Synergistic Effect of Tetraaryl Porphyrins Containing Corannulene and Other Polycyclic Aromatic Fragments as Hosts for Fullerenes. Impact of C60 in a Statistically Distributed Mixture of Atropisomers

Article abstract of DOI:10.1021/acs.joc.6b00454

Symmetric meso-tetraarylporphyrins bearing phenanthrene, pyrene, and corannulene moieties in meta positions have been synthesized in a straightforward procedure under microwave irradiation by quadruple Suzuki-Miyaura reactions. Their ¹H NMR spectra showed the typical pattern of four atropisomers distributed according to their statistical ratio not properly separable due to their fast isomerization. Their ability to bind buckminsterfullerene has been tested with the whole mixture, and different behaviors have been found, α₄ isomer corannulene-substituted porphyrins being the best hosts in the family.

Full text of DOI:10.1021/acs.joc.6b00454

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Note
Synergistic effect of tetraaryl porphyrins containing corannulene
and other polycyclic aromatic fragments as host for fullerenes.
Impact of C60 in a statistically distributed mixture of atropisomers.
Celedonio M. Alvarez, Héctor Barbero, Sergio Ferrero, and Daniel Miguel
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00454 • Publication Date (Web): 16 Jun 2016
Downloaded from http://pubs.acs.org on June 19, 2016
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Synergistic effect of tetraaryl porphyrins containing corannulene
and other polycyclic aromatic fragments as host for fullerenes. Im-
pact of C60 in a statistically distributed mixture of atropisomers.
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Celedonio M. Álvarez,* Héctor Barbero, Sergio Ferrero and Daniel Miguel
GIR MIOMeT, IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, Eꢀ47011, Valladolid,
Spain
ABSTRACT: Symmetric mesoꢀtetraaryl porphyrins bearing phenanthrene, pyrene and corannulene moieties in meta positions have
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been synthesized in a straightforward procedure under microwave irradiation by quadruple SuzukiꢀMiyaura reactions. Their H
NMR spectra showed the typical pattern of 4 atropisomers distributed accordingly to their statistical ratio not properly separable
due to their fast isomerization. Their ability to bind Buckminsterfullerene has been tested with the whole mixture and different
behaviors have been found, being α4 isomer corannuleneꢀsubstituted porphyrins the best hosts in the family.
Porphyrins are a vast family of naturally occurring macrocycles having multiple functions in living beings. Many applications have
been developed1 by using these astounding architectures, being one of them their use as hosts for fullerenes, especially for C60,
which is considered a very promising and potentially useful building block for new electronic devices.2 The main approach in order
to bind fullerenes by means of supramolecular forces has consisted of building structures with more than one porphyrin yielding
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molecular tweezers, trimers or strapped porphyrins leading to very high affinities.3 However, there are not examples in which a
single porphyrin shows binding abilities to C60 beyond cocrystallization,4 except for the work of Ishizuma and Kojima et al.5 whose
curved porphyrins were able to do such task.
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Under our research line regarding corannuleneꢀfunctionalized molecules to act as fullerenes hosts,6 we decided to link this molecule
to a porphyrin scaffold in order to sum association abilities of corannulene7 to the porphyrin core. Additionally, other planar aroꢀ
matic fragments were linked to the porphyrin core as well and tested for comparison purposes.
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Compounds 2HP1 and ZnP1 could be synthesized with the help of a microwave reactor with a modified method reported elseꢀ
where.8 From that point we reasoned that Suzuki reaction from borylated polyaromatic fragments with known Schlenk techniques
would lead to 2HP2a,b,c and ZnP2a,b,c families (see Schemes S1ꢀS3 for a description of all routes attempted), however a great
amount of homocoupling byꢀproducts were obtained as well as nonꢀnegligible amount of porphyrins with Pd in their cavity (Figures
S57ꢀS59). This mixture leads to a very cumbersome chromatographic separations. So we turned to a synthetic route in which pinaꢀ
col boronate fragment was located in the porphyrin core and reacted with brominated polyaromatic fragments as depicted in
Scheme 1. In order to get free base porphyrins, removal of Zn atom was preferred. Additionally, all coupling reactions were carried
out with microwave irradiation because reaction times were significantly improved.9
SCHEME 1 Best synthetic route towards porphyrin targets
Reagents and conditions: a) Propionic acid, nitrobenzene, MW, 200 ºC; b) Zn(OAc)2·2H2O, CHCl3, MW, 120 ºC; c) B2pin2, [PdCl2(dppf)], AcOK, dioxane,
MW. d) [PdCl2(dppf)], tBuONa, toluene, MW; e) CF3CO2H.
New porphyrins were fully characterized by spectroscopic methods. All of them have expected Soret bands around 430 nm and Q
bands between 500 and 600 nm (Figures S67ꢀS70) in their absorption spectra. 1H NMR spectra show clearly the presence of statisꢀ
tically distributed atropisomers,10 especially for H6 singlets (see Supporting Information for numbering of the system), as depicted
in Figure 1. Attempts to separate each atropisomer individually, both by preparative methods or HPLC, were unfruitful, even
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though HPLC chromatogram showed clearly four separated peaks. NMR tests of each fraction indicated the presence of the mixture
showing that isomerization occurred even at low temperature.11
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FIGURE 1 Schematic representation of the atropisomers and their statistical distribution.
