the identical reaction conditions, confirming that
1
chlorination proceeds before the reduction step. H NMR spectra of 13 showed multiplets pattern typical
for 1,2,4-trisubstituted phenyl rings as AB system doublet at 7.14 and at 8.12 ppm along with the doublet
of doublets at 7.92 ppm. 2D NOESY NMR spectrum showed correlation of β-pyrrolic protons of the
porphyrin fragment with the protons of 1,2,4-trisubstituted benzene ring as two cross-peaks (8.78 vs 7.92
ppm and 8.78 vs. 8.12 ppm), unequivocally demonstrating that the chlorination proceeded in ortho-
position with respect to nitro group. Alternative position for chlorination would result in only one cross-
peak of the protons of pyrrole and benzene rings.
Scheme 6. Chlorination-reduction of porphyrin 6c.
Condensation of the amino-porphyrins 12b-f with alkyl glyoxylates 3a-d followed by Lewis-acid
catalyzed nucleophilic addition of alkyl diazoacetates 4a-d gave aziridinyl-porphyrins 14 in 49-83%
yields. Aziridination of 6f was not successful as the reaction was accompanied by partial removal of
methoxy-groups, leading to very low yield (9%) of the target aziridine 14fa. In all cases (other than
compound 14fa), the reaction proceeded smoothly to selectively give cis-aziridines, in accord with the
previous reports on BF3·Et2O catalyzed reaction of imines with diazo compounds.[15,18]
Configuration of the aziridine ring was established based on the values of vicinal spin-spin coupling
13
constant on C-2-satellite doublets[24] of the aziridine protons, which comprised 6.9 Hz, typical for cis-
aziridines (6-7 Hz[17] vs. 0-3 Hz[16] in trans-aziridines). Independent confirmation of aziridine cis-
configuration was obtained in the case of reaction with amino-porphyrins 12c (CF3) and 12e (CH3O),
1
where trans-aziridines trans-14ca,ea were isolated in 10-12% yield and characterized by H-NMR.
Comparison of 1H-NMR spectra of cis- and trans-14ca,ea shows that the signal of the aziridine protons is
shifted downfield in trans-14ca,ea compared to the same signal in cis-14ca,ea (3.8 vs. 3.5 ppm). This
8

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downfield shift for trans-aziridines has been known well[24] and it can be ascribed to deshielding effect of
the ester carbonyl group. All other aziridines cis-14 show chemical shift of 3.4-3.5 ppm for the aziridine
protons, independently confirming the assignment of the aziridine configurations.
Aziridinyl-porphyrines 14 were reacted with fullerene C60 to give the target porphyrin-fullerene dyads 1
in 21-48% yield (Scheme 4). The reaction proceeded stereoselectively and gave exclusively trans-adducts
in accord with Woodward-Hoffman’s rules for the sequence of concerted processes: cis-aziridine ring-
opening to S-ylide followed by cycloaddition across C=C bond between two six-membered rings in
fullerene C60 forming the trans-pyrrolidine ring condensed to C60 skeleton.
1
HRMS data on the dyads were consistent with the proposed brutto-formulae. H NMR spectra showed
characteristic signals of fulleropyrrolidine fragment (singlet at ca. 6.7 ppm for CHCO2R) along with
characteristic signals of the porphyrin fragment (strong-field singlet for NH protons at ca. -2.7 − -2.8 ppm
and weak-field two AB systems at 8.8-9.0 ppm for β-pyrrolic protons). 13C NMR spectra showed
characteristic signals for the pyrrolidine ring carbons at 71 and 75 ppm along with broad singlet at 130-
131 ppm typical for β-pyrrolic carbons of the porphyrin ring. The configuration of the adducts was
established on the basis of chemical shift for the pyrrolidine protons (6.7-6.8 ppm).[10,24,25]
Steady-state absorption and emission measurements showed spectroscopic features characteristic of
porphyrin compounds[26] (Fig. S133, Supporting information): absorption spectra of benzonitrile solution
of dyads 1 showed a strong band at ca. 425 nm (Soret band) and four bands of much smaller intensities in
the range of 480-680 nm (refered to as Q-bands:[27] ca. 520, 555, 595 and 650 nm).
A comparison of the UV/Vis spectra of the dyads with the spectra of porphyrinyl aziridines 14 and
fulleropyrrolidines 5 shows that only a weak coupling of porphyrin and fullerene chromophores occurs in
the dyads because the absorption spectra of dyads 1 are roughly a superposition of the absorption spectra
of two separate chromophores in compounds 14 and 5. The UV/Vis spectra for compounds 1da, 14da and
5aa are presented on Fig. 1 as a typical example.
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Figure 1. UV/Vis absorption spectra of dyad 1da, porphyrin 14da and pyrrolofullerene 5aa in PhCN.
The emission spectra of dyads 1 showed emission peaks at ca. 656 and 724 nm (Fig. S135). The observed
fluorescence lifetime was ca. 1-3 ns, with the fluorescence quantum yield of less than 1%.
Conclusions
The synthetic protocol based on the incorporation of an aziridine pendant to porphyrin ring has been
demonstrated to afford structural diversity in the synthesis of porphyrin-fullerene dyads necessary in the
optimization of the molecular structures of this class of photoactive material. It has been shown that both
porphyrin and fulleropyrrolidine moieties can be modified by this synthetic approach, which allows us to
optimize the electronic properties of the porphyrin-fullerene donor acceptor system and design the
morphology of the material formed by these dyads through the modification of the intermolecular
interactions via a variability of the solubilizing alkyl ester group.
Experimental section
1
13
General. IR spectra were recorded on an FTIR-8400S Shimadzu spectrometer. H (400 MHz) and C
(100 MHz) NMR spectra were determined in CDCl3 on Bruker 400 spectrometer. Chemical shifts ( ) are
δ
reported in ppm downfield from Me4Si. HRMS was performed using a Bruker MaXis Q-TOF mass
spectrometer. Flash chromatography was performed on silica Merck 60.
Starting materials and known compounds. Commercial solvents were purified according to standard
techniques. Alkyl glyoxilates 3,[28] alkyl diazoacetates 4,[29,30] p-nitrophenyldipyrrometane (8),[31] 1,3,5-
10

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trimethoxybenzaldehyde 7f,[32] 4-(trifluoromethyl)benzaldehyde 7c[33] were obtained according to
published procedures.
General procedure for the synthesis of aziridines 2. A mixture of 4-methoxyaniline (1 eq), alkyl
glyoxylate 3 (1.5 eq) and anhydrous Na2SO4 (100 mg) in dry benzene (2 ml) was stirred at ambient
temperature for 30-40 min. Sodium sulfate was filtered off and the solvent was removed in vacuo. The
residue was dissolved in dry ether (8 ml) and 1-2 droplets of boron trifluoride etherate were added. A
solution of alkyl diazoacetate 4 (1.1 eq) in dry ether (2 ml) was added dropwise and the mixture was
stirred for another 2 h and quenched with 5 droplets of triethylamine. The mixture was diluted with water,
extracted with DCM and dried over Na2SO4. The desiccant was filtered off, the solvent was removed in
vacuo and the residue was separated by column chromatography (silica gel, petroleum ether – ethyl
acetate) to afford products as yellowish oils.
O-Ethyl-O-butyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (cis-2ab). Yield: 77% (247 mg,
1
3
0.77 mmol). H NMR (CDCl3, 400 MHz): δ=0.94 (t, J(H,H)=7.4 Hz, 3H; CH3CH2C), 1.31 (t,
3J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.34–1.45 (m, 2H; CH3CH2C), 1.62–1.71 (m, 2H; CH2CH2O), 3.00 (s,
2H; HCaz), 3.74 (s, 3H; CH3O), 4.20 (t, 3J(H,H)=6.7 Hz, 2H; CH2CH2O), 4.26 (q, 3J(H,H)=7.2 Hz, 2H;
CH3CH2O), 6.78 (AA'BB', 3J(H,H)=8.9 Hz, 2H; OC=CH), 6.94 (AA'BB', 3J(H,H)=8.9 Hz, 2H; NC=CH);
13C NMR (CDCl3, 100 MHz):
δ=13.6 (CH3CH2C), 14.0 (CH3CH2O), 18.9 (CH3CH2C), 30.4 (CH2CH2O),
43.1 (Caz), 43.2 (Caz), 55.4 (CH3O), 61.7 (CH3CH2O), 65.5 (CH2CH2O), 114.3 (OC=CH), 120.8
(NC=CH), 144.2 (NC=CH), 156.2 (OC=CH), 166.96 (C=O), 167.01 (C=O); IR (KBr): ν˜=1734, 1754
(C=O); HRMS (ESI): m/z: calcd for C17H23NO5Na+, 344.1468 [M+Na]+; found 344.1484.
O-Ethyl-O-butyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-2ab). Yield: 14% (44
1
3
mg, 0.14 mmol). H NMR (CDCl3, 400 MHz): δ=0.92 (t, J(H,H)=7.4 Hz, 3H; CH3CH2C), 1.24 (t,
3J(H,H)=7.1 Hz, 3H; CH3CH2O), 1.29–1.36 (m, 2H; CH3CH2C), 1.52–1.59 (m, 2H; CH2CH2O), 3.43
3
3
(AB, J(H,H)=2.4 Hz, 1H; HCaz), 3.44 (AB, J(H,H)=2.4 Hz, 1H; HCaz), 3.76 (s, 3H; CH3O), 4.04–4.14
3
(m, 2H; CH2CH2O), 4.15–4.21 (m, 2H; CH3CH2O), 6.78 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.84
3
(AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=13.6 (CH3CH2C), 14.0
(CH3CH2O), 18.9 (CH3CH2C), 30.4 (CH2CH2O), 42.3 (Caz), 42.4 (Caz), 55.4 (CH3O), 61.7 (CH3CH2O),
65.6 (CH2CH2O), 114.2 (OC=CH), 120.6 (NC=CH), 140.4 (NC=CH), 155.9 (OC=CH), 167.0 (C=O),
11

