Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT calculations

Article abstract of DOI:10.1016/j.tet.2018.07.007

Ethynyl-bridged porphyrin-corrole dyads and triads were synthesized by using Pd(0) mediated coupling reactions and their structures were characterized by NMR, FT-IR, UV/Vis and fluorescence techniques. Besides spectroscopic techniques, computational studi

Full text of DOI:10.1016/j.tet.2018.07.007

Tetrahedron xxx (2018) 1e13
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Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis,
properties and DFT calculations
Baris Temelli*, Mine Gündüz, Dilek Yüksel
Hacettepe University, Department of Chemistry, Beytepe Campus, 06800, Ankara, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Ethynyl-bridged porphyrin-corrole dyads and triads were synthesized by using Pd(0) mediated coupling
reactions and their structures were characterized by NMR, FT-IR, UV/Vis and fluorescence techniques.
Besides spectroscopic techniques, computational studies at B3LYP/6-311G(d,p) level of DFT were also
used to elucidate the minimum energy geometries and the molecular orbital characteristics of the new
dyads and triads. DFT calculations pointed out the presence of charge separated donor-acceptor property
between macrocycles of dyads and triads, and the emission studies indicated an excited state interaction
between macrocycles, and energy transfer from the porphyrin to the corrole unit.
Received 8 April 2018
Received in revised form
30 June 2018
Accepted 4 July 2018
Available online xxx
Keywords:
Porphyrin
Corrole
© 2018 Elsevier Ltd. All rights reserved.
Sonogashira coupling
DFT
1. Introduction
attention, their integration into porphyrin hybrid compounds has
remained limited. To date, only limited number of studies have
Porphyrins are macrocyclic tetrapyrrolic aromatic compounds
that play important roles in various metabolic systems such as
oxygen and electron transfer [1]. Metal complexes of porphyrins
are widely used in photodynamic therapy, dye-sensitized solar
cells, and catalytic applications [2]. Multiporphyrin compounds
have been the subject of intense research over the past few decades
because of their applications in sensors, artificial photosynthetic
systems and molecular wires [3]. However, these compounds
consist of a single chromophore group that absorbs only particular
wavelengths of the visible light. This limitation led to the use of
porphyrin hybrid compounds with different chromophore groups
such as, corroles [4], phythalocyanines [5], subporphyrins [6],
bodipy [7] and expanded porphyrins [8]. The investigation of multi
chromophore containing compounds and their excited state be-
haviors has made significant contributions to the applications on
the conversion of solar energy into chemical energy. In this regard,
corroles, contracted porphyrin analogs with direct pyrrole-pyrrole
linkage, have attracted the attention due to their trianionic char-
acter, higher fluorescence quantum yields and lower oxidation
potentials [9]. Although the applications of corroles as catalysts,
sensors, and dye sensitized solar cells have received much
reported on porphyrin-corrole conjugates and their applications
have not been extensively studied. Smith and co-workers reported
an approach to phenyl-linked porphyrin-corrole dyads via cycli-
zation of phenyl-linked a,c-biladiene salts [4a]. Also, Kadish, Guillar
and co-workers prepared metal complexes of cofacial porphyrin-
corrole dyads, which are linked by anthracene, bipheylene, diben-
zofuran, dibenzothiophene, dibenzofuran, dimethylxanthene, and
diphenyl ether bridges [4b,c]. The amide connected porphyrin-
corrole dyad was synthesized by Gryko and co-workers [4d].
Maes, Campagne and co-workers synthesized porphyrin-corrole
conjugates through phenolic bond [4e]. Recently, click reaction
was used to prepare zinc porphyrin-copper corrole dyads, triad and
pentad [4f,g]. In addition, directly linked porphyrin-corrole hybrids
were prepared by condensation reactions of formylated porphyrins
[4h,i] and the Suzuki-Miyaura coupling of 2-boryl-substituted
corrole [4j].
Though porphyrin-corrole conjugates have been connected by
several linker groups, there is no report on the ethynyl linked
example of these compounds. Very recently, we reported the syn-
thesis and spectroscopic properties of imine-bridged [10] and
directly-linked porphyrin-corrole dyads [11]. As a continuation of
our studies on porphyrin-corrole conjugates, we present herein the
investigation of the synthesis, some photo physical properties, and
DFT calculations of meso-meso linked ethynyl-bridged porphyrin-
corrole dyads and triads (Fig. 1).
* Corresponding author.
E-mail address: temelli@hacettepe.edu.tr (B. Temelli).
https://doi.org/10.1016/j.tet.2018.07.007
0040-4020/© 2018 Elsevier Ltd. All rights reserved.
Please cite this article in press as: B. Temelli, et al., Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
Fig. 1. Synthesized porphyrin-corrole dyads and triads.
2. Results and discussion
ethynyl-substituted porphyrins 8, 9, 13, and 14 (Scheme 2).
The metal free porphyrin-Cu(III) corrole dyad 15 and the triad 17
were synthesized under copper free Pd(0) coupling conditions at
40 ꢀC with Pd2(dba)3/AsPh3 catalyst. Reactions were monitored
with TLC and the pure dyad 15 and the triad 17 were obtained after
silica gel column chromatography in 64% and 48% yields respec-
tively. For the synthesis of the Zn-porphyrin Cu(III)-corrole dyad 16
and the triad 18, PdCl2(PPh3)2/CuI catalyzed Sonogashira reaction
protocol gave better yields than the copper free method. The dyad
16 was obtained in 68% yield, while the triad 18 was isolated in 40%
yield after column chromatography (Scheme 3).
The structures of dyads and triads were identified by NMR and
mass spectroscopy. The aromatic region of 1H NMR spectrum of the
dyad 15 and the comparison with those of its monomers 3 and 8 is
shown Fig. 2. In dyad 15, the resonances corresponding to the
porphyrin and corrole subunits are present. meso-Proton of
porphyrin subunit appeared at 10.31 ppm as a singlet. Although six
Sonogashira reactions of mono and bis ethynyl-substituted
porphyrins with bromophenyl-substituted Cu(III) corrole complex
were used to synthesize ethynyl-bridged dyads and triads. For
corrole part of the conjugates, 10-(4-bromophenyl)-5,15-
diphenylcorrole copper (III) (3) was synthesized in two steps ac-
cording to the reported methods [12]. 10-(4-Bromophenyl)-5,15-
diphenylcorrole (2) was prepared by the condensation of 5-
phenyldipyrromethane (1) with 4-bromobenzaldehyde and sub-
sequent oxidation of the reaction mixture with p-chloranil in CHCl3.
In the second step, 10-(4-bromophenyl)-5,15-diphenylcorrole (2)
was converted to its Cu(III) complex in 89% yield (Scheme 1).