Notwithstanding such limitation, we decided to analyze the ability of the whole mixture to bind C60 and, at the same time, to obꢀ
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serve potential differences among all individual atropisomers. H NMR was chosen to be the technique because, unlike UV/Vis
experiments, it is able to distinguish all isomers. This was complemented by Mass Spectrometry experiments. Before performing
any titration, we firstly attempted to know the stoichiometry of the adduct. Job plots were carried out for all compounds, however,
only H1 was observed as an average signal due to its inherent broadness, so only 2HP2 set could be properly analyzed (Figures
S77ꢀS79). Surprisingly, all porphyrins showed 1:1 adduct formation and this was confirmed by MS (Figures S60ꢀ66). We assumed
that this stoichiometry was maintained in ZnP2 derivatives because only 1:1 adducts were located in all mass spectra. Titrations of
phenanthrene and pyreneꢀsubstituted porphyrins ZnP2a,b and 2HP2a,b provided several little chemical shifts changes, indicating
supramolecular association for some atropisomers. This was not expected because it is known that compounds bearing this type of
PAHs do not establish adducts with C60 due to their low shape complementarity,12 this suggests that the hostꢀguest formation is
taking place due mainly to the porphyrin core.13 On the other hand, corannulene derivatives, 2HP2c and Zn2P2c, showed great
chemical shift changes, except for one atropisomer. Interestingly, we observed the same pattern in all chemical shift changes, and
especially for H1, H2 and H6 hydrogens in all compounds. This suggests a similar behavior.
In order to assign signals for each atropisomer, we carried out computational studies14 for 2HP2 set of isomers and the optimized
structures provided interesting features. Intramolecular association of PAHs units at the same side is so preferred that leads to deꢀ
formation of the porphyrin reaching a saddleꢀlike conformation for the most stable isomers, α4. On the other hand, αβαβ isomers
are the least stable and PAHs moieties are not interacting among them. This lack of interaction could be the reason for the low
stability. Thus, a quasiꢀplanar porphyrin core as well as vague preorganization as host are observed, as seen in Figure 2 for 2HP2c.
The other atropisomers present intermediate situations and stabilities (Tables S1ꢀS3 and Figures S80ꢀS91).
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FIGURE 2 Optimized structures of: (a) αβαβ2HP2c; (b) α42HP2c.
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Theoretical NMR predictions for H6 proton signal in 2HP2c gave, from lowest to highest field, this order: αβαβ < α3β(bottom) <
α3β(outer) < α2β2 < α3β(inner) < α4 as depicted in Figure 3.
FIGURE 3 Simulated H6 resonance in toluene of 2HP2c pattern and theoretical assignments with an integral ratio of 1:1:2:2:1:1.
From that starting point, we followed the evolution of singlet H6 during titration with C60. Simultaneously, the evolution of singlet
H2 proton (βꢀpyrrole) could be traced due to a great disruption observed upon addition of initial aliquots. It must be noted that these
H2 protons are all equivalent for αβαβ and α4 isomers, but there are two nonequivalent protons for α3β and α2β2 isomers. Additionꢀ
ally, this procedure was applied for ZnP2c compound to check similar behaviors and reproducibility.
First of all, α3β(bottom) and α3β(outer) predicted H6 chemical shifts changes were followed and their curves fitted yielding equal
constants. However, α3β(inner) H6 could not be followed due to spectral overlap with α2β2 H6 during titration. Once located and
determined those proton signals, another atropisomer could be directly assigned, α2β2 . Its H6 signal is the one left with a ratio of 2,
(Figure 3). The titration for this atropisomer gave a very different constant (threeꢀfold increase for 2HP2c and one order of magniꢀ
tude in ZnP2c). So, at this point, just two minor signals, corresponding to αβαβ and α4 isomers, were left to be matched with comꢀ
putational results. It was assumed that theoretical assignment was correct due to the accuracy observed for the other predictions.
Unfortunately, H6 proton for α4 atropisomer could not be followed because it got broadened after the first addition. These findings
are all gathered in Figure 4.
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Figure 4: 1H NMR showing H6 chemical shifts in deuterated toluene of ZnP2c (up) and 2HP2c (bottom) upon addition of aliquots
of C60. Colored domains enclose the assignments according to the pattern established in Figure 3. Note the overlap of H6 (inner)
proton in α3β isomer with H6 proton in α2β2 isomer and the 'disappearance' of H6 proton in α4 isomer after the first addition.