ACCEPTED MANUSCRIPT
167.1 (C=O); IR (KBr): ν˜=1738 (C=O); HRMS (ESI): m/z: calcd for C17H23NO5Na+, 344.1468 [M+Na]+;
found 344.1477.
O-Ethyl-O-hexyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (cis-2ac). Yield: 78% (273 mg,
1
3
0.78 mmol). H NMR (CDCl3, 400 MHz): δ=0.91 (t, J(H,H)=7.0 Hz, 3H; CH3CH2C), 1.33 (t,
3J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.30–1.42 (m, 6H; CH3(CH2)3), 1.65–1.74 (m, 2H; CH2CH2O), 3.03 (s,
2H; HCaz), 3.77 (s, 3H; CH3O), 4.22 (t, 3J(H,H)=7.0 Hz, 2H; CH2CH2O), 4.24–4.33 (m, 2H; CH3CH2O),
3
3
13
6.80 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.97 (AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH); C NMR
(CDCl3, 100 MHz): =13.9 (CH3CH2C), 14.1 (CH3CH2O), 22.5 (CH3CH2C), 25.4 (CH3CH2CH2), 28.4
δ
(CH3(CH2)2CH2), 31.3 (CH2CH2O), 42.2 (Caz), 42.3 (Caz), 55.4 (CH3O), 61.7 (CH3CH2O), 65.9
(CH2CH2O), 114.4 (OC=CH), 120.9 (NC=CH), 144.2 (NC=CH), 156.2 (OC=CH), 167.0 (C=O), 167.1
(C=O); IR (KBr): ν˜=1753, 1734 (C=O); HRMS (ESI): m/z: calcd for C19H27NO5Na+, 372.1781 [M+Na]+;
found 372.1797.
O-Ethyl-O-hexyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-2ac). Yield: 12% (42
1
3
mg, 0.12 mmol). H NMR (CDCl3, 400 MHz): δ=0.90 (t, J(H,H)=7.0 Hz, 3H; CH3CH2C), 1.24 (t,
3J(H,H)=7.0 Hz, 3H; CH3CH2O), 1.25–1.36 (m, 6H; CH3(CH2)3), 1.55–1.61 (m, 2H; CH2CH2O), 3.43
3
3
(AB, J(H,H)=2.4 Hz, 1H; HCaz), 3.44 (AB, J(H,H)=2.4 Hz, 1H; HCaz), 3.76 (s, 3H; CH3O), 4.03–4.14
3
(m, 2H; CH2CH2O), 4.14–4.22 (m, 2H; CH3CH2O), 6.78 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.85
3
(AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=13.9 (CH3CH2C), 14.0
(CH3CH2O), 22.4 (CH3CH2C), 25.4 (CH3CH2CH2), 28.3 (CH3(CH2)2CH2), 31.3 (CH2CH2O), 42.3 (Caz),
42.4 (Caz), 55.4 (CH3O), 61.7 (CH3CH2O), 65.9 (CH2CH2O), 114.2 (OC=CH), 120.7 (NC=CH), 140.4
(NC=CH), 155.9 (OC=CH), 167.05 (C=O), 167.12 (C=O); IR (KBr): ν˜=1738 (C=O); HRMS (ESI): m/z:
+
calcd for C19H28NO5 , 350.1962 [M+H]+; found 350.1969, calcd for C19H27NO5Na+, 372.1781 [M+Na]+;
found 372.1792.
O-Ethyl-O-octyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (cis-2ad). Yield: 73% (152 mg,
0.4 mmol). 1H NMR (CDCl3, 400 MHz): δ=0.89 (t, 3J(H,H)=6.8 Hz, 3H; CH3CH2C), 1.33 (t, 3J(H,H)=7.2
Hz, 3H; CH3CH2O), 1.23–1.41 (m, 10H; CH3(CH2)5), 1.66–1.74 (m, 2H; CH2CH2O), 3.03 (s, 2H; HCaz),
3
3.77 (s, 3H; CH3O), 4.21 (t, J(H,H)=6.9 Hz, 2H; CH2CH2O), 4.25–4.32 (m, 2H; CH3CH2O), 6.81
3
3
(AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.97 (AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR
(CDCl3, 100 MHz):
δ
=14.0 (CH3CH2C), 14.1 (CH3CH2O), 22.6 (CH3CH2C), 25.8 (CH3CH2CH2), 28.5
12

ACCEPTED MANUSCRIPT
(CH3(CH2)2CH2), 29.1 (CH3(CH2)3CH2), 29.2 (CH3(CH2)4CH2), 31.7 (CH2CH2O), 43.2 (Caz), 43.3 (Caz),
55.5 (CH3O), 61.8 (CH3CH2O), 66.0 (CH2CH2O), 114.4 (OC=CH), 120.9 (NC=CH), 144.3 (NC=CH),
156.2 (OC=CH), 167.06 (C=O), 167.10 (C=O); IR (KBr): ν˜=1739 (C=O); HRMS (ESI): m/z: calcd for
C21H31NO5Na+, 400.2094 [M+Na]+; found 400.2114.
O-Ethyl-O-octyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-2ad). Yield: 6% (12
1
3
mg, 0.03 mmol). H NMR (CDCl3, 400 MHz): δ=0.90 (t, J(H,H)=7.2 Hz, 3H; CH3CH2C), 1.24 (t,
3J(H,H)=7.0 Hz, 3H; CH3CH2O), 1.25–1.35 (m, 10H; CH3(CH2)5), 1.55–1.61 (m, 2H; CH2CH2O), 3.43
3
3
(AB, J(H,H)=2.3 Hz, 1H; HCaz), 3.44 (AB, J(H,H)=2.3 Hz, 1H; HCaz), 3.76 (s, 3H; CH3O), 4.05–4.14
3
(m, 2H; CH2CH2O), 4.14–4.23 (m, 2H; CH3CH2O), 6.78 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.85
3
(AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH);13C NMR (CDCl3, 100 MHz):
δ
=14.04 (CH3CH2C), 14.05
(CH3CH2O), 22.6 (CH3CH2C), 25.7 (CH3CH2CH2), 28.4 (CH3(CH2)2CH2), 29.10 (CH3(CH2)3CH2), 29.12
(CH3(CH2)4CH2), 31.7 (CH2CH2O), 42.3 (Caz), 42.4 (Caz), 55.4 (CH3O), 61.8 (CH3CH2O), 66.0
(CH2CH2O), 114.2 (OC=CH), 120.7 (NC=CH), 140.4 (NC=CH), 155.9 (OC=CH), 167.08 (C=O), 167.12
+
(C=O); IR (KBr): ν˜=1739 (C=O); HRMS (ESI): m/z: calcd for C21H32NO5 , 378.2275 [M+H]+; found
378.2276, calcd for C21H31NO5Na+, 400.2094 [M+Na]+; found 400.2101.
Dibutyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (cis-2bb). Yield: 82% (144 mg, 0.41
1
3
mmol). H NMR (CDCl3, 400 MHz): δ=0.96 (t, J(H,H)=7.3 Hz, 6H; CH3CH2C), 1.36–1.48 (m, 4H;
CH3CH2C), 1.64–1.74 (m, 4H; CH2CH2O), 3.03 (s, 2H; HCaz), 3.78 (s, 3H; CH3O), 4.23 (t, 3J(H,H)=6.8
3
3
Hz, 4H; CH2CH2O), 6.81 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.96 (AA'BB', J(H,H)=9.0 Hz, 2H;
13
NC=CH); C NMR (CDCl3, 100 MHz):
δ
=13.6 (CH3CH2C), 19.0 (CH3CH2C), 30.5 (CH2CH2O), 43.3
(Caz), 55.4 (CH3O), 65.6 (CH2CH2O), 114.4 (OC=CH), 120.9 (NC=CH), 144.3 (NC=CH), 156.2
+
(OC=CH), 167.1 (C=O); IR (KBr): ν˜=1734, 1754 (C=O); HRMS (ESI): m/z: calcd for C19H28NO5 ,
350.1962 [M+H]+; found 350.1968.
Dibutyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-2bb). Yield: 17% (30 mg, 0.09
1
3
mmol). H NMR (CDCl3, 400 MHz): δ=0.92 (t, J(H,H)=7.3 Hz, 6H; CH3CH2C), 1.29–1.36 (m, 4H;
CH3CH2C), 1.54–1.61 (m, 4H; CH2CH2O), 3.43 (s, 2H; HCaz), 3.76 (s, 3H; CH3O), 4.06–4.14 (m, 4H;
CH2CH2O), 6.78 (AA'BB', 3J(H,H)=9.0 Hz, 2H; OC=CH), 6.84 (AA'BB', 3J(H,H)=9.0 Hz, 2H; NC=CH);
13C NMR (CDCl3, 100 MHz):
δ=13.6 (CH3CH2C), 19.0 (CH3CH2C), 30.4 (CH2CH2O), 42.3 (Caz), 55.4
(CH3O), 65.6 (CH2CH2O), 114.2 (OC=CH), 120.6 (NC=CH), 140.4 (NC=CH), 155.9 (OC=CH), 167.1
13

ACCEPTED MANUSCRIPT
+
(C=O); IR (KBr): ν˜=1737 (C=O); HRMS (ESI): m/z: calcd for C19H28NO5 , 350.1962 [M+H]+; found
350.1971.
Dihexyl cis-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (cis-2cc). Yield: 86 % (174 mg, 0.43
1
3
mmol). H NMR (CDCl3, 400 MHz): δ=0.90 (t, J(H,H)=7.2 Hz, 6H; CH3CH2C), 1.25–1.41 (m, 12H;
CH3(CH2)3), 1.65–1.73 (m, 4H; CH2CH2O), 3.02 (s, 2H; HCaz), 3.76 (s, 3H; CH3O), 4.20 (t, 3J(H,H)=7.0
3
3
Hz, 4H; CH2CH2O), 6.80 (AA'BB', J(H,H)=9.0 Hz, 2H; OC=CH), 6.95 (AA'BB', J(H,H)=9.0 Hz, 2H;
NC=CH); 13C NMR (CDCl3, 100 MHz):
δ
=13.9 (CH3CH2C), 22.5 (CH3CH2C), 25.4 (CH3CH2CH2C),
28.4 (CH3(CH2)2CH2C), 31.4 (CH2CH2O), 43.3 (Caz), 55.4 (CH3O), 65.9 (CH2CH2O), 114.4 (OC=CH),
120.9 (NC=CH), 144.3 (NC=CH), 156.2 (OC=CH), 167.1 (C=O); IR (KBr): ν˜=1755, 1734 (C=O);
+
HRMS (ESI): m/z: calcd for C23H36NO5 , 406.2588 [M+H]+; found 406.2567, calcd for C23H35NO5Na+,
428.2407 [M+Na]+; found 428.2418.
Dihexyl trans-1-(4-methoxyphenyl)aziridine-2,3-dicarboxylate (trans-2cc). Yield: 10% (21 mg, 0.05
1
3
mmol). H NMR (CDCl3, 400 MHz): δ=0.90 (t, J(H,H)=7.0 Hz, 6H; CH3CH2C), 1.25–1.40 (m, 12H;
CH3(CH2)3), 1.53–1.63 (m, 4H; CH2CH2O), 3.43 (s, 2H; HCaz), 3.76 (s, 3H; CH3O), 4.04-4.20 (m, 4H;
CH2CH2O), 6.78 (AA'BB', 3J(H,H)=9.0 Hz, 2H; OC=CH), 6.84 (AA'BB', 3J(H,H)=9.0 Hz, 2H; NC=CH);
13C NMR (CDCl3, 100 MHz):
δ=13.9 (CH3CH2C), 22.5 (CH3CH2C), 25.4 (CH3CH2CH2C), 28.4
(CH3(CH2)2CH2C), 31.3 (CH2CH2O), 42.4 (Caz), 55.3 (CH3O), 65.9 (CH2CH2O), 114.2 (OC=CH), 120.6
(NC=CH), 140.4 (NC=CH), 155.9 (OC=CH), 167.2 (C=O); IR (KBr): ν˜=1739; HRMS (ESI): m/z: calcd
for C23H35NO5Na+, 428.2407 [M+Na]+; found 428.2429.
General procedure for the synthesis of pyrrolofullerenes 5. A solution of aziridine 2 (1 eq) and
fullerene C60 (1.33 eq) in dry o-dichlorobenzene (2 ml) was stirred at 100 °C until consumption of the
aziridine (control by TLC). Reaction mixture was separated by column chromatography (silica gel,
toluene) to afford product as brown solid.
1
Pyrrolofullerene trans-5ab. Reaction time: 12 h. Yield: 49% (39 mg, 0.037 mmol). H NMR (CDCl3,
3
3
400 MHz): δ=0.83 (t, J(H,H)=7.4 Hz, 3H; CH3CH2C), 1.17 (t, J(H,H)=7.1 Hz, 3H; CH3CH2O), 1.26–
1.28 (m, 2H; CH3CH2C), 1.53–1.55 (m, 2H; CH2CH2O), 3.89 (s, 3H; CH3O), 4.14–4.22 (m, 2H;
3
CH2CH2O), 4.22–4.30 (m, 2H; CH3CH2O), 6.50 (s, 2H, HCPyr), 7.02 (AA'BB', J(H,H)=8.9 Hz, 2H;
3
13
OC=CH), 7.36 (AB, J(H,H)=8.9 Hz, 2H; NC=CH); C NMR (CDCl3, 100 MHz): δ=13.6 (CH3CH2C),
14.2 (CH3CH2O), 19.0 (CH3CH2C), 30.5 (CH2CH2O), 55.5 (CH3O), 61.7 (CH3CH2O), 65.5 (CH2CH2O),
14