The synthesis of porphyrin part of the conjugates started with
mono and dibromination of 5,15-diphenylporphyrin (4) by
controlled addition of NBS. Mono brominated porphyrin 5 and
dibrominated porphyrin 10 were isolated in 55% and 86% yields,
respectively. Sonagashira reactions of porphyrins 5 and 10 with
trimethylsilylacetylene at 80 ꢀC in the presence of a catalytic
amount of PdCl2(PPh3)2 and CuI gave desired protected porphyrins
6 and 11. After metalation reactions of meso-trimethylsillylethynyl
substituted porphyrins with Zn(OAc)2, TMS deprotections of both
metal free porphrins (6 and 11) and Zn(II) porphyrin complexes (7
and 12) were carried out with TBAF in order to obtain meso-
b
-porphyrin protons in dyad 15 (between 9.00 and 9.40 ppm)
experienced slight downfield shifts compared with those of start-
ing compound 8, two -porphyrin protons shifted upfield from
b
9.75 ppm to 9.38 ppm. The line-broadening, which affects corrole
compounds, observed in corrole sub-unit 3, disappeared in dyad 15
and
b-protons of corrole subunit appeared at 7.74e7.78 ppm and
7.53e7.58 ppm as multiplets. Other signals in the spectrum of the
Scheme 1. Synthesis of 10-(4-bromophenyl)-5,15-diphenylcorrole copper (III) 3.
Please cite this article in press as: B. Temelli, et al., Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
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Scheme 2. Synthesis of 5-ethynyl- (8 and 9) and 5,15-diethynyl-substituted (13 and 14) porphyrins. Reagents and conditions: (a) NBS (1 equiv.), CH2Cl2/CH3OH (9:1), rt, 15 min; (b)
trimethylsilylacetylene (2 equiv.), PdCl2(Ph3P)2, CuI, Et3N/toluene; (c) Zn(OAc)2, CH3OH/toluene (1:4), reflux, 4 h; (d) TBAF (1.5 equiv.), CH2Cl2, rt, 30 min; (e) NBS (2.5 equiv.),
pyridine, CHCl3, 0 ꢀC, 1 h; (f) trimethylsilylacetylene (4 equiv.), PdCl2(Ph3P)2, CuI, Et3N/toluene; (g) TBAF (2 equiv.), CH2Cl2, rt, 30 min.
dyad 15 belong to phenyl protons of the compound. The disap-
pearance of the signal at 4.13 ppm corresponding to the ethynyl
proton confirmed the structure (Fig. S10). The Zn-porphyrin-
Cu(III)-corrole dyad 16 showed similar properties to dyad 15 and
same type of signal shifts were observed (Figs. S23eS25).
Fig. 4 shows the comparison of absorption spectra of the dyad 15,
the corrole 3 and the porphyrin 8. Though the dyad 15 showed a
similar Soret band with corrole monomer 3 at 412 nm, its Q bands
have different peak maxima than corresponding monomers at 508,
539, 581, and 649 nm. Similarly, the dyad 15, the Zn-porphyrin
containing dyad 16 showed different Q bands to those of constit-
uent macrocycles (Fig. S37) and only one absorption band was
determined at 548 nm. As shown in Fig. 5 and Fig. S38, absorption
spectra of the triads 17 and 18 are a linear combination of the
spectra of the corresponding monomers and interactions between
porphyrin and corrole sub-units are weak.
The emission properties of the dyads 15, 16 and the triads 17, 18
were studied by steady state fluorescence technique at room
temperature in chloroform in order to understand their excited
state dynamics. Fig. 6 and Fig. S39 show the emission spectra of the
dyads 15 and 16, their monomers and 1:1 mixtures of the corre-
While the dyads 15 and 16 are soluble in CDCl3, the triads 17 and
18 are more soluble in d-THF. The 1H NMR spectrum of the triad 18
(Fig. 3) shows symmetric two sets of
b-proton resonances of the
porphyrin sub-unit as doublets at 9.55 and 8.73 ppm.
b-Proton
resonances of the corrole sub-units appear with over-lapping sig-
nals with phenyl protons between 7.3 and 7.7 ppm. Significant
changes in the 1H NMR spectra of the dyads 15, 16 and the triads 17,
18, compared to the corresponding monomers, indicate in-
teractions of the porphyrin and the corrole units with each other in
the synthesized conjugates.
The absorption spectra of the corrole 3, the porphyrin mono-
mers, the dyads, and the triads were recorded in CHCl3 (Table 1).
sponding monomers at
l
¼ 420 nm. Cu(III)-corrole monomer 3 is
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Scheme 3. Synthesis of dyads (15 and 16) and triads (17 and 18).
Fig. 2. Comparison of the 1H NMR spectra of (i) corrole 3 (ii) porphyrin 8 and (iii) dyad 15.
nonfluorescent and the porphyrin monomer 8 showed two emis-
sions at 653 nm and 723 nm. The emission from the porphyrin
monomer was quenched by 70% in dyad 15. No significant
quenching was observed when 1:1 mixture of the porphyrin 8 and
corrole 3 was excited (Fig. 6). The emission spectrum of the dyad 16
showed emissions at 596 nm and 650 nm. The comparison of the
emission spectra of the dyad 16 and the monomer 9 indicates that
the emission from porphyrin unit decreased at 596 nm, while the
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
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Fig. 3. The 1H NMR spectra of triad 18.
Table 1
Absorption data for dyads (15, 16) and triads (17, 18) and their corresponding monomers recorded in chloroform.
Comp.
Soret band
l
[nm] (log ε)
Q bands
l [nm] (log ε)
3
8
9
13
14
15
16
17
18
412 (4.69)
420 (5.50)
419 (5.01)
427 (5.32)
430 (5.29)
413 (4.13)
418 (4.47)
427 (4.83)
441 (4.59)
528 (3.59)
517 (4.20)
550 (3.68)
531 (4.02)
575 (3.90)
508 (3.14)
548 (3.36)
532 (3.76)
531 (3.65)
603 (3.40)
552 (3.90)
587 (3.33)
571 (4.24)
622 (4.11)
539 (2.62)
593 (3.68)
608 (3.64)
581 (2.68)
649 (3.34)
670 (3.83)
649 (1.84)
670 (3.58)
571 (3.91)
575 (3.76)
609 (3.46)
622 (3.90)
1.4
1.2
1
0.15
0.1
0.05
0
15
3
8
0.8
0.6
0.4
0.2
0
450
500
550
600
650
600
700
350
400
450
500
550
650
700
Wavelenght (nm)
Fig. 4. Absorption spectra of dyad 15 and its monomers corrole 3 and porphyrin 8 in CHCl3 (10ꢁ5 M).
emission at 650 nm increasing (Fig. S39).
systems in the literature [4f,4g,13].
Same type of quenching properties and energy transfer from the
porphyrin to the corrole sub-unit was observed for the triads 17 and
18. The comparison of fluorescence spectra of the triad 17 with its
monomers shows that the emission from metal free-porphyrin unit
was quenched by 95%. The same amount of emission was obtained
when 1:1 mixture of the porphyrin 13 and corrole 3 compounds
was excited (Fig. 7). Similarly, the emission from porphyrin-Zn
complex was also quenched by 76% in triad 18 (Fig. S40). These
results suggest that there is a significant intermolecular association
between the sub-units and the energy transfer from the porphyrin
to the corrole unit in the dyads and triads. Similar type of obser-
vations were noted in related porphyrin donor-corrole acceptor
2.1. Computational results
Based on the structures given in Scheme 3 (3, 8, 9, 13e18), nine
model geometries were designed for the computational studies. All
structures were optimized to their lowest energy geometries at
B3LYP/6-311G(d,p) level of DFT.