On the other hand, H2 protons (βꢀpyrrole) evolution was followed as well in order to identify each signal in the course of titration
experiments. Each chemical shift change observed was systematically subjected to a fitting process covering all possibilities until
association constants matched those previously estimated for H6. Fortunately, signals corresponding to αβαβ and α3β isomers,
especially for ZnP2c, were located easily due to the lack of spectral overlap during titration. Spectral changes of α2β2 atropisomer
(which, depending on FID processing, can be seen as one big broad signal or two resolved shifts) were also easily followed. A
crossover with a broad chemical shift change that unexpectedly raised in the beginning of the titration was observed in the last
additions. This new signal was accepted to come from the remaining α4 atropisomer, so we carried out the same fitting procedure,
resulting in a new association constant. This discussion is shown in Figure 5.15
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Figure 5: 1H NMR showing H2 chemical shifts in deuterated toluene of ZnP2c (up) and 2HP2c (bottom) upon addition of aliquots
of C60.Colored domains enclose the assignments according to the pattern established in Figure 3. Note the crossover between green
and yellow domains.
This protocol was applied for phenanthrene and pyreneꢀsubstituted porphyrins (ZnP2a, ZnP2b, 2HP2a and 2HP2b) resulting in
very similar findings, but less pronounced changes of chemical shifts were obserbed.
These results were not consistent with our initial assumptions, because we thought that αβαβ2HP2c ideally had a good preorganiꢀ
zation in a double tweezer mode and could lead to moderate association. However, we did not find chemical shift changes big
enough to be measured in any of all αβαβ atropisomers. Furthermore, as stated previously, structures of optimized minima clearly
showed that preorganization of this atropisomer to adapt fullerene shape is not efficient, while other atropisomers preorganizations
are much more efficient.
The best results were obtained for corannuleneꢀfunctionalized porphyrins, especially ZnP2c. α4ZnP2c and α2β2ZnP2c showed the
best association constants in the mixture of atropisomers, which are 22330 and 12140 Mꢀ1, respectively. The presence of the metal
favors supramolecular adduct formation.
As commented above, 2HP2 (freeꢀbase) porphyrins possess average signals coming from internal hydrogens (H1) and could be
followed during titration experiments., so an average association constant could be given, concluding that our corannuleneꢀbased
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porphyrins are very good host for C60 because their association constants are one order of magnitude better than those bearing plaꢀ
nar polycyclic hydrocarbons. In light of these findings, synergy between a porphyrin core and well adapted corannulene groups to
bind Buckminsterfullerene is suggested. All constants estimated are gathered in Table 1.
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TABLE 1. Summary of Ka of new porphyrins vs C60 estimated in tolueneꢀd8.
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ZnP2a
180
0d
2HP2a
N/Aa
0d
ZnP2b
790
0d
2HP2b
1180
540
ZnP2c
22330b
1730
2HP2c
7700b
α4
α3β
1820
240
0 d
130
0 d
690
0 d
1240
0 d
12140
0 d
5890
0 d
(5.4±0.2) 103
α2β2
αβαβ
Average
N/Ac (4.5±0.05)102 N/Ac
(4.6±0.05)102 N/Ac
a Could not be estimated due to spectral overlap. b Determined from ꢀδ change of H2 βꢀpyrrole protons only. Not measured (no
c
average signal). d ꢀδ very low to estimate a constant reasonably.
In summary, a set of six tetrasubstituted porphyrins in meso positions with polycyclic aromatic hydrocarbons have been prepared
very easily by using microwave irradiation. The existence of a statistically distributed mixture of atropisomers was identified by
NMR and assigned with the help of a combination of titration experiments of the whole mixture with C60 and computational studꢀ
ies. Complexation studies were carried out and a great difference was observed for each individual atropisomer, being the best
hosts, α4 and α2β2 porphyrins bearing corannulene as substituent whose crude estimated association constants were among the
highest of those reported for singleꢀporphyrin hosts. Theoretical calculations have suggested that preorganization of corannulene
moieties in a tweezerꢀlike fashion are crucial. This initial research has opened new possibilities to design more complex 'picket
fence' (α4 atropisomer) porphyrins having multiple corannulene fragments with the objective to increase their affinity towards fullꢀ
erenes thanks to a synergy between porphyrin and nonꢀplanar polycyclic hydrocarbon.