ACCEPTED MANUSCRIPT
71.2 (C3/4), 71.23 (C3/4), 74.6 (C2/5), 74.9 (C2/5), 114.8 (OC=CH), 121.0 (NC=CH), 136.32, 136.34,
136.97, 137.0 (Cfullerene), 138.5 (NC=CH), 139.6, 139.7, 140.2 (2C), 141.8 (2C), 141.81, 141.83, 141.9
(4C), 142.16 (2C), 142.22, 142.23, 142.7 (2C), 142.8 (2C), 143.1 (2C), 144.5 (2C), 144.6 (2C), 145.3
(2C), 145.4 (2C), 145.6, 145.61, 145.62 (2C), 145.73, 145.74 (2C), 145.75, 145.76, 145.8, 146.1 (4C),
146.38, 146.39, 146.42, 146.44, 147.5 (2C), 150.6, 150.7, 153.35, 153.40 (Cfullerene), 155.4 (OC=CH),
+
170.2 (C=O), 170.4 (C=O); IR (KBr): ν˜=1724, 1751 (C=O); HRMS (ESI): m/z: calcd for C77H24NO5 ,
1042.1649 [M+H]+; found 1042.1692.
Pyrrolofullerene cis-5ab. Reaction time: 18 h. Yield: 48% (22 mg, 0.021 mmol). 1H NMR (CDCl3, 400
3
3
MHz): δ=0.81 (t, J(H,H)=7.3 Hz, 3H; CH3CH2C), 1.15 (t, J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.19–1.26
(m, 2H; CH3CH2C), 1.46–1.52 (m, 2H; CH2CH2O), 3.90 (s, 3H; CH3O), 4.09–4.18 (m, 2H; CH2CH2O),
3
4.18–4.25 (m, 2H; CH3CH2O), 5.69 (s, 1H, HCPyr), 5.72 (s, 1H, HCPyr), 7.05 (AA'BB', J(H,H)=9.0 Hz,
3
2H; OC=CH), 7.78 (AB, J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=13.6
(CH3CH2C), 14.2 (CH3CH2O), 19.0 (CH3CH2C), 30.5 (CH2CH2O), 55.5 (CH3O), 61.8 (CH3CH2O), 65.6
(CH2CH2O), 71.40 (C3/4), 71.44 (C3/4), 77.9 (C2/5), 78.2 (C2/5), 114.5 (OC=CH), 126.5 (NC=CH), 135.55,
135.59, 137.75 (Cfullerene), 137.76 (NC=CH), 137.79, 139.7, 139.8, 139.9 (2C), 141.8 (2C), 141.89, 141.91,
142.01 (3C), 142.03, 142.19, 142.20, 142.3 (2C), 143.73 (2C), 142.74 (2C), 143.1, 143.2, 144.41, 144.42,
144.67, 144.68, 145.32 (2C), 145.34 (2C), 145.4, 145.48, 145.49 (2C), 145.6, 145.76, 145.77 (2C),
146.10 (2C), 146.13 (2C), 146.25, 146.27, 146.34 (2C), 146.46, 146.47, 147.5 (2C), 150.9, 151.0, 152.4,
152.5 (Cfullerene), 158.0 (OC=CH), 168.3 (C=O), 168.4 (C=O); IR (KBr): ν˜=1729, 1755 (C=O); HRMS
+
(ESI): m/z: calcd for C77H24NO5 , 1042.1649 [M+H]+; found 1042.1671.
1
Pyrrolofullerene trans-5ac. Reaction time: 19 h. Yield: 57% (41 mg, 0.038 mmol). H NMR (CDCl3,
3
3
400 MHz): δ=0.85 (t, J(H,H)=7.0 Hz, 3H; CH3CH2C), 1.17 (t, J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.17–
1.27 (m, 6H; CH3(CH2)3C), 1.50–1.59 (m, 2H; CH2CH2O), 3.87 (s, 3H; CH3O), 4.12–4.21 (m, 2H;
CH2CH2O), 4.21–4.30 (m, 2H; CH3CH2O), 6.50 (s, 1H, HCPyr), 6.51 (s, 1H, HCPyr), 7.02 (AA'BB',
3
3J(H,H)=9.0 Hz, 2H; OC=CH), 7.35 (AB, J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ
=14.0 (CH3CH2C), 14.2 (CH3CH2O), 22.5 (CH3CH2C), 25.6 (CH3CH2CH2), 28.5 (CH3(CH2)2CH2), 31.3
(CH2CH2O), 55.5 (CH3O), 61.7 (CH3CH2O), 65.9 (CH2CH2O), 71.21 (C3/4), 71.24 (C3/4), 74.6 (C2/5), 74.9
(C2/5), 114.8 (OC=CH), 120.9 (NC=CH), 136.32, 136.34, 136.97, 136.98, (Cfullerene), 138.5 (NC=CH),
139.6, 139.7, 140.15, 140.17, 141.79, 141.80, 141.81, 141.83, 141.9 (4C), 142.16, 142.17, 142.22 (2C),
15

ACCEPTED MANUSCRIPT
142.7 (2C), 142.8 (2C), 143.1 (2C), 144.50, 144.51, 144.56, 144.57, 145.3 (2C), 145.4 (2C), 145.59,
145.62 (2C), 145.63, 145.73 (3C), 145.76, 145.78, 145.82, 146.1 (4C), 146.38 (2C), 146.43, 146.44,
147.49 (2C), 150.65, 150.68, 153.37, 153.41 (Cfullerene), 155.4 (OC=CH), 170.2 (C=O), 170.4 (C=O); IR
+
(KBr): ν˜=1730, 1755 (C=O); HRMS (ESI): m/z: calcd for C79H28NO5 , 1070.1962 [M+H]+; found
1070.1984; calcd for C79H27NO5Na+, 1092.1781 [M+Na]+; found 1092.1799.
Pyrrolofullerene cis-5ac.
1
Reaction time: 19 h. Yield: 59% (42 mg, 0.039 mmol). H NMR (CDCl3, 400 MHz): δ=0.84 (t,
3
3J(H,H)=7.2 Hz, 3H; CH3CH2C), 1.15 (t, J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.17–1.27 (m, 6H; CH-
3(CH2)3C), 1.47–1.54 (m, 2H; CH2CH2O), 3.90 (s, 3H; CH3O), 4.10–4.18 (m, 2H; CH2CH2O), 4.18–4.26
3
(m, 2H; CH3CH2O), 5.70 (s, 1H, HCPyr), 5.72 (s, 1H, HCPyr), 7.05 (AA'BB', J(H,H)=8.9 Hz, 2H;
3
13
OC=CH), 7.78 (AB, J(H,H)=8.9 Hz, 2H; NC=CH); C NMR (CDCl3, 100 MHz): δ=14.0 (CH3CH2C),
14.2 (CH3CH2O), 22.5 (CH3CH2C), 25.5 (CH3CH2CH2), 28.5 (CH3(CH2)2CH2), 31.3 (CH2CH2O), 55.5
(CH3O), 61.7 (CH3CH2O), 66.0 (CH2CH2O), 71.38 (C3/4), 71.43 (C3/4), 77.9 (C2/5), 78.1 (C2/5), 114.5
(OC=CH), 126.4 (NC=CH), 135.5, 135.6, 137.73 (Cfullerene), 137.75 (NC=CH), 137.78, 139.66, 139.72,
139.89, 139.90, 141.7 (2C), 141.88, 141.89, 141.99 (3C), 142.01, 142.17, 142.19, 142.23, 142.24, 142.70
(2C), 142.72 (2C), 143.0, 143.2, 144.39, 144.41, 144.7 (2C), 145.30 (2C), 145.32 (2C), 145.43, 145.47
(2C), 145.49, 145.6, 145.73, 145.75 (2C), 146.09 (2C), 146.11 (2C), 146.23, 146.24, 146.32 (2C), 146.45
(2C), 147.4 (2C), 150.8, 151.0, 152.43, 152.45 (Cfullerene), 158.0 (OC=CH), 168.3 (C=O), 168.4 (C=O); IR
+
(KBr): ν˜=1729, 1746 (C=O); HRMS (ESI): m/z: calcd for C79H28NO5 , 1070.1962 [M+H]+; found
1070.1915; calcd for C79H27NO5Na+, 1092.1781 [M+Na]+; found 1092.1819.
1
Pyrrolofullerene trans-5ad. Reaction time: 18 h. Yield: 38% (26 mg, 0.024 mmol). H NMR (CDCl3,
3
3
400 MHz): δ=0.86 (t, J(H,H)=6.9 Hz, 3H; CH3CH2C), 1.17 (t, J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.11–
1.33 (m, 10H; CH3(CH2)5), 1.50–1.60 (m, 2H; CH2CH2O), 3.87 (s, 3H; CH3O), 4.13–4.21 (m, 2H;
CH2CH2O), 4.21–4.30 (m, 2H; CH3CH2O), 6.50 (s, 1H, HCPyr), 6.51 (s, 1H, HCPyr), 7.02 (AA'BB',
3
3J(H,H)=8.9 Hz, 2H; OC=CH), 7.35 (AB, J(H,H)=8.9 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ
=14.1 (CH3CH2C), 14.2 (CH3CH2O), 22.6 (CH3CH2C), 25.9 (CH3CH2CH2), 28.6 (CH3(CH2)2CH2),
29.13 (CH3(CH2)3CH2), 29.14 (CH3(CH2)4CH2), 31.8 (CH2CH2O), 55.5 (CH3O), 61.7 (CH3CH2O), 66.0
(CH2CH2O), 71.22 (C3/4), 71.24 (C3/4), 74.6 (C2/5), 74.9 (C2/5), 114.8 (OC=CH), 120.9 (NC=CH), 136.3,
136.4, 136.97, 137.0 (2C) (Cfullerene), 138.5 (NC=CH), 139.66, 139.71, 140.16, 140.17, 141.80, 141.81,
16