Due to the noninnocence character of the corrole ligand, and the
proposed equilibrium between singlet corrole-copper(III) and
triplet corrole-copper(II) radical cation [14,15], geometry optimi-
zations were performed according to three different spin states,
which are closed shell singlet, triplet and open shell singlet states.
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
1.8
1.6
1.4
1.2
1
0.6
0.4
0.2
0
18
3
0.8
0.6
0.4
0.2
0
14
450
550
650
350
400
450
500
550
600
650
700
Wavelenght (nm)
Fig. 5. Absorption spectra of triad 18 and its monomers corrole 3 and porphyrin 14 in CHCl3 (10ꢁ5 M).
between the least square planes of corrole and porphyrin moieties
is 54.6 degrees for 15 and 53.9 degrees for 16. In triads 17 and 18,
the angle between each corrole plane and the porphyrin plane is
50.6 and 50.8 degrees, respectively, and the angle between the two
corrole planes are 102.3 degrees. More detailed data about the
optimized geometries and the cartesian coordinates of the model
structures are available in Supporting Information.
240
190
140
90
8
3
15
3+8
Calculated orbital energy levels from HOMO-5 to LUMOþ5 for
the model molecules are presented in Table 2 and Fig. 8. The energy
gap (Eg) between the HOMO and the LUMO for corrole monomer 3
and porphyrin monomers 8, 9, 13 and 14 are 2.607(1.552), 2.631,
40
-10
600
650
700
750
800
Wavelenght (nm)
2.704, 2.457 and 2.527 eV, respectively. Eg a and b, in parentheses,
Fig. 6. Emission spectra of corrole 3, porphyrin 8, dyad 15 and the mixture of 3 and 8 at
room temperature (CHCl3,
¼ 420 nm).
for the corresponding dyads (15, 16) and the triads (17, 18) are 1.543
(2.115), 1.544 (2.180), 1.270 (1.270) and 1.270 (1.270), respectively. It
is seen that the dyads and triads have considerably smaller Eg
values than their corresponding porphyrin components. Especially
orbital energy levels of the triads are very close to each other, and
degenerated frontier molecular orbitals were observed.
To investigate charge separation and donor-acceptor properties
between macrocycles of the dyads (15 and 16) and the triads (17
and 18), molecular models shown in Fig. 9 a and b were used.
The electron density distributions and corresponding energies
for the selected molecular orbitals of 15e18 are shown in Figs. 10
and 11 (See also S46eS49). Related molecular orbital composi-
tions calculated at B3LYP/6-311G(d,p) level are given in Tables 3 and
4.
l
Open shell singlet state was found as the ground state for corrole-
copper containing structures (3, 15e18), which is more stable than
the corresponding closed shell singlet state by 0.153, 0.156, 0.156,
0.313, and 0.314 eV for 3, 15, 16, 17 and 18, respectively
(Figs. S41eS45). This result is also in agreement with previous
experimental and computational studies suggesting an antiferro-
magnetically coupled Cu(II) corrole radical cation as the ground
state for copper corrole [16e19]. For other structures (8, 9, 13 and
14) closed shell singlet state is the ground state.
Calculated bond lengths and bond angles of the corrole 3 and
the porphyrin monomers 8, 9, 13 and 14 are found similar to their
formerly reported analogs [10]. In the optimized geometries of both
the dyads (15 and 16) and the triads (17 and 18), porphyrin moieties
lie approximately on the same plane with the bridging phenyl
groups, where corrole components lie in different planes. The angle
In the dyads 15 and 16, the HOMO
molecular orbitals are located on the corrole moiety, whereas the
LUMO molecular orbital locates on the porphyrin moiety in great
extent (Fig. 10 and Table 3). Calculated electronic spectra (Table 5)
a, HOMOb and the LUMOa
b
240
190
140
90
13
17
3
13+3
40
-10
600
620
640
660
680
700
720
740
760
780
800
Wavelenght (nm)
Fig. 7. Emission spectra of corrole 3, porphyrin 13, triad 17 and the mixture of 3 and 13 at room temperature (CHCl3,
l
¼ 420 nm).
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
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Table 2
Selected orbital energies (eV) calculated at B3LYP/6-311G(d,p) level.
3
a
3
b
8
9
13
14
15
a
15
b
16
a
16
b
17
a
,b
18a,b
LUMOþ5
LUMOþ4
LUMOþ3
LUMOþ2
LUMOþ1
LUMO
ꢁ0.520
ꢁ0.770
ꢁ0.781
ꢁ1.751
ꢁ2.082
ꢁ2.384
ꢁ4.991
ꢁ5.193
ꢁ6.533
ꢁ6.631
ꢁ6.781
ꢁ6.834
2.607
ꢁ0.500
ꢁ0.736
ꢁ0.762
ꢁ1.749
ꢁ2.091
ꢁ3.669
ꢁ5.221
ꢁ5.596
ꢁ6.486
ꢁ6.573
ꢁ6.715
ꢁ6.808
1.552
ꢁ0.452
ꢁ0.485
ꢁ0.494
ꢁ1.052
ꢁ2.546
ꢁ2.679
ꢁ5.310
ꢁ5.581
ꢁ6.584
ꢁ6.701
ꢁ6.985
ꢁ7.067
2.631
ꢁ0.420
ꢁ0.448
ꢁ0.454
ꢁ0.964
ꢁ2.438
ꢁ2.590
ꢁ5.294
ꢁ5.480
ꢁ6.771
ꢁ6.798
ꢁ6.798
ꢁ6.831
2.704
ꢁ0.485
ꢁ0.524
ꢁ0.527
ꢁ1.226
ꢁ2.589
ꢁ2.881
ꢁ5.338
ꢁ5.650
ꢁ6.609
ꢁ6.745
ꢁ6.989
ꢁ7.096
2.457
ꢁ0.455
ꢁ0.487
ꢁ0.491
ꢁ1.151
ꢁ2.497
ꢁ2.791
ꢁ5.317
ꢁ5.554
ꢁ6.720
ꢁ6.851
ꢁ6.888
ꢁ6.892
2.527
ꢁ1.186
ꢁ1.700
ꢁ2.017
ꢁ2.557
ꢁ2.752
ꢁ3.600
ꢁ5.142
ꢁ5.231
ꢁ5.525
ꢁ5.601
ꢁ6.412
ꢁ6.416
1.543
ꢁ1.224
ꢁ1.672
ꢁ1.999
ꢁ2.310
ꢁ2.561
ꢁ2.762
ꢁ4.877
ꢁ5.114
ꢁ5.262
ꢁ5.604
ꢁ6.453
ꢁ6.458
2.115
ꢁ1.130
ꢁ1.684
ꢁ2.008
ꢁ2.460
ꢁ2.674
ꢁ3.589
ꢁ5.133
ꢁ5.214
ꢁ5.507
ꢁ5.516
ꢁ6.403
ꢁ6.406
1.544
ꢁ1.168
ꢁ1.663
ꢁ1.985
ꢁ2.301
ꢁ2.464
ꢁ2.684
ꢁ4.865
ꢁ5.104
ꢁ5.246
ꢁ5.510
ꢁ6.446
ꢁ6.449
2.180
ꢁ2.039
ꢁ2.051
ꢁ2.330
ꢁ2.601
ꢁ2.979
ꢁ3.630
ꢁ4.899
ꢁ5.138
ꢁ5.167
ꢁ5.218
ꢁ5.548
ꢁ5.675
1.270
ꢁ2.031
ꢁ2.038
ꢁ2.324
ꢁ2.522
ꢁ2.906
ꢁ3.620
ꢁ4.890
ꢁ5.130
ꢁ5.159
ꢁ5.207
ꢁ5.540
ꢁ5.588
1.270
aHOMO
aHOMO-1
aHOMO-2
aHOMO-3
aHOMO-4
aHOMO-5
Eg
a
For structures at their open shell singlet states (3, 15e18) singly occupied.