EXPERIMENTAL SECTION
All reagents were purchased from regular vendors and used without further purification. Solvents were either used as purchased or
dried according to procedures described elsewhere.16 Microwave reactions were carried out with an Anton Paar Monowave 300
Reactor. Column chromatography was carried out using Silica gel 60 (particle size 0.040ꢀ0.063 mm; 230ꢀ400 mesh) as the stationꢀ
ary phase and TLC were performed on precoated silica gel plates (0.25 mm thick, 60 F254) and observed under UV light and/or
dipping in anisaldehyde. NMR spectra were recorded in 400 MHz and 500 MHz instruments. 1H and 13C NMR chemical shifts (δ)
are reported in parts per million (ppm) and are referenced to TMS, using solvents as an internal reference. Coupling constants (J)
are reported in hertz (Hz). Standard abbreviations used to indicate multiplicity: s = singlet, d = doublet, t = triplet, m = multiplet, br
= broad. 13C{1H} spectra for all porphyrin derivatives had to be recorded with the following acquisition parameters due to their fast
relaxation: 90º pulse, relaxation delay of 5ms and acquisition time of 250ms. H and 13C assignments were performed by utilizing
1
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2D NMR methods band selective HSQC and band selective HMBC. High resolution mass spectra were recorded with a MALDIꢀ
TOF system with N2 laser (337 nm, pulse energy 100 ꢁJ, 1 ns). Acceleration voltage of 19 kV and reflector positive mode were
used. UV/Vis absorption spectra wavelengths (λ) are reported in nanometers (nm) and molar absorption coefficient (ε) are reported
in Mꢀ1·cmꢀ1 units. Corannulene and bromocorannulene were prepared according to literature procedures.17
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General method for polyaromatic boronate esters preparation: Bromoarene (0.4 mmol), bis(pinacolato)diboron (152 mg,
0.6 mmol), [PdCl2(dppf)] (15 mg, 0.02 mmol) and AcOK (118 mg, 1.2 mmol) were mixed in a Schlenk flask under inert atmosꢀ
phere. 2 mL of dry dioxane were added and the mixture was degassed. Then, it was refluxed overnight. Solvent was removed under
vacuum before a purification by column chromatography with SiO2 gel, hexane/AcOEt (5:1 for 9ꢀ( pinacolatoboron)phenanthrene)
(1), (20:1 for 1ꢀ(pinacolatoboron)pyrene (2) and 1ꢀ(pinacolatoboron) corannulene) (3). Yields over 85%. Spectral data are in
agreement to those published.18
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2HP1: pyrrole (277 ꢁl, 4 mmol), 3ꢀbromobenzaldehyde (468.0 ꢁl, 4 mmol), propionic acid (12 ml, 160 mmol) and nitrobenzene (7
ml, 68 mmol) were mixed in a sealed reactor specifically designed for microwave irradiation. The mixture was stirred inside miꢀ
crowave reactor at 200 ºC for 15 minutes (a pressure of 5 bar was achieved). The resulting black crude obtained after cooling at
room temperature was taken up and MeOH was added (50 mL), precipitating a purple solid. Filtered in a Büchner funnel and
washed thoroughly with more MeOH. The solid was collected, placed in an oven and kept under reduced pressure (200 ºC, 24
hours, 50 mbar) to finally get pure 2HP1 whose spectroscopic data agree with those reported19 (0.295 g, 32% yield).
ZnP1: 2HP1 (0.25 0g, 0.268 mmol) and Zn(AcO)2·2H2O (0.294 g, 1.34 mmol) were mixed in a sealed reactor specifically deꢀ
signed for microwave irradiation and dissolved in 12 ml of CHCl3. The solution was stirred at 130 ºC for 2.5 hours (a pressure of 6
bar was achieved). Once finished, solvent was removed in vacuo. The resulting solid was washed several times with water and
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dried to get a purple solid corresponding to ZnP1 (0.203 g, 76 % yield). H NMR (500 MHz, CDCl3) δ 8.96 (s, 2H, H2), 8.38 (s,
1H, H6), 8.16 (br, 1H, H10), 7.95 (d, J = 8.2 Hz, 1H, H8), 7.64 (d, J = 8.2 Hz, 1H, H9). 13C{1H} NMR (101 MHz, CDCl3) δ 150.0
(C3), 144.5 (C5), 137.1 (C6), 132.9 (C10), 132.1 (C2), 130.9 (C8), 128.0 (C9), 110.0 (C4). HRMS (MALDIꢀTOF): m/z = 987.8010
[M]+ (calcd. 987.8026 for C44H24Br4N4Zn). UV/Vis (toluene) λ 404 (ε: 17033), 424 (ε: 195165), 550 (ε: 10220), 588 (ε: 2308).
ZnP2: ZnP1 (80 mg, 0.08 mmol), bis(pinacolato)diboron (122 mg, 0.48 mmol), [PdCl2(dppf)] (12 mg, 0.016 mmol) and AcOK
(94 mg, 0.96 mmol) were mixed in a reactor specifically designed for microwave irradiation inside a twoꢀnecked roundꢀbottom
flask in order to put the mixture under inert atmosphere. 1.8 mL of dry dioxane and 116 ꢁL of dry pyridine were added and the
mixture was degassed before sealing the vial. Then, it was stirred inside microwave reactor at 150 ºC for 2 hours (a pressure of 3
bar was achieved). Solvent was removed under vacuum and the resulting dark residue was redissolved in a mixture of
CHCl3/MeOH 95:5 before quickly passing it through a plug of SiO2 gel. The deep red filtrate was concentrated to afford a purple
solid (85 mg, 90% yield). 1H NMR (500 MHz, CDCl3) δ 8.91 (s, 2H, H2), 8.66 (br, 1H, H6), 8.31 (d, J = 7.5 Hz, 1H, H10), 8.21 (d, J
= 7.5 Hz, 1H, H8), 7.76 (t, J = 7.5 Hz, 1H, H9), 1.38 (s, 12H, H12). 13C{1H} NMR (126 MHz, CDCl3) δ 150.3 (C3), 142.5 (C5), 140.5
(C6), 137.1 (C10), 133.9 (C8), 132.1 (C2), 127.8 (C7), 126.1 (C9), 121.1 (C4), 84.1 (C11), 25.1 (C12). HRMS (MALDIꢀTOF): m/z =
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1180.5043 [M]+ (calcd. 1180.5047 for C68H72B4N4O8Zn). UV/Vis (toluene) λ 402 (ε: 17927), 425 (ε: 324268), 550 (ε: 16098), 590
(ε: 3049).