ACCEPTED MANUSCRIPT
141.82, 141.84, 141.9 (4C), 142.17 (2C), 142.23, 142.24, 142.7 (2C), 142.8 (2C), 143.12, 143.13, 144.51,
144.52, 144.57, 144.58, 145.3 (2C), 145.4 (2C), 145.61, 145.63 (2C), 145.64, 145.7 (3C), 145.77, 145.79,
145.82, 146.1 (4C), 146.40 (2C), 146.44, 146.5, 147.5, 150.65, 150.70, 153.37, 154.41 (Cfullerene), 155.4
(OC=CH), 170.2 (C=O), 170.4 (C=O); IR (KBr): ν˜=1731, 1754 (C=O); HRMS (ESI): m/z: calcd for
+
C81H32NO5 , 1098.2275 [M+H]+; found 1098.2297.
Pyrrolofullerene cis-5ad. Reaction time: 19 h. Yield: 42% (20 mg, 0.018 mmol). 1H NMR (CDCl3, 400
3
3
MHz): δ=0.86 (t, J(H,H)=7.2 Hz, 3H; CH3CH2C), 1.15 (t, J(H,H)=7.2 Hz, 3H; CH3CH2O), 1.16–1.35
(m, 10H; CH3(CH2)5), 1.47–1.55 (m, 2H; CH2CH2O), 3.90 (s, 3H; CH3O), 4.10–4.18 (m, 2H; CH2CH2O),
3
4.19–4.25 (m, 2H; CH3CH2O), 5.70 (s, 1H, HCPyr), 5.72 (s, 1H, HCPyr), 7.05 (AA'BB', J(H,H)=9.0 Hz,
3
2H; OC=CH), 7.77 (AB, J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=14.1
(CH3CH2C), 14.2 (CH3CH2O), 22.6 (CH3CH2C), 25.9 (CH3CH2CH2), 28.6 (CH3(CH2)2CH2), 29.14 (2C,
CH3(CH2)3CH2, CH3(CH2)4CH2), 31.8 (CH2CH2O), 55.5 (CH3O), 61.8 (CH3CH2O), 66.0 (CH2CH2O),
71.40 (C3/4), 71.44 (C3/4), 77.9 (C2/5), 78.1 (C2/5), 114.5 (OC=CH), 126.5 (NC=CH), 135.55, 135.58,
137.75 (Cfullerene), 137.76 (NC=CH), 137.80, 139.68, 139.74, 139.90, 139.91, 141.8 (2C), 141.89, 141.91,
142.00 (3C), 142.03, 142.19 (2C), 142.25 (2C), 142.72, 142.73, 142.74 (2C), 143.1, 143.2, 144.41,
144.42, 144.7 (2C), 145.31 (2C), 145.34 (2C), 145.45, 145.48 (2C), 145.50, 145.6, 145.74, 145.76 (2C),
146.10 (2C), 146.13 (2C), 146.25, 146.26, 146.34 (2C), 146.5 (2C), 147.5 (2C), 150.85, 150.97, 152.43,
152.46 (Cfullerene), 158.0 (OC=CH), 168.3 (C=O), 168.4 (C=O); IR (KBr): ν˜=1728, 1755 (C=O); HRMS
(ESI): m/z: calcd for C81H31NO5Na+, 1120.2094 [M+Na]+; found 1120.2073.
Pyrrolofullerene trans-5bb.
1
Reaction time: 16 h. Yield: 57% (41 mg, 0.038 mmol). H NMR (CDCl3, 400 MHz): δ=0.83 (t,
3J(H,H)=7.3 Hz, 6H; CH3CH2C), 1.20–1.30 (m, 4H; CH3CH2C), 1.49–1.56 (m, 4H; CH2CH2O), 3.88 (s,
3
3H; CH3O), 4.14–4.25 (m, 4H; CH2CH2O), 6.51 (s, 2H, HCPyr), 7.02 (AA'BB', J(H,H)=8.9 Hz, 2H;
3
13
OC=CH), 7.35 (AB, J(H,H)=8.9 Hz, 2H; NC=CH); C NMR (CDCl3, 100 MHz): δ=13.6 (CH3CH2C),
19.0 (CH3CH2C), 30.5 (CH2CH2O), 55.5 (CH3O), 65.5 (CH2CH2O), 71.3 (2C, C3/4), 74.8 (2C, C2/5), 114.8
(OC=CH), 121.0 (NC=CH), 136.4 (2C), 137.0 (2C) (Cfullerene), 138.5 (NC=CH), 139.7 (2C), 140.1 (2C),
141.8 (2C), 141.84 (2C), 141.94 (4C), 142.16 (2C), 142.23 (2C), 142.68 (2C), 142.75 (2C), 143.1 (2C),
144.5 (2C), 144.6 (2C), 145.3 (2C), 145.4 (2C), 145.6 (2C), 145.63 (2C), 145.7 (4C), 145.8 (2C), 146.1
(4C), 146.39 (2C), 146.42 (2C), 147.5 (2C), 150.7 (2C), 153.40 (2C) (Cfullerene), 155.4 (OC=CH), 170.3
17

ACCEPTED MANUSCRIPT
+
(C=O); IR (KBr): ν˜=1728, 1753 (C=O); HRMS (ESI): m/z: calcd for C79H28NO5 , 1070.1962 [M+H]+;
found 1070.2000.
1
Pyrrolofullerene cis-5bb. Reaction time: 5 h. Yield: 25% (18 mg, 0.017 mmol). H NMR (CDCl3, 400
3
MHz): δ=0.81 (t, J(H,H)=7.2 Hz, 6H; CH3CH2C), 1.19–1.29 (m, 4H; CH3CH2C), 1.46–1.53 (m, 4H;
CH2CH2O), 3.90 (s, 3H; CH3O), 4.08–4.21 (m, 4H; CH2CH2O), 5.71 (s, 2H, HCPyr), 7.05 (AA'BB',
3
3J(H,H)=8.9 Hz, 2H; OC=CH), 7.77 (AB, J(H,H)=8.9 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ
=13.6 (CH3CH2C), 19.0 (CH3CH2C), 30.5 (CH2CH2O), 55.5 (CH3O), 65.6 (CH2CH2O), 71.40 (2C, C3/4),
78.2 (2C, C2/5), 114.5 (OC=CH), 126.5 (NC=CH), 135.6 (2C; Cfullerene), 137.8 (3C; 2Cfullerene + NC=CH),
139.7 (2C), 139.9 (2C), 141.8 (2C), 141.9 (2C), 142.01 (2C), 142.03 (2C), 142.2 (2C), 142.3 (2C), 142.72
(2C), 142.73 (2C), 143.1, 143.2, 144.4 (2C), 144.7 (2C), 145.31 (2C), 145.33 (2C), 145.4 (2C), 145.5
(2C), 145.6, 145.76 (2C), 145.78, 146.10 (2C), 146.13 (2C), 146.27 (2C), 146.34 (2C), 146.5 (2C), 147.5
(2C), 151.0 (2C), 152.4 (2C) (Cfullerene), 158.1 (OC=CH), 168.4 (C=O); IR (KBr): ν˜=1727, 1753 (C=O);
+
HRMS (ESI): m/z: calcd for C79H28NO5 , 1070.1962 [M+H]+; found 1070.1941.
Pyrrolofullerene trans-5cc.
1
Reaction time: 19 h. Yield: 50% (38 mg, 0.034 mmol). H NMR (CDCl3, 400 MHz): δ=0.86 (t,
3J(H,H)=7.0 Hz, 6H; CH3CH2C), 1.16–1.29 (m, 12H; CH3(CH2)3C), 1.50–1.58 (m, 4H; CH2CH2O), 3.87
3
(s, 3H; CH3O), 4.10–4.22 (m, 4H; CH2CH2O), 6.51 (s, 2H, HCPyr), 7.02 (AA'BB', J(H,H)=9.0 Hz, 2H;
3
OC=CH), 7.35 (AA'BB', J(H,H)=9.0 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=14.0
(CH3CH2C), 22.5 (CH3CH2C), 25.6 (CH3CH2CH2), 28.5 (CH3(CH2)2CH2), 31.3 (CH2CH2O), 55.4
(CH3O), 65.9 (CH2CH2O), 71.2 (2C, C3/4), 74.8 (2C, C2/5), 114.8 (OC=CH), 121.0 (NC=CH), 136.3 (2C),
137.0 (2C) (Cfullerene), 138.5 (NC=CH), 139.7 (2C), 140.1 (2C), 141.78 (2C), 141.83 (2C), 141.92 (2C),
141.93 (2C), 142.16 (2C), 142.22 (2C), 142.67 (2C), 142.75 (2C), 143.1 (2C), 144.5 (2C), 144.6 (2C),
145.29 (2C), 145.35 (2C), 145.59 (2C), 145.62 (2C), 145.7 (4C), 145.8 (2C), 146.1 (4C), 146.38 (2C),
146.42 (2C), 147.5 (2C), 150.7 (2C), 153.40 (2C) (Cfullerene), 155.4 (OC=CH), 170.3 (C=O); IR (KBr):
ν˜=1728, 1752 (C=O); HRMS (ESI): m/z: calcd for C83H35NO5Na, 1148.2407 [M+Na]+; found 1148.2396.
Pyrrolofullerene cis-5cc.
1
Reaction time: 19 h. Yield: 58% (32 mg, 0.028 mmol). H NMR (CDCl3, 400 MHz): δ=0.84 (t,
3J(H,H)=7.0 Hz, 6H; CH3CH2C), 1.15–1.25 (m, 12H; CH3(CH2)3C), 1.46–1.55 (m, 4H; CH2CH2O), 3.89
3
(s, 3H; CH3O), 4.08–4.20 (m, 4H; CH2CH2O), 5.71 (s, 2H, HCPyr), 7.04 (AA'BB', J(H,H)=8.9 Hz, 2H;
18