porphyrin unit in the dyads and the triads were quenched signifi-
cantly by corrole unit. On the basis of the DFT calculations, geo-
metric and electronic properties of the new molecules have been
discussed. Charge separated donor-acceptor property between
porphyrin and corrole moieties has been observed for the dyads
and the triads.
4. Experimental section
4.1. General
All solvents and reagents were obtained from Aldrich Chemicals
and Acros Organics. NMR spectra were recorded by using Bruker
DPX-400 Ultra Shield spectrometer and chemical shifts are re-
ported in parts per million (ppm) relative to TMS. Mass spectra
were recorded with Agilent 6224 TOF LC-MS instrument. Infrared
spectra were measured by using a Thermo Scientific, Nicolet IS10
spectrometer. Absorption spectra were obtained with PG T80.
Fluorescence spectra were recorded with Varian Cary Eclipse
spectrometer. Flash column chromatography was performed on
Silica (Merck, Kiesegel, 230e400 mesh). 2,2’-(Phenylmethylene)
bis(1H-pyrrole) (1) [20], 5,15-diphenylporphyrin (4) [21], 5-bromo-
10,20-diphenylporphyrin (5) [22], and 5,15-dibromo-10,20-
diphenylporphyrin (10) [15] were synthesized by the reported
methods.
Fig. 8. Orbital energy levels (from HOMO-5 to LUMOþ5) calculated at B3LYP/6-
311G(d,p) level (red lines represent
b molecular orbitals for the structures at open
▪
shell singlet state). (For interpretation of the references to colour in this figure legend,
indicates that the lowest energy UVevis transition in the dyads was
between the HOMOb and the LUMOb, and charge separation be-
tween these two orbitals has been observed. In the triads 17 and 18,
again the HOMO and the LUMO are located greatly on the corrole
moieties (Fig. 11 and Table 4), and charge separation has been
achieved via transition between the HOMO and the LUMOþ1
orbitals.
4.2. 10-(4-Bromophenyl)-5,15-diphenylcorrole (2)
2,2’-(Phenylmethylene)bis(1H-pyrrole) (1) (1.00 g, 4.50 mmol)
and p-bromobenzaldehyde (0.42 g, 2.25 mmol) were dissolved in
CH3OH (225 mL) and a HCl solution (36%, 11.25 mL) in H2O (225 mL)
was added to the reaction mixture at room temperature. After 1 h,
the aqueous phase was extracted with CHCl3 (3 ꢂ 100 mL) and
diluted to 750 mL. p-Chloranil (1.66 g, 6.75 mmol) was added and
the reaction mixture was stirred 24 h. The solvent was removed
3. Conclusions
The first synthesis of ethynyl-bridged porphyrin-corrole dyads
and triads was achieved by using Sonogashira coupling reactions.
The absorption and emission spectra indicate that the emission of
Fig. 9. Model structures for dyads (a) and triads (b).
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8
B. Temelli et al. / Tetrahedron xxx (2018) 1e13
Fig. 10. Selected FMOs of the dyads 15 and 16.
under reduced pressure. The crude product was purified by flash
column chromatography (CH2Cl2/hexanes 1:6) to provide
(463 mg, 34%) as a green solid: m.p.> 300 ꢀC; Rf: 0.55 (EtOAc/hex-
anes 1:10); IR (ATR, cmꢁ1
3393, 3345, 1803, 1754, 1687, 1550,
J ¼ 7.2 Hz, 4H, Ph-H), 7.55 (d, J ¼ 3.7 Hz, 2H,
b-H), 7.53e7.38 (m, 10H,
2
Ph-H), 7.26 (d, J ¼ 4.0 Hz, 2H,
b
-H), 7.14 (d, J ¼ 4.3 Hz, 2H,
b-H);
HRMS (ESI): m/z calcd for C37H23BrCuN4 [MþH]þ 665.0397, found
)
n
665.0348.
1480,1461,1437, 1413,1381,1333,1309,1283,1239,1225,1212,1174,
1109, 1069, 1033, 1010, 961, 922, 909, 874, 845, 820, 785, 756, 717,
700, 663; UV/Vis (CHCl3) lmax (log ε): 416 (4.49), 575 (3.61), 614
4.4. 5-Trimethylsilylethynyl-10,20-diphenylporphyrin (6)
(3.50), 647 3.43) nm; 1H NMR (400 MHz, CDCl3)
d
8.85 (br s, 4H),
8.51 (br s, 4H), 8.33 (d, J ¼ 6.8 Hz, 4H, Ph-H), 8.01 (d, J ¼ 7.5 Hz, 2H,
Ph-H), 7.91e7.69 (m, 8H); 13C NMR (100 MHz, CDCl3)
143.2, 136.3,
A solution of 5-bromo-10,20-diphenylporphyrin (5) (0.300 g,
0.554 mmol),
trimethylsilylacetylene
(15
mL,
1.11 mmol),
d
PdCl2(Ph3P)2 (11.4 mg, 0.0161 mmol), and copper(I) iodide
(3.35 mg, 0.0177 mmol) in Et3N/toluene (2:1, 50 mL) was deoxy-
genated and stirred at 80 ꢀC under N2 atmosphere. After 6 h, the
mixture was cooled to room temperature and filtered. The solvent
was removed under reduced pressure. The crude product was pu-
rified by flash column chromatography (CHCl3:hexanes 1:2) to
provide 6 (162 mg, 60%) as a purple solid: m.p.> 300 ꢀC; Rf: 0.70
135.2, 132.4, 131.8, 130.8, 130.7, 130.6, 128.9e127.5 (overlapping
peaks), 118.9, 108.2; HRMS (ESI): m/z calcd for C37H26BrN4 [MþH]þ
605.1335, found 605.1348.