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General procedure for quadruple C-C cross coupling: Porphyrin derivative (2HP1, ZnP1 or ZnP2) (0.02 mmol), PAH deꢀ
rivative (9ꢀBromophenanthrene, 1ꢀBromopyrene, Bromocorannulene, 1, 2 or 3) (0.08 mmol), [PdCl2(dppf)] (11.7 mg, 0.016 mmol)
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and BuONa (23.1 mg, 0.24 mmol) were mixed in a reactor specifically designed for microwave irradiation inside a twoꢀnecked
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roundꢀbottom flask in order to put the mixture under inert atmosphere. 2.2 ml of dry and degassed toluene were added as well as 30
ꢁL of dry pyridine before sealing the vial. The mixture was then sonicated thoroughly and stirred vigorously inside microwave
reactor at 130 ºC for 1 hour (a pressure of 3 bar was achieved). After such time, solvent was removed under vacuum and the black
residue was subjected to a purification by column chromatography yielding the pure purple solid corresponding with the expected
product.
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ZnP2a: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (10:1 ꢀ 5:1 ꢀ 1:1 ꢀ AcOEt). 98% yield. 1H NMR (500
MHz, CDCl3) δ: 9.20 (s, 2H, H2), 8.85 – 8.75 (m, 1H, H17), 8.75 – 8.65 (m, 1H, H20), 8.50 – 8.41 (m, 1H, H6), 8.41 – 8.35 (m, 1H,
H23), 8.35 – 8.27 (m, 1H, H10), 8.05 – 7.96 (m, 2H, H12+H8), 7.96 – 7.86 (m, 2H, H14+H9), 7.73 – 7.51 (m, 4H, H16+H21+H15+H22).
13C{1H} NMR (126 MHz, CDCl3) δ: 150.4 (C3), 143.1 (C5), 139.2 (C7), 138.7 (C11), 136.4 (C6), 133.7 (C10), 132.3 (C2), 131.7 (C24),
131.4 (C19), 130.9 (C13), 130.2 (C18), 129.4 (C8), 128.8 (C14), 128.2 (C12), 127.1 – 126.7 (C9+C15+C16+C21+C22+C23), 123.1 (C17),
122.6 (C20), 121.1 (C4). HRMS (MALDI): m/z = 1380.4075 [M]+ (calcd. 1380.4104 for C100H60N4Zn). UV/Vis (toluene) λ 300 (ε:
38806), 400 (ε: 14179), 426 (ε: 211940), 552 (ε: 11642), 590 (ε: 4627).
ZnP2b: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (5:1 ꢀ 1:1 ꢀ AcOEt). 92% yield. 1H NMR (500 MHz,
CDCl3) δ: 9.26 – 9.21 (m, 2H, H2), 8.68 – 8.59 (m, 1H, H23), 8.59 – 8.47 (m, 1H, H6), 8.45 – 8.35 (m, 1H, H10), 8.35 – 8.22 (m, 2H,
H12+H13), 8.22 – 7.86 (m, 8H, H22+H8+H9+H19+H16+H18+H20+H15). 13C{1H} NMR (126 MHz, CDCl3) δ: 150.4 (C3), 143.3 (C5),
139.5 (C7), 137.6 (C11), 137.0 (C6), 133.6 (C10), 132.2 (C2), 131.6 – 130.7 (C26+C17+C21+C14), 129.8 (C8), 128.9 (C24), 128.1 (C12),
127.8 (C22 or C16), 127.5 (C22 or C16), 126.7 (C9), 126.0 (C19), 125.4 (C23), 125.2 – 124.8 (C13+C15+C18+C20+C25), 121.0 (C4).
HRMS (MALDI): m/z = 1476.4104 [M]+ (calcd. 1476.4104 for C108H60N4Zn). UV/Vis (toluene) λ 329 (ε: 36774), 347 (ε: 48548),
405 (ε: 20806), 428 (ε: 195161), 551 (ε: 12903), 591 (ε: 4839).
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ZnP2c: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (5:1 ꢀ 1:1 – AcOEt – CHCl3) 85% yield. H NMR
(500 MHz, CDCl3) δ: 9.18 (s, 2H, H2), 8.74 – 8.65 (m, 1H, H6), 8.42 – 8.31 (m, 1H, H10), 8.28 – 8.21 (m, 1H, H8), 8.21 – 8.11 (m,
2H, H24+H12), 8.00 – 7.90 (m, 1H, H9), 7.90 – 7.72 (m, 7H, H14+H15+H17+H18+H20+H21+H23).13C{1H} NMR (126 MHz, CDCl3) δ:
150.3 (C3), 145.2 (C25 or C27), 143.5 (C5), 137.7 (C7), 136.2 (C6), 133.9 (C10), 132.1 (C2), 123.0 (C25 or C27), 129.0 (C8), 127.5 (C24),
127.2 – 126.7 (C9 + C14 + C15 + C17 + C18 + C20 + C21 + C23), 126.2 (C12), 120.9 (C4). HRMS (MALDI): m/z = 1668,4133 [M]+ (calcd.