ACCEPTED MANUSCRIPT
3
OC=CH), 7.77 (AA'BB', J(H,H)=8.9 Hz, 2H; NC=CH); 13C NMR (CDCl3, 100 MHz):
δ=14.0
(CH3CH2C), 22.5 (CH3CH2C), 25.6 (CH3CH2CH2C), 28.5 (CH3(CH2)2CH2C), 31.3 (CH2CH2O), 55.4
(CH3O), 66.0 (CH2CH2O), 71.4 (2C, C3/4), 78.1 (2C, C2/5), 114.5 (OC=CH), 126.5 (NC=CH), 135.6 (2C;
Cfullerene), 137.8 (3C; 2Cfullerene + NC=CH), 139.7 (2C), 139.9 (2C), 141.7 (2C), 141.9 (2C), 142.00 (2C),
142.03 (2C), 142.20 (2C), 142.25 (2C), 142.71 (2C), 142.73 (2C), 143.1, 143.2, 144.4 (2C), 144.7 (2C),
145.31 (2C), 145.33 (2C), 145.4 (2C), 145.5 (2C), 145.6, 145.7 (3C), 146.10 (2C), 146.12 (2C), 146.27
(2C), 146.34 (2C), 146.5 (2C), 147.5 (2C), 151.0 (2C), 152.4 (2C) (Cfullerene), 158.0 (OC=CH), 168.4
(C=O); IR (KBr): ν˜=1729, 1757 (C=O); HRMS (ESI): m/z: calcd for C83H36NO5 , 1126.2588 [M+H]+;
+
found 1126.2567; calcd for C83H35NO5Na+, 1148.2407 [M+Na]+; found 1148.2398.
General procedure for the synthesis of nitro-porphyrins 6b-e. Iodine (25 mg, 0.1 mmol) was added to
a solution of aldehyde 7 (0.75 mmol), p-nitrophenyldipyrromethane (8) (67 mg, 0.25 mmol) and pyrrole
(34 mg, 0.5 mmol) in DCM (100 ml) at 35 °C and the mixture was stirred for 1¼–3 h (depending on the
substrate, denoted as “condensation time” below). The solution was cooled to room temperature with cold
water bath, chloranil (185 mg, 0.75 mmol) was immediately added and stirring was continued for another
15 min. The reaction mixture was quenched with 10% aq NaOH, washed with water and brine and dried
over Na2SO4. The desiccant was filtered off, the solvent was removed in vacuo and the residue was
separated by column chromatography (silica gel, DCM-hexane, 1:1) to afford products as violet crystals.
5,10,15-tris(4-bromophenyl)-20-(4-nitrophenyl)porphyrin (6b). Condensation time: 2.5 h. Yield: 13%
1
3
(28.6 mg, 0.032 mmol). H NMR (CDCl3, 400 MHz):
δ=-2.84 (s, 2H; NH), 7.92 (AA'BB', J(H,H)=8.3
Hz, 6H; HCAr), 8.08 (AA'BB', 3J(H,H)=8.3 Hz, 6H; HCAr), 8.39 (AA'BB', 3J(H,H)=8.7 Hz, 2H; HCArNO2),
3
3
8.65 (AA'BB', J(H,H)=8.7 Hz, 2H; HCArNO2), 8.77 (AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.87 (s, 4H; HCβ),
8.88 (AB, 3J(H,H)=4.7 Hz, 2H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ
=117.2, 119.3, 119.6, 121.9, 122.8,
126.4, 128.6, 129.7, 130.1, 131.2, 131.6 (br s), 135.1, 135.8, 140.66, 140.68, 147.8, 148.8; IR (KBr):
+
ν
˜=3316 (N-H), 1518, 1339 cm–1 (NO2); HRMS (ESI): m/z: calcd for C44H27Br3N5O2 , 893.9709 [M+H]+;
found: 893.9710.
5,10,15-tris(4-(trifluoromethyl)phenyl)-20-(4-nitrophenyl)porphyrin (6c). Condensation time: 3 h.
1
Yield: 9% (20 mg, 0.023 mmol). H NMR (CDCl3, 400 MHz):
δ
=-2.81 (s, 2H; NH), 8.07 (AA'BB',
3
3J(H,H)=8.1 Hz, 6H; HCAr), 8.35 (AA'BB', 3J(H,H)=8.1 Hz, 6H; HCAr), 8.41 (AA'BB', J(H,H)=8.7 Hz,
19

ACCEPTED MANUSCRIPT
3
3
2H; HCArNO2), 8.67 (AA'BB', J(H,H)=8.7 Hz, 2H; HCArNO2), 8.80 (AB, J(H,H)=4.8 Hz, 2H; HCβ), 8.83
(s, 4H; HCβ), 8.85 (AB, 3J(H,H)=4.8 Hz, 2H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ
=117.7, 119.2, 119.3,
4
1
3
122.0, 123.9 (q, J(C,F)=3.7 Hz), 124.0 (q, J(C,F)=272.1 Hz), 130.4 (q, J(C,F)=32.6 Hz), 131.5 (br s),
2
134.6, 135.1, 145.4 (q, J(C,F)=1.3 Hz), 147.9, 148.6 (CAr); IR (KBr):
ν
˜=3316 (N-H), 1520, 1324 cm–1
+
(NO2); HRMS (ESI): m/z: calcd for C47H27F9N5O2 , 864.2016 [M+H]+; found 864.1997.
5,10,15-tris(4-methylphenyl)-20-(4-nitrophenyl)porphyrin (6d). Condensation time: 1.5 h. Yield: 18%
(31.4 mg, 0.045 mmol). 1H NMR (CDCl3, 400 MHz): δ=-2.72 (s, 2H; NH), 2.73 (s, 9H; CH3), 7.57-7.58
3
(m, 6H; HCAr), 8.10-8.12 (m, 6H; HCAr), 8.39 (AA'BB', J(H,H)=8.7 Hz, 2H; HCArNO2), 8.62 (AA'BB',
3
3J(H,H)=8.7 Hz, 2H; HCArNO2), 8.73 (AB, J(H,H)=4.8 Hz, 2H; HCβ), 8.90 (s, 4H; HCβ) 8.93 (AB,
3J(H,H)=4.8 Hz, 2H; HCβ); HRMS (ESI): m/z: calcd for C47H36N5O2 , 702.2864 [M+H]+; found
+
702.2859. 1H NMR spectrum matches literature data. [34]
5,10,15-tris(4-methoxyphenyl)-20-(4-nitrophenyl)porphyrin (6e). Condensation time: 1¼ h.
Compound was used in the following step without chromatographic separation from porphyrin by-
products.
5,10,15-tris(2,4,6-trimethoxyphenyl)-20-(4-nitrophenyl)porphyrin (6f). Iodine (25 mg, 0.1 mmol) was
added to
a
solution of 2,4,6-trimethoxybenzaldehyde 7f (147 mg, 0.75 mmol), p-
nitrophenyldipyrromethane 8 (67 mg, 0.25 mmol) and pyrrole (34 mg, 0.5 mmol) in CHCl3 (100 ml) at 61
°C and the mixture was mechanically stirred for 1 h. The solution was cooled to 0 °C with ice bath,
chloranil (185 mg, 0.75 mmol) was immediately added and stirring was continued for another 15 min.
The reaction mixture was quenched with 10% aq NaOH, washed with water and brine and dried over
Na2SO4. The desiccant was filtered off, the solvent was removed in vacuo and the residue was separated
by column chromatography (silica gel, CHCl3) to afford porphyrin 6f as violet crystals. Yield: 12% (28.1
1
mg, 0.031 mmol). H NMR (CDCl3, 400 MHz):
δ
=-2.56 (s, 2H; NH), 3.50 (s, 12H; CH3), 3.52 (s, 6H;
CH3), 4.09 (s, 9H; CH3), 6.58 (s, 6H; HCAr), 8.40 (AA'BB', 3J(H,H)=8.7 Hz, 2H; HCArNO2), 8.60 (AA'BB',
3
3J(H,H)=8.7 Hz, 2H; HCArNO2), 8.64 (AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.77 (s, 4H; HCβ) 8.82 (AB,
3J(H,H)=4.7 Hz, 2H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ=55.6, 56.02, 56.03 (CH3), 90.8, 90.9, 111.6,
111.9, 112.7, 112.9, 115.2, 121.6, 129.5 (br s), 130.6 (br s), 135.1, 147.4, 150.1, 161.11, 161.13, 161.78,
20

ACCEPTED MANUSCRIPT
161.82 (CAr); IR (KBr): ν
˜=3320 (N-H), 1520, 1335 cm–1 (NO2); HRMS (ESI): m/z: calcd for
+
C53H48N5O11 , 930.3345 [M+H]+; found 930.3372.
General procedure for the synthesis of amino-porphyrins 12b-f. The mixture of nitro-porphyrin 6 and
tin (II) chloride dihydrate in concentrated hydrochloric acid (5 ml) was stirred under argon at 70 °C for 1
to 5 h, depending on the substrate. The reaction mixture was poured on ice, neutralized with aqueous
ammonia to pH 8, extracted with chloroform, washed with water and dried over Na2SO4. The desiccant
was filtered off, the solvent was removed in vacuo and the residue was separated by column
chromatography (silica gel, DCM) to afford products as violet crystals.
5-(4-aminophenyl)-10,15,20-tris(4-bromophenyl)porphyrin (12b). Reaction time: 5 h. Yield: 41% (15
mg, 0.017 mmol). 1H NMR (CDCl3, 400 MHz): δ=-2.78 (s, 2H; NH), 4.02 (br s, 2H; NH2), 7.05 (AA'BB',
3
3
3J(H,H)=8.4 Hz, 2H; HCArNH2), 7.89 (AA'BB', J(H,H)=8.2 Hz, 6H; HCAr), 7.98 (AA'BB', J(H,H)=8.4
3
Hz, 2H; HCArNH2), 8.07 (AA'BB', J(H,H)=8.2 Hz, 6H; HCAr), 8.82-8.84 (m, 6H; HCβ), 8.98 (AB,
13
3J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100 MHz): δ=113.5, 118.3, 118.6, 121.6, 122.49, 122.50,
129.90, 129.93, 130.9 (br s), 131.2, 132.0, 135.7, 135.8, 140.97, 141.05, 146.2 (CAr); IR (KBr): ν˜=3318
+
(NH), 3374, 3436 cm–1 (NH2); HRMS (ESI): m/z: calcd for C44H29Br3N5 , 863.9968 [M+H]+; found
863.9953. NMR spectra match literature data. [35]
5-(4-aminophenyl)-10,15,20-tris(4-(trifluoromethyl)phenyl)porphyrin (12c). Reaction time: 5 h.
Yield: 6% (14 mg, 0.016 mmol) for two steps from 7c. In a separate experiment, the reduction was
performed at 90 °C under argon atmosphere for 26h and the reaction mixture was treated as in general
technique, which gave porphyrin 12c in 26% yield (based on 6c) along with porphyrin 13.
1
Porphyrin 12c. H NMR (CDCl3, 400 MHz):
δ
=-2.76 (s, 2H; NH), 4.05 (br s, 2H; NH2), 7.08 (AA'BB',
3J(H,H)=8.4 Hz, 2H; HCArNH2), 8.00 (AA'BB', 3J(H,H)=8.4 Hz, 2H; HCArNH2), 8.04 (AA'BB', 3J(H,H)=8.0
Hz, 6H; HCAr), 8.34 (AA'BB', 3J(H,H)=8.0 Hz, 6H; HCAr), 8.78 (AB, 3J(H,H)=4.7 Hz, 2H; HCβ), 8.80 (s,
3
13
4H, HCβ), 9.00 (AB, J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100 MHz):
δ=113.5, 118.0, 118.5,
4
4
1
122.1, 123.72 (q, J(C,F)=3.7 Hz), 123.74 (q, J(C,F)=3.7 Hz), 124.5 (q, J(C,F)=272 Hz), 130.2 (q,
3J(C,F)=32.5 Hz), 130.9 (br s), 131.8, 134.6, 135.8, 145.7 (q, 2J(C,F)=1.4 Hz), 145.8 (q, 2J(C,F)=1.4 Hz),
+
146.3 (CAr); IR (KBr):
ν
˜=3329 (NH), 3360, 3454 cm–1 (NH2); HRMS (ESI): m/z: calcd for C47H29F9N5 ,
834.2274 [M+H]+; found 834.2274.
21