4.3. 10-(4-Bromophenyl)-5,15-diphenylcorrole-copper(III) (3)
10-(4-Bromophenyl)-5,15-diphenylcorrole
(2)
(0.200 g,
(EtOAc/hexanes 1:6); IR (ATR, cmꢁ1
) n 2955, 2919, 2850, 2138, 1737,
0.330 mmol) and Cu(OAc)2.H2O (0.200 g, 0.990 mmol) were dis-
solved in THF (45 mL) and the reaction mixture was stirred at room
temperature for 30 min. The solvent was removed under reduced
pressure and the product was purified by flash column chroma-
tography (CHCl3) to provide 3 (196 mg, 89%) as a green solid: m.p.>
1597, 1556, 1456, 1440, 1404, 1341, 1245, 1197, 1181, 1153, 1118, 1064,
1051, 1031, 1001, 991, 957, 839, 749, 739, 724, 702, 690, 655; UV/Vis
(CHCl3) lmax (log ε): 424 (5.25), 522 (3.93), 558 (3.86), 595 (3.50),
653 (3.34) nm; 1H NMR (400 MHz, CDCl3)
d
9.93 (s, 1H, meso-H),
-H), 9.06 (br s, 2H, -H), 8.84 (d,
-H), 8.78 (d, J ¼ 3.6 Hz, 2H, -H), 8.10e8.06 (m, 4H,
Ph-H), 7.66e7.63 (m, 6H, Ph-H), 0.52 (s, 9H, CH3), ꢁ2.81 (s, 2H, NH);
13C NMR (100 MHz, CDCl3)
140.9, 134.3, 131.2, 130.8, 130.5, 127.5,
9.65 (d, J ¼ 4.7 Hz, 2H,
b
b
300 ꢀC; Rf: 0.62 (EtOAc/hexanes 1:10); IR (ATR, cmꢁ1
)
n
3358, 1678,
J ¼ 4.6 Hz, 2H,
b
b
1565, 1517, 1491, 1466, 409, 1365, 1338, 1309, 1251, 1191, 1108, 1070,
1052, 1020, 1009, 982, 881, 843, 811, 789, 768, 756, 731, 706, 675,
661; UV/Vis (CHCl3) lmax (log ε): 412 (4.69), 528 (3.59), 603 (3.40)
d
126.5, 120.1, 107.1, 106.2, 101.5, 99.1, 0.00; HRMS (ESI): m/z calcd for
nm; 1H NMR (400 MHz, CDCl3)
d
7.80 (br s, 2H,
b
-H), 7.67 (d,
C
37H31N4Si [MþH]þ 559.2312, found 559.2323.
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
9
Fig. 11. Selected FMOs of the triads.
Table 3
Energies and percent compositions of selected frontier molecular orbitals of dyads.
Species
a
MO
Energy (eV)
% compositions
b
MO
Energy (eV)
% compositions
C
B
P
C
B
P
dyad 15
Lþ2
Lþ1
L
ꢁ2.557
ꢁ2.752
ꢁ3.600
ꢁ5.142
ꢁ5.231
ꢁ5.525
ꢁ2.460
ꢁ2.674
ꢁ3.589
ꢁ5.133
ꢁ5.214
ꢁ5.507
0
3
0
12
5
0
19
0
0
13
5
0
20
0
100
85
2
0
78
1
100
84
2
0
77
100
Lþ2
Lþ1
L
ꢁ2.310
ꢁ2.561
ꢁ2.762
ꢁ4.877
ꢁ5.114
ꢁ5.262
ꢁ2.301
ꢁ2.464
ꢁ2.684
ꢁ4.865
ꢁ5.104
ꢁ5.246
99
0
2
86
99
10
99
0
1
0
13
7
1
16
1
0
14
8
1
0
100
85
7
0
73
0
100
84
7
0
72
94
100
3
98
0
H
H
H-1
H-2
Lþ2
Lþ1
L
H
H-1
H-2
H-1
H-2
Lþ2
Lþ1
L
H
H-1
H-2
dyad 16
3
94
100
3
3
85
99
11
0
17
H: highest energy singly occupied molecular orbital, L: lowest energy unoccupied molecular orbital, P: porphyrin moiety C: corrole moiety B: bridge.
4.5. 5-Trimethylsilylethynyl-10,20-diphenylporphyrinato-zinc(II)
(7)
in a mixture of CH3OH (6 mL) and toluene (22 mL). The mixture was
refluxed for 4 h. in the dark and cooled to room temperature. The
solvent was removed under reduced pressure. The crude product
was washed with hot water and dried to provide 7 (106 mg, 95%) as
a purple solid: m.p.> 300 ꢀC; Rf: 0.85 (EtOAc/hexanes 1:3); IR (ATR,
5-Trimethylsilylethynyl-10,20-diphenylporphyrin (6) (0.100 g,
0.18 mmol) and Zn(OAc)2.2H2O (0.138 g, 0.63 mmol) were dissolved
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10
B. Temelli et al. / Tetrahedron xxx (2018) 1e13
Table 4
Energies and percent compositions of selected frontier molecular orbitals of triads.
Species
a
MO
Energy (eV)
% compositions
b
MO
Energy (eV)
% compositions
C1
B1
P
B2
C2
C1
B1
P
B2
C2
triad 17
Lþ2
Lþ1
L
ꢁ2.601
ꢁ2.979
ꢁ3.630
ꢁ4.899
ꢁ5.138
ꢁ5.167
ꢁ2.522
ꢁ2.906
ꢁ3.620
ꢁ4.890
ꢁ5.130
ꢁ5.159
0
2
0
84
100
0
0
3
0
11
0
7
0
0
0
10
5
1
100
75
2
7
0
0
10
5
1
0
0
0
11
0
8
0
3
93
0
0
100
0
2
Lþ2
Lþ1
L
ꢁ2.601
ꢁ2.979
ꢁ3.630
ꢁ4.899
ꢁ5.138
ꢁ5.167
ꢁ2.522
ꢁ2.906
ꢁ3.620
ꢁ4.890
ꢁ5.130
ꢁ5.159
0
3
93
0
0
100
0
2
0
10
5
1
0
0
0
11
0
8
100
75
2
7
0
0
11
0
7
0
0
0
10
5
1
0
2
0
84
100
0
0
3
H
H
H-1
H-2
Lþ2
Lþ1
L
H
H-1
H-2
H-1
H-2
Lþ2
Lþ1
L
H
H-1
H-2
0
0
triad 18
100
74
2
8
0
100
74
2
8
0
93
0
0
0
0
93
0
0
83
100
0
83
100
0
0
0
0
0
0
0
0
0
100
0
0
100
H: highest energy singly occupied molecular orbital, L: lowest energy unoccupied molecular orbital, P: porphyrin moiety C: corrole moiety B: bridge.
Table 5
Calculated lowest energy UVevis electronic transition data for dyads and triads.