1668,4104 for C124H60N4Zn). UV/Vis (toluene) λ 296 (ε: 146667), 400 (ε: 27407), 427 (ε: 438889), 551 (ε: 22037), 590 (ε: 4630).
General procedure for Zn removal: Zinc porphyrin derivatives (ZnP2a, ZnP2b or ZnP2c) (0.02 mmol) were dissolved in 2
mL of DCM. To the deep red solution, 2 ml of CF3CO2H were added at once and the color turned immediately to green. The mixꢀ
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ture was stirred at room temperature overnight. Then, it was diluted with 6 mL of DCM and a saturated solution of Na2CO3 in water
was added portionwise with vigorous stirring until the evolution of gas ceased and the organic layer became deep red again. It was
separated from the aqueous phase and washed three times with water. The solution was finally dried with anhydrous MgSO4, filꢀ
tered and concentrated to afford the expected demetalated product as a purple solid.
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2HP2a: from quadruple cross coupling of 1 and 2HP1: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (10:1
ꢀ 5:1 ꢀ 1:1 ꢀ AcOEt). 73% yield. From demetalation of ZnP2a, quantitative yield. 1H NMR (500 MHz, CDCl3) δ: 9.10 (s, 2H, H2),
8.85 – 8.76 (m, 1H, H17), 8.76 – 8.66 (m, 1H, H20), 8.50 – 8.40 (m, 1H, H6), 8.40 – 8.26 (m, 2H, H23+H10), 8.06 – 7.95 (m, 2H,
H12+H8), 7.95 – 7.85 (m, 2H, H23+H8), 7.75 – 7.56 (m, 4H, H22+H21+H15+H16), ꢀ2.70 (br, 0.5H, H1). 13C{1H} NMR (126 MHz,
CDCl3) δ: 142.4 (C5) , 139.4 (C7), 138.6 (C11), 136.4 (C6), 133.9 (C10), 131.7 (C24), 131.4 (C13), 130.9 (C19), 130.2 (C18), 129.6 (C8),
128.9 (C14), 128.2 (C12), 127.0 (C23), 126.8 ꢀ 126.7 (C9+C22+C16+C21+C15), 123.2 (C17), 122.7 (C20), 120.2 (C4). HRMS (MALDI):
m/z = 1318.4946 [M]+ (calcd. 1318.4969 for C100H62N4). UV/Vis (toluene) λ 300 (ε: 35455), 400 (ε: 34364), 422 (ε: 250727), 517
(ε: 11091), 551 (ε: 5091).
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2HP2b: from quadruple cross coupling of 2 and 2HP1: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (5:1 ꢀ
1:1 ꢀ AcOEt). 57% yield. From demetalation of ZnP2b, quantitative yield. 1H NMR (500 MHz, CDCl3) δ: 9.15 (s, 2H, H2), 8.68 –
8.56 (m, 1H, H23), 8.56 – 8.48 (m, 1H, H6), 8.45 – 8.34 (m, 1H, H10), 8.34 – 8.23 (m, 2H, H12+H13), 8.23 – 7.88 (m, 8H,
H19+H9+H16+H8+H20+H18+H15+H22), ꢀ2.65 (br, 0.5H, H1). 13C{1H} NMR (126 MHz, CDCl3) δ: 142.5 (C5), 139.8 (C7), 137.4 (C11),
137.0 (C6), 133.7 (C10), 131.6 – 130.7 (C26+C17+C21+C14), 130.2 (C8), 128.9 (C24), 128.1 (C12), 127.9 (C22), 127.6 (C16), 126.9 (C9),
126.1 (C19), 125.3 – 124.9 (C13+C15+C18+C20+C23+C25), 120.2 (C4). HRMS (MALDI): m/z = 1414.4981 [M]+ (calcd. 1414.4969 for
C108H62N4). UV/Vis (toluene) λ 333 (ε: 28462), 348 (ε: 35692), 405 (ε: 19846), 424 (ε: 93077), 517 (ε: 6923), 551 (ε: 4769).
2HP2c: from quadruple cross coupling of 3 and 2HP1: chromatography conditions: SiO2 gel, hexane/AcOEt gradient elution (5:1 ꢀ
1:1 ꢀ AcOEt ꢀ CHCl3). 47% yield. From demetalation of ZnP2c, quantitative yield. 1H NMR (500 MHz, CDCl3) δ: 9.07 (s, 2H, H2),
8.72 – 8.63 (m, 1H, H6), 8.41 – 8.31 (m, 1H, H10), 8.27 – 8.21 (m, 1H, H8), 8.20 – 8.11 (m, 2H, H12+H24), 8.00 – 7.90 (m, 1H, H9),
7.90 – 7.70 (m, 7H, H14+H15+H17+H18+H20+H21+H23), ꢀ2.65 (br, 0.5H, H1). 13C{1H} NMR (126 MHz, CDCl3) δ 142.8 (C5), 141.5
(C25 or C27), 138.2 (C7), 136.3 (C6), 135.9 (C11), 135.5 (C10), 134.1 (C2), 131.1 (C25 or C27), 129.5 (C8), 127.7 (C24), 127.6 ꢀ 126.8
(C9+C14+C15+C17+C18+C20+C21+C23), 126.6 (C12), 120.1 (C4).