ACCEPTED MANUSCRIPT
Porphyrin 13.5-(4-amino-3-chlorophenyl)-10,15,20-tris(4-(trifluoromethyl)phenyl)porphyrin (13)
NMR 1H (CDCl3, 400 MHz), δ: -2.80 s (2H, NH), 4.47 s (2H, NH2), 7.17 d (1Н, J 8.1 Hz, HCArNH2), 7.92
dd (1H, J1 8.1 Hz, J2 2.0 Hz, HCArNH2), 8.05 d (AA'BB') (6H, J 7.8 Hz, HCAr), 8.12 d (1H, J 2.0 Hz,
HCArNH2), 8.35 d (AA'BB') (6H, J 7.8 Hz, HCAr), 8.79–8.83 m (6H, HCβ), 8.98 d (AB) (2Н, J 4.8 Гц,
HCβ); NMR 13C (CDCl3, 100 МГц), δ: 114.1, 118.1, 118.4, 118.7, 120.1, 123.8, 124.5 (q, J 272 Hz),
130.3 (q, J 32.5 Hz), 130.9 br s, 132.5, 134.0, 134.6, 135.2, 142.9, 145.7;
HRMS (ESI): m/z: calcd for C47H28F9ClN5 , 868.1884 [M+nH]+; found 868.1898.5-(4-aminophenyl)-
+
10,15,20-tris(4-methylphenyl)porphyrin (12d). Reaction time: 5 h. Yield: 84% (26.4 mg, 0.039 mmol).
1H NMR (CDCl3, 400 MHz): δ=-2.71 (s, 2H; NH), 2.72 (s, 9H; CH3), 3.99 (br s, 2H; NH2), 7.05 (AA'BB',
3
3
3J(H,H)=8.4 Hz, 2H; HCArNH2), 7.57 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.01 (AA'BB', J(H,H)=8.4
3
Hz, 2H; HCArNH2), 8.12 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.87-8.89 (m, 6H; HCβ), 8.94 (AB,
3J(H,H)=4.7 Hz, 2H; HCβ); IR (KBr): ν˜=3318 (NH), 3370, 3456 cm–1 (NH2); HRMS (ESI): m/z: calcd for
+
C47H38N5 , 672.3122 [M+H]+; found 672.3125. 1H NMR spectrum matches literature data. [36]
5-(4-aminophenyl)-10,15,20-tris(4-methoxyphenyl)porphyrin (12e). Reaction time: 5 h. Yield: 9%
1
(33.7 mg, 0.047 mmol) for two steps (from 9e). H NMR (CDCl3, 400 MHz): δ=-2.71 (s, 2H; NH), 4.02
3
(br s, 2H; NH2), 4.11 (s, 9H; CH3), 7.07 (AA'BB', J(H,H)=8.4 Hz, 2H; HCArNH2), 7.29 (AA'BB',
3
3J(H,H)=8.7 Hz, 6H; HCAr), 8.00 (AA'BB', 3J(H,H)=8.4 Hz, 2H, HCArNH2)), 8.14 (AA'BB', J(H,H)=8.7
3
13
Hz, 6H; HCAr), 8.86-8.88 (m, 6H; HCβ), 8.94 (AB, J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100
MHz): δ=55.6 (CH3), 112.2, 113.4, 119.5, 119.6, 120.6, 130.9, 132.5, 134.7, 134.8, 135.6, 135.7, 146.0,
+
159.4 (CAr); IR (KBr): ν˜=3318 (NH), 3378, 3460 cm–1 (NH2); HRMS (ESI): m/z: calcd for C47H38N5O3 ,
720.2969 [M+H]+; found 720.2976. 1H NMR spectrum matches literature data.[37]
5-(4-aminophenyl)-10,15,20-tris(2,4,6-trimethoxyphenyl)porphyrin (12f). Reaction time: 1 h. Yield:
55% (8 mg, 0.009 mmol). 1H NMR (CDCl3, 400 MHz):
δ
=-2.56 (s, 2H; NH), 3.48 (s, 12H; CH3), 3.50 (s,
3
6H; CH3), 3.98 (br s, 2H; NH2), 4.09 (s, 9H; CH3), 6.57 (s, 6H; HCAr), 7.02 (AA'BB', J(H,H)=8.2 Hz,
3
2H; HCArNH2) 7.98 (AA'BB', J(H,H)=8.2 Hz, 2H; HCArNH2), 8.72–8.76 (m, 6H; HCβ), 8.83 (AB,
13
3J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100 MHz):
δ
=55.6, 56.1 (CH3), 90.9, 91.0, 110.3, 111.2.
113.0, 113.2, 113.3, 119.3, 130.4 (br s), 133.0, 135.4, 145.7, 161.2, 161.7 (CAr); IR (KBr): ν˜=3320 (NH),
+
3394, 3474 cm–1 (NH2); HRMS (ESI): m/z: calcd for C53H50N5O9 , 900.3603 [M+H]+; found 900.3599.
22

ACCEPTED MANUSCRIPT
General procedure for the synthesis of aziridines 14. A mixture of amino-porphyrin 12 (1 eq), alkyl
glyoxylate 3 (1.33 eq) and anhydrous Na2SO4 (100 mg) in dry benzene (10 ml) was stirred at ambient
temperature until completion of the reaction (controlled by TLC, observed reaction times are reported
below). Sodium sulfate was filtered off and the solvent was removed in vacuo. The residue was dissolved
in dry 1,4-dioxane (2 ml) and 3 droplets of boron trifluoride etherate were added. A solution of alkyl
diazoacetate 4 (1.33 eq) in 1,4-dioxane (0.5 ml) was added dropwise and the mixture was stirred for
another 2.5 h and quenched with 5 droplets of triethylamine. The mixture was diluted with water,
extracted with DCM and dried over Na2SO4. The desiccant was filtered off, the solvent was removed in
vacuo and the residue was separated by column chromatography (silica gel, CHCl3) to afford products as
violet crystals.
Diethyl
cis-1-{4-[10,15,20-tris(4-bromophenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
(14ba). Reaction time: 50 min. Yield: 70% (20.2 mg, 0.020 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.82
3
(s, 2H; NH), 1.45 (t, J(H,H)=7.1 Hz, 6H; CH3), 3.50 (s, 2H; HCaz), 4.43 (q, 3J(H,H)=7.1 Hz, 4H; CH2),
3
7.46 (AA'BB', J(H,H)=8.4 Hz, 2H; HCArN), 7.90 (AA'BB', 6H, HCAr), 8.06–8.08 (m, 6H; HCAr), 8.12
3
13
(AA'BB', J(H,H)=8.4 Hz, 2H; HCArN), 8.83–8.86 (m, 8H; HCβ); C NMR (CDCl3, 100 MHz):
δ=14.2
(CH3), 43.3 (CAz), 62.0 (CH2), 118.5, 118.7, 118.8, 120.0, 122.6, 129.9, 130.0, 131.1 (br s), 131.3, 135.2,
˜=3316 (N-H), 1703 cm–1 (C=O);
135.8, 137.8, 140.87, 140.89, 150.5 (CAr), 167.0 (C=O); IR (KBr):
ν
UV/Vis (PhCN): λmax (lg
ε
)=424 (5.24), 486 (3.24), 518 (3.87), 553 (3.64), 593 (3.38), 650 nm (3.38);
+
HRMS (ESI): m/z: calcd for C52H39Br3N5O4 , 1034.0547 [M+H]+; found 1034.0555.
Diethyl
dicarboxylate (14ca). Reaction time: 50 min. Yield: 52% (11.6 mg, 0.012 mmol). 1H NMR (CDCl3, 400
=-2.81 (s, 2H; NH), 1.44 (t, 3J(H,H)=7.1 Hz, 6H; CH3), 3.49 (s, 2H; HCaz), 4.42 (q, 3J(H,H)=7.1
cis-1-{4-[10,15,20-tris(4-(trifluoromethyl)phenyl)porphyrin-5-yl]phenyl}aziridine-2,3-
MHz):
δ
3
3
Hz, 4H; CH2), 7.47 (AA'BB', J(H,H)=8.4 Hz, 2H; HCArN), 8.05 (AA'BB', J(H,H)=8.0 Hz, 6H; HCAr),
3
3
8.13 (AA'BB', J(H,H)=8.4 Hz, 2H; HCArN), 8.35 (AA'BB', J(H,H)=8.0 Hz, 6H; HCAr), 8.80–8.81 (m,
6H, HCβ), 8.86 (AB, 3J(H,H)=4.9 Hz, 2H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ=14.2 (CH3), 43.3 (CAz),
4
62.1 (CH2), 118.5, 118.6, 118.8, 120.4, 123.8 (q, J(C,F)=3.7 Hz), 124.5 q (1J(C,F)=272 Hz), 130.3 q
(3J(C,F)=32.5 Hz), 131.4 (br s), 134.6, 135.2, 137.6, 145.6, 150.6 (CAr), 167.0 (C=O); IR (KBr):
ν˜=3447
23