Species
Eg/eV
lmax/nm(eV)
f
Major Contributions
Transitiona
dyad 15
dyad 16
triad 17
triad 18
1.277
1.276
1.270
1.270
665 (1.864)
651 (1.904)
745 (1.665)
722 (1.717)
0.1744
0.1841
0.5997
0.6192
HOMO
HOMO
b
b
/ LUMO
/ LUMO
b
b
(64%)
(60%)
C/P
C/P
C/P
C/P
HOMO /LUMOþ1 (47%)
HOMO /LUMOþ1 (45%)
a
P: porphyrin moiety C: corrole moiety.
cmꢁ1
)
n
3110, 3059, 2962, 2907, 2853, 2118, 2102, 1806, 1593, 1488,
30 min, CH3CO2H (21
mL) and CH3OH (7 mL) were added to the
1440, 1379, 1314, 1247, 1213, 1155, 1064, 1004, 994, 835, 785, 749,
reaction. The solvent was removed under reduced pressure and the
crude product was purified by flash column chromatography
(EtOAc/hexanes 1:3) to provide 9 (63 mg, 96%) as a purple solid:
731, 696, 667, 657; UV/Vis (CHCl3) lmax (log ε): 424 (5.57), 554
(4.21), 592 (3.85) nm; 1H NMR (400 MHz, CDCl3)
d
10.08 (s, 1H,
-H), 9.23 (d, J ¼ 4.5 Hz, 2H, -H),
-H), 8.93 (d, J ¼ 4.4 Hz, 2H, -H), 8.17e8.11
(m, 4H, Ph-H), 7.76e7.69 (m, 6H, Ph-H), 0.54 (s, 9H, CH3); 13C NMR
(100 MHz, CDCl3) 151.7, 149.9, 149.4, 148.8, 141.9, 134.1, 132.4,
meso-H), 9.72 (d, J ¼ 4.6 Hz, 2H,
b
b
m.p.> 300 ꢀC; Rf: 0.71 (EtOAc/hexanes 1:1); IR (ATR, cmꢁ1
) n 3260,
8.95 (d, J ¼ 4.6 Hz, 2H,
b
b
2918, 2849, 2069, 1800, 1724, 1595, 1523, 1487, 1462, 1440, 1379,
1314, 1258, 1212, 1173, 1155, 1123, 1066, 993, 935, 917, 908, 867, 823,
785, 744, 733, 715, 697, 672, 656; UV/Vis (CHCl3) lmax (log ε): 419
(5.01), 550 (3.68), 587 (3.33) nm; 1H NMR (400 MHz, d8-THF)
d
131.9, 131.4, 130.6, 127.1, 126.2, 120.9, 107.3, 106.9, 100.9, 99.5, 0.01;
HRMS (ESI): m/z calcd for C37H29N4SiZn [MþH]þ 621.1447, found
621.1435.
d
10.05 (s, 1H, meso-H), 9.61 (d, J ¼ 4.6 Hz, 2H,
J ¼ 4.4 Hz, 2H, -H), 8.82 (d, J ¼ 4.5 Hz, 2H, -H), 8.78 (d, J ¼ 4.4 Hz,
2H, -H), 8.09e8.05 (m, 4H, Ph-H), 7.65e7.62 (m, 6H, Ph-H), 4.45 (s,
1H, C^CH); 13C NMR (100 MHz, d8-THF)
151.7, 150.0, 149.2 (two
b-H), 9.18 (d,
b
b
b
d
4.6. 5-Ethynyl-10,20-diphenylporphyrin (8)
peaks), 142.6, 134.1, 132.3, 131.7, 131.3, 131.2, 130.2, 129.9, 128.2,
126.8, 125.9, 123.9, 120.4, 106.8, 97.6, 86.2, 83.1; HRMS (ESI): m/z
calcd for C34H21N4Zn [MþH]þ 549.1052, found 549.1048.
5-Trimethylsilylethynyl-10,20-diphenylporphyrin (6) (0.070 g,
0.125 mmol) was dissolved in 4 mL of CH2Cl2 and TBAF (0.188 mL
0.188 mmol) was added to the solution. After 30 min, CH3CO2H
(21 mL) and CH3OH (7 mL) were added to the reaction. The mixture
4.8. 5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrin (11)
was filtered after 30 min and the solid product was washed with
methanol to provide 8 (46 mg,76%) as a purple solid: m.p.> 300 ꢀC;
A
solution of 5,15-dibromo-10,20-diphenylporphyrin (10)
Rf: 0.79 (EtOAc/hexanes 1:3); IR (ATR, cmꢁ1
) n 3274, 3053, 2091,
(0.750 g, 1.21 mmol), trimethylsilylacethylene (0.522 g, 5.32 mmol),
PdCl2(Ph3P)2 (0.085 g, 0.121 mmol) and copper(I) iodide (0.025 g,
0.133 mmol) in Et3N/toluene (3:1, 100 mL) was deoxygenated and
stirred at 80 ꢀC under N2 atmosphere. After 7 h, the mixture was
cooled to room temperature and filtered. The solvent was removed
under reduced pressure. The crude product was purified by flash
column chromatography (EtOAc/hexanes 1:10) to provide 11
(634 mg, 80%) as a green solid: m.p.> 300 ꢀC; Rf: 0.67 (EtOAc/hex-
1809, 1596, 1551, 1481, 1436, 1402, 1341, 1250, 1196, 1178, 1156, 1071,
1056, 959, 917, 859, 789, 726, 698; UV/Vis (CHCl3) lmax (log ε): 420
(5.50), 517 (4.20), 552 (3.90), 593 (3.68), 649 (3.34) nm; 1H NMR
(400 MHz, CDCl3)
H), 9.22 (d, J ¼ 4.5 Hz, 2H,
d
10.13 (s, 1H, meso-H), 9.69 (d, J ¼ 4.5 Hz, 2H,
b-
b
-H), 8.90 (d, J ¼ 4.7 Hz, 2H, -H), 8.88 (d,
b
J ¼ 4.0 Hz, 2H,
b-H), 8.17e8.13 (m, 4H, Ph-H), 7.77e7.68 (m, 6H, Ph-
H), 4.13 (s, 1H, C^CH), ꢁ2.80 (br s, 2H, NH); 13C NMR (100 MHz,
anes 1:10); IR (ATR, cmꢁ1
) n 3320, 3065, 2955, 2358, 2140, 1739,
1557, 1470, 1441, 1397, 1345, 1246, 1196, 1137, 1064, 1050, 972, 836,
794, 759, 746, 720, 699, 688, 660; UV/Vis (CHCl3) lmax (log ε): 432
(5.50), 542 (4.06), 582 (4.62), 618 (3.73), 678 (4.20) nm; 1H NMR
CDCl3)
d 141.3, 134.7, 131.8, 131.7, 131.3, 130.8, 127.9, 127.0, 120.5,
106.8, 85.9, 84.0; HRMS (ESI): m/z calcd for C34H23N4 [MþH]þ
487.1917, found 487.1932.