HRMS (MALDI): m/z = 1606,4985 [M]+ (calcd 1606,4969 for
C124H62N4). UV/Vis (toluene) λ 294 (ε: 131250), 404 (ε: 47000), 424 (ε: 279750), 516 (ε: 13000), 551 (ε: 6500).
General procedure for complexation measurements: A 10ꢀ4 M solution of each compound in deuterated toluene was prepared
and a known volume was transferred to a NMR tube (500 ꢁL). It was titrated by adding known portions of a stock solution of C60
1
(10ꢀ3 M) in deuterated toluene covering a wide range of equivalents. A H NMR spectrum was recorded at room temperature after
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each addition. Once obtained all data, changes in chemical shifts (ꢂδ) for selected protons (H1, H2 and/or H6) were plotted as a
function of guest molar fraction and the resulting curve was fitted by a nonlinear method.
ASSOCIATED CONTENT
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Supporting Information
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Synthesis overview of both synthetic methods, atom numbering, one and twoꢀdimensional NMR spectra of all new compounds, MS specꢀ
tra, UVꢀVis spectra, details of association constants estimation and computational calculations are gathered in the Supporting Information.
This material is available free of charge via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
* Eꢀmail: celedonio.alvarez@uva.es
Author Contributions
The manuscript was written through contributions of all authors.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was funded by the Spanish Ministerio de Economía y Competitividad (CTQ 2013ꢀ41067ꢀP). H.B. acknowledge with thanks a
MECꢀFPI grant. Allocation of computer facilities at IQTCUB is also acknowledged.
REFERENCES AND NOTES
1
(a) Kadish, K. M.; Smith, K. M.; Guilard R. (Eds.) The Porphyrin Handbook. Twenty volumes (particularly interesting
Volume 6: Applications: Past, Present and Future). Elsevier, 2000. (b) Kadish, K. M.; Smith, K. M.; Guilard R. (Eds.)
Handbook of Porphyrin Science. Thirty five volumes (particularly interesting Volumes 1, 4, 10, 11, 12, 18, 21, 27, 28, 33,
34). World Scientific, 2010.
2 Bonifazi, D.; Enger, O.; Diederich, F.; Chem. Soc. Rev. 2007, 36, 390ꢀ 414 and references therein.
3
(a) Fang, X.; Zhu, Y.ꢀZ.; Zheng, J.ꢀY. J. Org. Chem. 2014, 79, 1184ꢀ1191. (b) Zhu, B.; Chen, H.; Lin, W.; Ye, Y.; Wu, J.;
Li, S. J. Am. Chem. Soc. 2014, 136, 15126ꢀ15129. (c) GarcíaꢀSimón, C.; GarciaꢀBorràs, M.; Gómez, L.; Parella, T.; Osuna,
S.; Juanhuix, J.; Imaz, I.; Maspoch, D.; Costas, M.; Ribas, X. Nat. Commun. 2014, 5.
4
(a) Olmstead, M. M.; Costa, D. A.; Maitra, K.; Noll, B. C.; Phillips, S. L.; Van Calcar, P. M.; Balch, A. L. J. Am. Chem.
Soc. 1999, 121, 7090ꢀ7097. (b) Evans, D. R.; Fackler, N. L. P.; Xie, Z.; Rickard, C. E. F.; Boyd, P. D. W.; Reed, C. A. J. Am.
Chem. Soc. 1999, 121, 8466ꢀ8474. (c) Boyd, P. D. W.; Hodgson, M. C.; Rickard, C. E. F.; Oliver, A. G.; Chaker, L.; Brothꢀ
ers, P. J.; Bolskar, R. D.; Tham, F. S.; Reed, C. A. J. Am. Chem. Soc. 1999, 121, 10487ꢀ10495.
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5 Saegusa, Y.; Ishizuka, T.; Kojima, T.; Mori, S.; Kawano, M.; Kojima, T. Chem. Eur. J. 2015, 21, 5302ꢀ5306.
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(a) Álvarez, C. M.; GarcíaꢀEscudero, L. A.; GarcíaꢀRodríguez, R.; MartínꢀÁlvarez, J. M.; Miguel, D.; Rayón, V. M. Dalton
Trans. 2014, 43, 15693ꢀ15696. (b) Álvarez, C. M.; Aullón, G.; Barbero, H.; GarcíaꢀEscudero, L. A.; MartínezꢀPérez, C.;
MartínꢀÁlvarez, J. M.; Miguel, D. Org. Lett. 2015, 17, 2578ꢀ2581.