ACCEPTED MANUSCRIPT
(N-H), 1712 cm–1 (C=O); UV/Vis (PhCN):
λ
max (lg
ε
)=423 (5.11), 486 (3.05), 517 (3.78), 553 (3.46), 593
+
(3.25), 650 nm (3.19); HRMS (ESI): m/z: calcd for C55H39F9N5O4 , 1004.2853 [M+H]+; found 1004.2824.
Diethyl
trans-1-{4-[10,15,20-tris(4-(trifluoromethyl)phenyl)porphyrin-5-yl]phenyl}aziridine-2,3-
dicarboxylate (trans-14ca). Yield: 10% (2.0 mg, 0.002 mmol). 1H NMR (CDCl3, 400 MHz):
δ
=-2.81 (s,
2H; NH), 1.39 (t, 3J(H,H)=7.1 Hz, 6H; CH3), 3.76 (s, 2H; HCaz), 4.30-4.40 (m, 4H; CH2), 7.82 (AA'BB',
3J(H,H)=8.5 Hz, 2H; HCArN), 8.05 (AA'BB', 3J(H,H)=8.0 Hz, 6H; HCAr), 8.09 (AA'BB', 3J(H,H)=8.5 Hz,
3
3
2H; HCArN), 8.35 (AA'BB', J(H,H)=8.0 Hz, 6H; HCAr), 8.79 (AB, J(H,H)=4.6 Hz, 2H; HCβ), 8.81 (s,
+
4H, HCβ), 8.87 (AB, 3J(H,H)=4.6 Hz, 2H; HCβ); HRMS (ESI): m/z: calcd for C55H39F9N5O4 , 1004.2853
[M+H]+; found 1004.2857.
Diethyl cis-1-{4-[10,15,20-tris(4-methylphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
(14da). Reaction time: 4 h. Yield: 78% (25.4 mg, 0.030 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.77 (s,
3
2H; NH), 1.43 (t, J(H,H)=7.1 Hz, 6H; CH3), 2.72 (s, 9H; ArCH3), 3.48 (s, 2H; HCAz), 4.41 (q,
3
3
3J(H,H)=7.1 Hz, 4H; CH2), 7.44 (AA'BB', J(H,H)=8.4 Hz, 2H; HCArN), 7.56 (AA'BB', J(H,H)=7.8 Hz,
3
6H; HCAr), 8.09–8.13 (m, 2H+6H; HCArN + HCAr), 8.78 (AB, J(H,H)=4.9 Hz, 2H; HCβ), 8.86–8.88 (m,
6H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ=14.2 (CH3), 21.5 (ArCH3), 43.2 (Caz), 62.0 (CH2), 118.4,
119.0, 120.2, 120.3, 127.4, 130.7 (br s), 131.2, 134.5, 135.2, 137.32, 137.33, 138.2, 139.21, 139.23,
˜=3316 (N-H), 1736 cm–1 (C=O); UV/Vis (PhCN):
λmax (lg ε)=424
150.2, (CAr) 167.0 (C=O); IR (KBr):
ν
(5.50), 486 (3.51), 518 (4.10), 555 (3.92), 594 (3.62), 650 nm (3.63); HRMS (ESI): m/z: calcd for
+
C55H48N5O4 , 842.3701 [M+H]+; found 842.3690.
Diethyl cis-1-{4-[10,15,20-tris(4-methoxyphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
(14ea). Reaction time: 24 h. Yield: 58% (24.3 mg, 0.028 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.71 (s,
3
2H; NH), 1.45 (t, J(H,H)=7.1 Hz, 6H; CH3), 3.49 (s, 2H; HCAz), 4.095 (s, 3H; OCH3), 4.098 (s, 6H,
3
3
OCH3), 4.43 (q, J(H,H)=7.1 Hz, 4H; CH2), 7.29 (AA'BB', J(H,H)=8.5 Hz, 6H; HCAr), 7.46 (AA'BB',
3
3J(H,H)=8.2 Hz, 2H; HCArN), 8.12–8.15 (m, 2H+6H; HCArN + HCAr), 8.81 (AB, J(H,H)=4.7 Hz, 2H;
13
HCβ), 8.89–8.90 (m, 6H, HCβ); C NMR (CDCl3, 100 MHz):
δ
=14.2 (CH3), 43.3 (Caz), 55.5 (OCH3),
62.0 (CH2), 112.19, 112.20, 118.4, 119.0, 119.8, 120.0, 130.5, 131.0 (br s), 134.6, 135.2, 135.6, 138.2,
146.6 (br s), 150.3, 159.4 (CAr), 167.0 (C=O); IR (KBr): ν
˜=3316 (N-H), 1742 cm–1 (C=O); UV/Vis
24

ACCEPTED MANUSCRIPT
(PhCN): λmax (lg
ε
)=428 (4.89), 490 (2.95), 523 (3.48), 563 (3.48), 598 (3.03), 657 nm (3.20); HRMS
+
(ESI): calcd for C55H48N5O7 , 890.3548 [M+H]+; found 890.3518.
Diethyl
trans-1-{4-[10,15,20-tris(4-methoxyphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-
dicarboxylate (trans-14ea). Yield: 12% (5.0 mg, 0.006 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.75 (s,
2H; NH), 1.39 (t, 3J(H,H)=7.2 Hz, 6H; CH3), 3.76 (s, 2H; HCAz), 4.11 (s, 9H; OCH3), 4.30-4.40 (m, 4H;
3
3
CH2), 7.30 (AA'BB', J(H,H)=8.3 Hz, 6H; HCAr), 7.31 (AA'BB', J(H,H)=8.2 Hz, 2H; HCArN), 8.10
3
3
(AA'BB', J(H,H)=8.2 Hz, 2H; HCArN), 8.13 (AA'BB', J(H,H)=8.3 Hz, 6H; HCAr), 8.81 (AB,
3J(H,H)=4.9 Hz, 2H; HCβ), 8.85–8.90 (m, 6H; HCβ).
Diethyl
cis-1-{4-[10,15,20-tris(2,4,6-trimethoxyphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-
dicarboxylate (14fa). Reaction time: 24 h. Yield: 9% (2 mg, 0.002 mmol). 1H NMR (CDCl3, 400 MHz):
δ
=-2.61 (s, 2H; NH), 1.43 (t, 3J(H,H)=7.1 Hz, 6H; CH3), 3.45 (s, 2H; HCaz), 3.49 (s, 12H; OCH3), 3.51 (s,
3
6H; OCH3), 4.10 (s, 9H; OCH3), 4.40 (q, J(H,H)=7.1 Hz, 4H; CH2), 6.57 (s, 6H; HCAr), 7.38 (AA'BB',
3J(H,H)=8.3 Hz, 2H; HCArN), 8.09 (AA'BB', 3J(H,H)=8.3 Hz, 2H; HCArN), 8.68 (AB, 3J(H,H)=4.7 Hz, 2H;
HCβ), 8.72 (AB, 3J(H,H)=4.7 Hz, 2H; HCβ), 8.75 (AB, 3J(H,H)=4.7 Hz, 2H; HCβ), 8.76 (AB, 3J(H,H)=4.7
+
Hz, 2H; HCβ); HRMS (ESI): m/z: calcd for C61H60N5O13 , 1070.4182 [M+H]+; found 1070.4150.
Dibutyl cis-1-{4-[10,15,20-tris(4-methylphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
(14db). Reaction time: 4 h. Yield: 49% (53.1 mg, 0.059 mmol). 1H NMR (CDCl3, 400 MHz): δ=-2.78 (s,
3
2H; NH), 1.06 (t, J(H,H)=7.3 Hz, 6H; CH3), 1.50 – 1.59 (m, 4H; CH2), 1.79 – 1.86 (m, 4H; CH2), 2.73
3
(s, 9H, ArCH3), 3.51 (s, 2H, HCaz), 4.38 (t, J(H,H)=6.7 Hz, 4H; O-CH2), 7.45 – 7.49 (m, 2H; HCArN),
3
3
7.58 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.14 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.16 – 8.18 (m,
3
13
2H; HCArN), 8.84 (AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.89 – 8.93 (m, 6H; HCβ); C NMR (CDCl3, 100
MHz): =13.7, 19.1, 21.5, 30.6, 43.3, 65.9, 118.4, 119.0, 120.2, 120.3, 127.4, 130.9, 131.0 (br. s.), 134.5,
δ
135.2, 137.31, 137.33, 138.2, 139.2, 139.3, 146.2 (br. s.), 150.4, 167.1; IR (CHCl3): ν˜=3320 (N-H), 1745
+
cm–1 (C=O); HRMS (ESI): m/z: calcd for C59H56N5O4 , 898.4327 [M+H]+; found 898.4335.
Dihexyl cis-1-{4-[10,15,20-tris(4-methylphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
(14dc). Reaction time: 4 h. Yield: 79% (36.0 mg, 0.04 mmol). 1H NMR (CDCl3, 400 MHz): δ=-2.70 (s,
3
2H; NH), 0.99 (t, J(H,H)=7.0 Hz, 6H; CH3), 1.40 – 1.45 (m, 8H; CH3(CH2)2), 1.45 – 1.55 (m, 4H;
CH2(CH2)2O), 1.79 – 1.88 (m, 4H; CH2CH2O), 2.74 (s, 9H, ArCH3), 3.51 (s, 2H, HCaz), 4.37 (t,
25

ACCEPTED MANUSCRIPT
3J(H,H)=6.9 Hz, 4H; OCH2), 7.47 (AA'BB', 3J(H,H)=8.2 Hz, 2H; HCArN), 7.58 (AA'BB', 3J(H,H)=7.7 Hz,
3
3
6H; HCAr), 8.14 (AA'BB', J(H,H)=7.7 Hz, 6H; HCAr), 8.16 (AA'BB', J(H,H)=8.2 Hz, 2H; HCArN), 8.84
3
(AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.89 – 8.93 (m, 6H; HCβ); 13C NMR (CDCl3, 100 MHz):
δ
=14.0, 21.5,
22.6, 25.5, 28.5, 31.5, 43.3, 66.2, 118.4, 119.0, 120.2, 120.3, 127.4, 131.0 (br. s.), 134.5, 135.2, 137.31,
137.33, 138.2, 139.2, 139.3, 150.4, 167.1; IR (KBr): ν
˜=3317 (N-H), 1752, 1736 cm–1 (C=O); HRMS
+
(ESI): m/z: calcd for C63H64N5O4 , 954.4953 [M+H]+; found 954.4974.
Dioctyl
cis-1-{4-[10,15,20-tris(4-methylphenyl)porphyrin-5-yl]phenyl}aziridine-2,3-dicarboxylate
1
(14dd). Reaction time: 4 h. Yield: 83% (23 mg, 0.022 mmol). H NMR (CDCl3, 400 MHz): δ=-2.76 (s,
2H; NH), 0.92 (t, 3J(H,H)=6.8 Hz, 6H; CH3), 1.30 – 1.40 (m, 20H; CH2), 1.77 – 1.84 (m, 4H; CH2), 2.72
3
(s, 9H; ArCH3), 3.48 (s, 2H, HCaz), 4.34 (t, J(H,H)=6.9 Hz, 4H; O-CH2), 7.42 – 7.46 (m, 2H; HCArN),
3
3
7.57 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.11 (AA'BB', J(H,H)=7.8 Hz, 6H; HCAr), 8.12 – 8.16 (m,
3
13
2H; HCArN), 8.80 (AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.87 – 8.91 (m, 6H; HCβ); C NMR (CDCl3, 100
MHz): =14.1, 21.5, 22.6, 25.9, 28.6, 29.20, 29.25, 31.8, 43.3, 66.2, 118.4, 119.0, 120.2, 120.3, 127.4,
δ
130.9, 131.1 (br. s.), 134.5, 135.2, 137.32, 137.34, 138.2, 139.2, 139.3, 150.4, 167.1; HRMS (ESI): m/z:
+
calcd for C67H72N5O4 , 1010.5579 [M+H]+; found 1010.5595.
General procedure for porphyrin-fullerene dyads 1. A solution of cis-aziridine 14 (1 eq) and fullerene
C60 (2 eq) in chlorobenzene (2 ml) was stirred at 100 °C for 8 h. Reaction mixture was separated by
column chromatography (silica gel, benzene) to afford product as purple-brown solid.
Dyad 1ba (Br, Et). Yield: 28% (4 mg, 0.002 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.80 (s, 2H; NH),
3
1.34 (t, J(H,H)=7.1 Hz, 6H; CH3), 4.42–4.50 (m, 4H; CH2), 6.76 (s, 2H; HCPyr), 7.71 (AA'BB',
3J(H,H)=8.6 Hz, 2H; HCArN), 7.92–7.96 (m, 6H, HCAr), 8.09–8.13 (m, 6H, HCAr), 8.31 (AA'BB',
3
3J(H,H)=8.6 Hz, 2H; HCArN), 8.86 (s, 4H; HCβ), 8.88 (AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.97 (AB,
3J(H,H)=4.7 Hz, 2H; HCβ); 13C NMR (CDCl3, 100 MHz): =14.4 (CH3), 62.2 (CH2), 71.0 (Cq), 74.7
δ
(CH), 117.1, 118.8, 118.9, 120.4, 122.60, 122.62, 130.00, 130.03, 131.2 (br s), 135.6, 135.8, 135.86,
135.90, 136.7, 139.4, 139.9, 140.97, 141.01, 141.4, 141.5 (2C), 141.6, 141.77, 141.80, 142.2, 142.4,
142.7, 142.8 (2C), 144.0, 144.1, 144.9, 145.0, 145.2, 145.3, 145.35, 145.38, 145.41, 145.76, 145.80,
145.9, 146.1, 147.2, 150.1, 153.0 (CAr), 170.2 (C=O); IR (CHCl3): ν
˜=3307 (N-H), 1733 cm–1 (C=O);
26