4.7. 5-Ethynyl-10,20-diphenylporphyrinato-zinc(II) (9)
(400 MHz, CDCl3)
4H,
d
9.54 (d, J ¼ 4.7 Hz, 4H, -H), 8.75 (d, J ¼ 4.7 Hz,
b
b
-H), 8.10 (d, J ¼ 7.3 Hz, 4H, Ph-H), 7.74e7.67 (m, 6H, Ph-H), 0.54
5-Trimethylsilylethynyl-10,20-diphenylporphyrinato-zinc(II)
(7) (0.074 mg, 0.120 mmol) was dissolved in 4 mL of CH2Cl2 and
TBAF (0.180 mL, 0.180 mmol) was added to the solution. After
(s, 18 H, CH3), ꢁ2.29 (br s, 2H, NH); 13C NMR (100 MHz, CDCl3)
d
141.3, 134.5, 128.0, 126.9, 121.8, 106.8, 102.7, 100.8, 0.00; HRMS
(ESI): m/z calcd for C42H39N4Si2 [MþH]þ 655.2708, found 655.2708.
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B. Temelli et al. / Tetrahedron xxx (2018) 1e13
11
4.9. 5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrinato-
zinc(II) (12)
(3 ꢂ 10 mL). The solvent was removed under reduced pressure. The
crude product was purified by flash column chromatography
(CHCl3/hexanes 1:1) to provide 15 (96 mg, 64%) as a purple solid:
5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrin
(11)
m.p.> 300 ꢀC; Rf: 0.80 (CHCl3/hexanes 1:1); IR (ATR, cmꢁ1
) n 3646,
(0.070 g, 0.107 mmol) and Zn(OAc)2.2H2O (0.219 g, 0.374 mmol)
were dissolved in a mixture of CH3OH (3 mL) and toluene (11 mL).
The mixture was refluxed for 4 h. in the dark and cooled to room
temperature. The crude product was washed with hot water and
purified by flash column chromatography (EtOAc/hexanes 1:20) to
provide 12 (60 mg, 78%) as a purple solid: m.p.> 300 ꢀC; Rf: 0.87
3630, 2957, 2925, 2855, 2361, 1717, 1668, 1648, 1430, 1390, 1363,
1314, 1247, 1231, 1215, 1197, 1158, 1120, 1103, 1072, 1054, 1026, 972,
961, 931, 885, 860, 825, 809, 775, 769, 755, 740, 723, 700, 658, 652;
UV/Vis (CHCl3) lmax (log ε): 413 (4.13), 508 (3.14), 539 (2.62), 581
(2.68), 649 (1.84) nm; 1H NMR (400 MHz, CDCl3)
d
10.32 (s, 1H,
-H), 9.30 (d, J ¼ 4.8 Hz, 2H,
-H), 9.07 (d, J ¼ 4.6 Hz, 2H,
b-H), 8.30e8.26 (m, 4H, Ph-H), 7.87e7.80 (m, 6H, Ph-H),
meso-H), 9.39 (d, J ¼ 4.6 Hz, 2H, porp
b
b
(EtOAc/hexanes 1:6); IR (ATR, cmꢁ1
)
n
2954, 2927, 2855, 2129, 2104,
porp
porp
b
-H), 9.10 (d, J ¼ 4.8 Hz, 2H, porp
1738,1596,1504,1456,1442,1377,1342,1308,1245,1211,1176,1162,
1064, 1004, 993, 838, 792, 755, 737, 705, 664, 654; UV/Vis (CHCl3)
lmax (log ε): 434 (5.51), 573 (4.07), 618 (4.40) nm; 1H NMR
7.79e7.75 (m, 4H, cor b-H), 7.60e7.52 (m, 4H, cor b-H), 7.36e7.29
(m, 6H, Ph-H), 7.20e7.14 (m, 8H, Ph-H), ꢁ3.03 (br s, 2H, NH); 13C
(400 MHz, CDCl3)
4H,
-H), 8.05 (d, J ¼ 7.0 Hz, 4H, Ph-H), 7.70e7.60 (m, 6H, Ph-H),
0.48 (s, 18 H, CH3); 13C NMR (100 MHz, CDCl3)
156.7, 153.2,
d
9.56 (d, J ¼ 4.6 Hz, 4H,
b
-H), 8.78 (d, J ¼ 4.4 Hz,
NMR (100 MHz, CDCl3) d 169.4, 150.5, 140.7, 135.7, 133.2, 131.4,
b
130.3, 128.8, 128.2, 127.2, 126.5, 125.5, 124.9, 122.7, 121.5, 93.0, 88.6;
HRMS (ESI): m/z calcd for C71H44CuN8 [MþH]þ 1071.2979, found
1071.2892.
d
152.2, 150.2, 142.1, 138.0, 134.4, 132.8, 131.3, 127.7, 126.7; HRMS
(ESI): m/z calcd for
717.1826.
C
42H37N4Si2Zn [MþH]þ 717.1843, found
4.13. Dyad 16
4.10. 5,15-Diethynyl-10,20-diphenylporphyrin (13)
A solution of 10-(4-Bromophenyl)-,15-diphenylcorrole-cop-
per(III)
(3)
(0.055 g,
0.0826 mmol),
(9) (0.050 g,
5-ethynyl-10,20-
0.091 mmol),
5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrin
(11)
diphenylporphyrinato-zinc(II)
(0.050 g, 0.080 mmol) was dissolved in CH2Cl2 (3 mL) and TBAF
(0.162 mL, 0.162 mmol) was added to the solution. After 30 min,
CH3CO2H (13 mL) and CH3OH (4 mL) were added to the reaction. The
PdCl2(PPh3)2 (0.003 g, 0.0041 mmol) and CuI (0.001 g,
0.0041 mmol) in 5 mL of Et3N (5 mL) and toluene (3 mL) was
deoxygenated and stirred at 40 ꢀC under N2 atmosphere. After 8 h,
the mixture was cooled to room temperature and H2O (5 mL) was
added. The aqueous phase was extracted with CH2Cl2 (3 ꢂ 5 mL).
The solvent was removed under reduced pressure. The crude
product was purified by flash column chromatography (CHCl3/
hexanes 1:1) to provide 16 (64 mg, 68%) as a puꢁrp1le solid: m.p.>
mixture was filtered after 30 min and the solid product was washed
with methanol to provide 13 (27 mg, 65%) as a puꢁrp1le solid: m.p.>
300 ꢀC; Rf: 0.62 (EtOAc/hexanes 1:10); IR (ATR, cm
) n 3265, 2968,
2085, 1806, 1593, 1560, 1475, 1442, 1401, 1347, 1260, 1199, 1159,
1093, 1064, 1028, 969, 913, 877, 794, 786, 749, 732, 716, 699, 676,
659; UV/Vis (CHCl3) lmax (log ε): 427 (5.32), 531 (4.02), 571 (4.24),
300 ꢀC; Rf: 0.83 (CHCl3/hexanes 1:1); IR (ATR, cm
) n 2957, 2924,
608 (3.64), 670 (3.83) nm; 1H NMR (400 MHz, CDCl3)
d
9.59 (d,
2853, 1731, 1600, 1492, 1461, 1377, 1272, 1210, 1122, 1093, 1073,
1044, 1002, 993, 877, 847, 820, 793, 781, 749, 21, 699, 668, 656; UV/
Vis (CHCl3) lmax (log ε): 418 (4.47), 548 (3.36) nm; 1H NMR
J ¼ 4.4 Hz, 4H,
b
-H), 8.79 (d, J ¼ 3.9 Hz, 4H,
b
-H), 8.11 (d, J ¼ 7.3 Hz,
4H, Ph-H), 7.79e7.68 (m, 6H, Ph-H), 4.14 (s, 2H, C^CH), ꢁ2.40 (br s,
2H, NH); HRMS (ESI): m/z calcd for C36H23N4 [MþH]þ 511.1917,
found 511.1920.