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(a) Stuparu, M. C. Angew. Chem., Int. Ed. 2013, 52, 7786−7790. (b) Yanney, M.; Fronczek, F. R.; Sygula, A. Angew.
Chem. Int. Ed. 2015, 54, 11153ꢀ11156. (c) Kuragama, P. L. A.; Fronczek, F. R.; Sygula, A. Org. Lett. 2015, 17, 5292ꢀ5295.
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(a) Chauhan, S. M. S.; Sahoo. B. B., Srinivas, K. A. Synth. Commun. 2001, 31, 33ꢀ37. (b) Nascimento, B. F. O.; Pineiro,
M.; Gonsalves, A. M. R.; Silva, M. R.; Beja, A. M.; Paixão, J. A. J. Porphyrins Phthalocyanines 2007, 11, 77ꢀ84. (c) Paula,
R. D.; Faustino, M. A. F.; Pinto, D. C. G. A.; Neves, M. G. P. M. S.; Cavaleiro, J. A. S. J. Heterocyclic Chem. 2008, 45, 453ꢀ
459.
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For instance, Miyaura reaction was complete after 2 hours, while 72 hours were needed to reach the same conversion if
refluxed under conventional methods.
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(a) Crossley, M. J.; Field, L. D.; Forster, A. J.; Harding, M. M.; Sternhell, S. J. Am. Chem. Soc. 1987, 109, 341ꢀ348. (b)
Meunier, B.; R. Song; A. Robert; Bernadou, J. Analusis 1999, 27, 464ꢀ467. (c) Silva, A. M. S.; Tomé, A. C.; Alkorta, I.;
Elguero, J. J. Porphyrins Phthalocyanines 2011, 15, 1ꢀ28.
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There are many works in which all atropisomers could be isolated, but all authors stated that only orthoꢀsubstituted porꢀ
phyrins gave satisfactory results. Some few examples: (a) Crossley, M. J.; Field, L. D.; Forster, A. J.; Harding, M. M.; Sternꢀ
hell, S. J. Am. Chem. Soc. 1987, 109, 341ꢀ348. (b) Rose, E.; CardonꢀPilotaz, A.; Quelquejeu, M.; Bernard, N.; Kossanyi; A.
J. Org. Chem. 1995, 60, 3919ꢀ3920. (c) Spasojević, I.; Menzeleev, R.; White, P. S.; Fridovich, I. Inorg. Chem. 2002, 41,
5874ꢀ5881. (d) Hunter, C. A.; Misuraca, M. C.; Turega, S. M. J. Am. Chem. Soc. 2011, 133, 582ꢀ594. (e) Sun, H.; Guo, K.;
Gan, H.; Li, X.; Hunter, C. A. Org. Biomol. Chem. 2015, 13, 8053ꢀ8066.
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(a) Zhao, Y.ꢀL.; Stoddart, J. F. Acc. Chem. Res. 2009, 42, 1161–1171. (b) Gavrel, G.; Jousselme, B.; Filoramo A.; Camꢀ
pidelli, S. Top. Curr. Chem. 2014, 348, 95–126.
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Porphyrins 2HP1, ZnP1 and ZnP2 were also tested to investigate their properties to bind Buckminsterfullerene, but both
MS and 1H NMR spectra gave negative results, indicating that PAHs subunits slightly contribute to form the adduct.
14 See Supporting Information for details about the computational model followed.
15 Additional possibilities were also tested, implying other initial assignments for H6 as reported by Sternhell et al. or Bernarꢀ
dou and Meunier et al.10a,b but none of them was reasonable in our case due, mainly, to inconsistencies when fitting curves
and no reproducibility when compared to H2 chemical shift changes.
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a) Purification of Laboratory Chemicals, Fifth Edition, W. L. E Armarego, C. L. L. Chai, ButterworthꢀHeinemann Ed.
2003; b) D. Bradley, G. Williams and M. Lawton, J. Org. Chem., 2010, 75, 8351ꢀ8354.
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(a) Lentz, D.; Topolinski, B.; Schmidt, B. M.; Kathan, M.; Troyanov, S. I. Chem. Commun. 2012, 48, 6298ꢀ6300. (b)
Siegel, J. S.; Butterfield, A. M.; Gilomen, B. Org. Process Res. Dev. 2012, 16, 664ꢀ676.
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(a) T. M. Boller, J. M. Murphy, M. Hapke, T. Ishiyama, N. Miyaura, J. F. Hartwig, J. Am. Chem. Soc. 2005, 127,
14263−14278; (b) M. Beinhoff, W. Weigel, M. Jurczok, W. Rettig, C. Modrakowski, I. Brüdgam, H. Hartl, A. D. Schlüter,
Eur. J. Org. Chem. 2001, 3819ꢀ3829; (c) H. A. Wegner, L. T. Scott, A. de Meijere, J. Org. Chem. 2003, 68, 883ꢀ887.
19 C. A. Hunter, M. C. Misuraca, S. M. Turega, J. Am. Chem. Soc. 2011, 133, 582ꢀ594.
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