ACCEPTED MANUSCRIPT
UV/Vis (PhCN): λmax (lg
ε
)=425 (5.53), 489 (3.76), 518 (4.22), 555 (4.02), 593 (3.72), 651 nm (3.64);
+
HRMS (ESI): m/z: calcd for C112H39Br3N5O4 , 1754.0547 [M+H]+; found 1754.0492.
Dyad 1ca (CF3, Et). Yield: 21% (5 mg, 0.003 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.77 (s, 2H; NH),
3
1.34 (t, J(H,H)=7.1 Hz, 6H; CH3), 4.42-4.50 (m, 4H; CH2), 6.77 (s, 2H; HCPyr), 7.73 (AA'BB',
3J(H,H)=8.5 Hz, 2H; HCArN), 8.07-8.10 (m, 6H; HCAr), 8.33 (AA'BB', 3J(H,H)=8.5 Hz, 2H; HCArN), 8.36-
8.40 (m, 6H; HCAr), 8.83–8.85 (m, 6H; HCβ), 9.01 (d, 3J(H,H)=4.6 Hz, 2H; HCβ); 13C NMR (CDCl3, 100
MHz):
δ
=14.4 (CH3), 62.2 (CH2), 71.0 (Cq), 74.7 (CH), 96.1, 117.1, 118.5, 118.8, 120.8, 123.8, 124.5 (q,
3
1J(C,F)=272 Hz), 130.3 (q, J(C,F)=32.5 Hz), 131.3 (br s), 134.6, 135.4, 135.7, 135.9, 136.7, 139.4,
139.9, 141.46, 141.50, 141.6, 141.79, 141.82, 142.3, 142.4, 142.7, 142.8, 144.1, 144.2, 144.9, 145.0,
145.2, 145.3, 145.38, 145.41, 145.42, 145.5, 145.68, 145.72, 145.79, 145.83, 145.9, 146.1, 147.2, 150.1,
153.0 (CAr), 170.2 (C=O); IR (CHCl3):
)=424 (5.89), 487 (4.12), 518 (4.61), 553 (4.36), 593 (4.14), 649 nm (4.01); HRMS (ESI): m/z: calcd for
ν
˜=3313 (N-H), 1736 cm–1 (C=O); UV/Vis (PhCN): λmax (lg
ε
+
C115H39F9N5O4 , 1724.2853 [M+H]+; found 1724.2843.
1
Dyad 1da (CH3, Et). Yield: 42% (17 mg, 0.011 mmol). H NMR (CDCl3, 400 MHz): δ=-2.73 (s, 2H;
3
NH), 1.35 (t, J(H,H)=7.1 Hz, 6H; CH3), 2.73 (s, 6H; ArCH3), 2.74 (s, 3H; ArCH3), 4.42–4.50 (m, 4H;
3
CH2), 6.78 (s, 2H; HCPyr), 7.58–7.61 (m, 6H, HCAr), 7.71 (AA'BB', J(H,H)=8.6 Hz, 2H; HCArN), 8.12–
3
8.15 (m, 6H, HCAr), 8.33 (AA'BB', J(H,H)=8.6 Hz, 2H; HCArN), 8.88 (s, 4H; HCβ) 8.91 (AB,
3
13
3J(H,H)=4.7 Hz, 2H; HCβ), 8.94 (AB, J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100 MHz):
δ=14.4
(CH3), 21.5 (ArCH3), 62.2 (CH2), 71.0 (Cq), 74.7 (CH), 117.0, 119.4, 120.2, 120.3, 127.4, 130.9, 131.2
(br s), 134.5, 134.6, 135.6, 136.0, 136.1, 136.8, 137.4 (2C), 139.3 (2C), 139.5, 139.9, 141.5, 141.57 (2C),
141.64, 141.9, 142.3, 142.5, 142.8, 144.15, 144.23, 145.0, 145.1, 145.2, 145.3, 145.41, 145.45 (2C),
145.5, 145.8, 145.9, 146.0, 146.2, 147.3, 150.2, 153.1 (CAr), 170.3 (C=O); IR (CHCl3): ν˜=3316 (N-H),
1733 cm–1 (C=O); UV/Vis (PhCN):
λ
max (lg
ε
)= 425 (5.05), 487 (3.40), 519 (3.74), 556 (3.61), 595 (3.33),
+
651 nm (3.29); HRMS (ESI): m/z: calcd for: C115H48N5O4 , 1562.3701 [M+H]+; found 1562.3728.
Dyad 1ea (OMe, Et). Yield: 27% (10.2 mg, 0.007 mmol). 1H NMR (CDCl3, 400 MHz):
δ=-2.72 (s, 2H;
3
NH), 1.33 (t, J(H,H)=7.1 Hz, 6H; CH3), 4.12 (s, 6H; OCH3), 4.13 (s, 3H; OCH3), 4.41–4.49 (m, 4H;
3
CH2), 6.74 (s, 2H; HCPyr), 7.31–7.35 (m, 6H, HCAr), 7.71 (AA'BB', J(H,H)=8.6 Hz, 2H; HCArN), 8.15
3
3
(AA'BB', J(H,H)=8.6 Hz, 4H; HCAr), 8.18 (AA'BB', J(H,H)=8.6 Hz, 2H, HCAr), 8.32 (AA'BB',
27

ACCEPTED MANUSCRIPT
3J(H,H)=8.6 Hz, 2H; HCArN), 8.89 (AB, 3J(H,H)=4.6 Hz, 2H; HCβ), 8.90 (AB, 3J(H,H)=4.6 Hz, 2H; HCβ),
3
3
8.91 (AB, J(H,H)=4.6 Hz, 2H; HCβ), 8.93 (AB, J(H,H)=4.6 Hz, 2H; HCβ); 13C NMR (CDCl3, 100
MHz):
δ
=14.4 (CH3), 55.6 (ArOCH3), 62.1 (CH2), 71.0 (Cq), 74.7 (CH), 112.26, 112.27, 117.0, 119.4,
119.9, 120.0, 131.1 (br s), 134.69, 134.71, 135.57, 135.61, 135.8, 136.1, 136.6, 139.3, 139.7, 141.3,
141.35, 141.40, 141.42, 141.6, 141.7, 142.1, 142.3, 142.6, 143.9, 144.0, 144.8, 144.9, 145.0, 145.18,
145.21, 145.3, 145.4, 145.6, 145.67, 145.73, 146.0, 147.1, 150.1, 152.9, 159.4 (CAr), 170.3 (C=O); IR
(KBr):
ν
˜=3316 (N-H), 1733 cm–1 (C=O). UV/Vis (PhCN):
λ
max (lg
ε
)=427 (5.67), 491 (3.85), 521 (4.26),
+
559 (4.20), 596 (3.79), 654 nm (3.85); HRMS (ESI): m/z: calcd for C115H48N5O7 , 1610.3548 [M+H]+;
found 1610.3547.
1
Dyad 1db (CH3, Bu). Yield: 48% (39.1 mg, 0.024 mmol). H NMR (CDCl3, 400 MHz): δ=-2.72 (s, 2H;
3
NH), 0.92 (t, J(H,H)=7.4 Hz, 6H; CH3), 1.40 – 1.48 (m, 4H; CH2), 1.65 – 1.77 (m, 4H; CH2), 2.74 (s,
9H; ArCH3), 4.33 – 4.44 (m, 4H; O-CH2), 6.79 (s, 2H, HCPyr), 7.59 (AA'BB', 3J(H,H)=7.3 Hz, 6H; HCAr),
7.70 (m, 2H; HCArN), 8.11 – 8.16 (m, 6H; HCAr), 8.32 – 8.34 (m, 2H; HCArN), 8.89 (s, 4H; HCβ), 8.92
3
3
13
(AB, J(H,H)=4.7 Hz, 2H; HCβ), 8.95 (AB, J(H,H)=4.7 Hz, 2H; HCβ); C NMR (CDCl3, 100 MHz):
δ
=13.7, 19.2, 21.5, 30.6, 65.9, 71.0, 74.8, 116.9, 119.4, 120.2, 127.4, 130.7, 130.0 (br. s.), 134.5, 135.6,
135.9, 136.1, 136.6, 137.3, 139.35, 139.41, 139.8, 141.4, 141.48, 141.50, 141.70, 141.72, 142.2, 142.3,
142.6, 144.0, 144.1, 144.8, 144.9, 145.16, 145.18, 145.3, 145.4, 145.6, 145.7, 145.8, 146.0, 147.1, 150.2,
+
153.0, 170.5; IR (KBr):
ν
˜=3320 (N-H), 1731 cm–1 (C=O); HRMS (ESI): m/z: calcd for C119H56N5O4 ,
1618.4327 [M+H]+; found 1618.4378.
1
Dyad 1dc (CH3, Hex). Yield: 47% (27 mg, 0.016 mmol). H NMR (CDCl3, 400 MHz): δ=-2.69 (s, 2H;
NH), 0.82 (t, 3J(H,H)=7.2 Hz, 6H; CH3), 1.20 – 1.35 (m, 8H; CH2), 1.35 – 1.46 (m, 4H; CH2), 1.68 – 1.78
(m, 4H; CH2), 2.75 (s, 9H; ArCH3), 4.32 – 4.45 (m, 4H; O-CH2), 6.81 (s, 2H, HCPyr), 7.58-7.63 (m, 6H;
3
3
HCAr), 7.72 (AB, J(H,H)=8.5 Hz, 2H; HCArN), 8.11 – 8.18 (m, 6H; HCAr), 8.34 (AB, J(H,H)=8.5 Hz,
3
3
2H; HCArN), 8.90 (s, 4H; HCβ), 8.93 (AB, J(H,H)=4.8 Hz, 2H; HCβ), 8.97 (AB, J(H,H)=4.8 Hz, 2H;
HCβ); 13C NMR (CDCl3, 100 MHz):
δ
=14.0, 21.5, 22.6, 25.8, 28.7, 31.4, 66.3, 71.1, 74.9, 117.0, 119.4,
120.2, 127.4, 131.0 (br. s.), 134.5, 135.6, 136.1, 136.8, 137.3, 139.3, 139.6, 140.0, 141.55, 141.66,
141.69, 141.9, 142.4, 142.5, 142.9, 144.2, 144.3, 145.0, 145.1, 145.2, 145.4, 145.5, 145.9, 146.1, 146.2,
28