(400 MHz, CDCl3)
porp
-H), 9.38 (d, J ¼ 4.5 Hz, 2H, porp
-H), 8.22 (br s, 4H, Ph-H), 7.80e7.75 (m, 6H, Ph-H), 7.74e7.69 (m,
4H, cor -H), 7.55e7.51 (m, 4H, cor -H), 7.30e7.20 (m, 12H, Ph-H),
7.19e7.10 (m, 8H, Ph-H); 13C NMR (100 MHz, CDCl3)
169.5, 151.5,
d
10.26 (s, 1H, meso-H), 9.56 (d, J ¼ 4.6 Hz, 2H,
b
b
-H), 9.08e9.04 (m, 4H, porp
b
4.11. 5,15-Diethynyl-10,20-diphenylporphyrinato-zinc(II) (14)
b
b
d
5,15-Bis(trimethylsilylethynyl)-10,20-diphenylporphyrinato-
zinc(II) (12) (0.086 mmol) was dissolved in CH2Cl2 (4 mL) and TBAF
(0.175 mL, 0.175 mmol) was added to the solution. After 30 min,
145.4, 140.7, 135.7, 135.6, 134.5, 132.4, 131.4, 128.8, 128.3, 128.2,
126.6, 125.5, 124.9, 93.4, 92.0; HRMS (ESI): m/z calcd for
C
71H42CuN8Zn [MþH]þ 1133.2114, found 1133.2076.
CH3CO2H (15 mL) and CH3OH (5 mL) were added to the reaction. The
mixture was filtered after 30 min and the solid product was washed
with methanol to provide 14 (34 mg, 68%) as a purple solid: m.p.>
4.14. Triad 17
300 ꢀC; Rf: 0.78 (EtOAc/hexanes 1:3); IR (ATR, cmꢁ1
)
n
3259, 2090,
10-(4-Bromophenyl)-5,15-diphenylcorrole-copper(III)
(3)
1803, 1595, 1498, 1441, 1342, 1308, 1262, 1229, 1211, 1173, 1066,
1003, 995, 969, 934, 915, 847, 828, 791, 750, 737, 712, 699, 673, 663,
654; UV/Vis (CHCl3) lmax (log ε): 430 (5.29), 575 (3.90), 622 (4.11)
(186 mg, 0.280 mmol) and 5,15-dibromo-10,20-diphenylporphyrin
(13) (72 mg, 0.140 mmol) were dissolved in Et3N/toluene (1:3,
80 mL) and the mixture was deoxygenated. AsPh3 (0.060 g,
0.240 mmol) and Pd2(bda)3 (0.024 g, 0.120 mmol) were added to
the reaction and the mixture was stirred for 12 h at 40 ꢀC under N2
atmosphere. The reaction was quenched with H2O (10 mL). The
aqueous phase was extracted with CHCl3 (3 ꢂ 10 mL). The solvent
was removed under reduced pressure. The crude product was pu-
rified by flash column chromatography (CHCl3/hexanes 1:1) to
provide 17 (113 mg, 48%) as a purple solid: m.p.> 300 ꢀC; Rf: 0.71
nm; 1H NMR (400 MHz, d8-THF)
(d, J ¼ 4.6 Hz, 4H,
d
9.55 (d, J ¼ 4.6 Hz, 4H,
b-H), 8.72
b
-H), 8.06 (d, J ¼ 7.6 Hz, 4H, Ph-H), 7.60e7.70 (m,
6H, Ph-H), 4.52 (s, 2H, C^CH); HRMS (ESI): m/z calcd for
C
36H21N4Zn [MþH]þ 573.1052, found 573.1055.
4.12. Dyad 15
10-(4-Bromophenyl)-5,15-diphenylcorrole-copper(III)
(3)
(CHCl3/hexanes 1:1); IR (ATR, cmꢁ1
) n 2963, 2925, 2850, 2358,
(93 mg, 0.14 mmol) and 5-ethynyl-10,20-diphenylporphyrin (8)
(68 mg, 0.14 mmol) were dissolved in Et3N/toluene (1:3, 60 mL) and
the mixture was deoxygenated. AsPh3 (0.030 g, 0.120 mmol) and
Pd2(dba)3 (0.012 g, 0.060 mmol) were added to the reaction and the
mixture was stirred for 12 h at 40 ꢀC. The reaction was quenched
with H2O (10 mL). The aqueous phase was extracted with CHCl3
2328,1717, 1679, 1653, 1559, 1507, 1457, 1376,1259, 1215,1160, 1106,
1072, 1011, 885, 799, 712, 668; UV/Vis (CHCl3) lmax (log ε): 427
(4.83), 532 (3.76), 571 (3.91), 609 (3.46), 670 (3.58); 1H NMR
(400 MHz, d8-THF)
d
9.56 (d, J ¼ 4.6 Hz, 4H, porp
-H), 8.12e8.07 (m, 4H, Ph-H), 7.90e7.85 (m,
-H), 7.68e7.62 (m, 8H, Ph-H),
b-H), 8.74 (d,
J ¼ 5.0 Hz, 4H, porp
b
4H, cor
b
-H), 7.74e7.70 (m, 6H, cor
b
Please cite this article in press as: B. Temelli, et al., Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT
calculations, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.07.007

12
B. Temelli et al. / Tetrahedron xxx (2018) 1e13
Academic Press, San Diego, 2000.
7.60e7.57 (m, 4H, cor
b-H), 7.54e7.51 (m, 4H, cor
b
-H), 7.50e7.45
[2] (a) J.-H. Chou, M.E. Kosal, H.S. Nalwa, N.A. Rakow, K.S. Suslick, in: K. Kadish,
K. Smith, R. Guilard (Eds.), Porphyrin Handbook, vol. 6, Academic Press, New
York, 2000, pp. 43e131;
(m, 8H, 4 cor b-H, 4 Ph-H), 7.45e7.42 (m, 8H, Ph-H), 7.27e7.24 (m,
4H, Ph-H), 7.15e7.12 (m, 4H, Ph-H), ꢁ2.35 (br s, 2H, NH); 13C NMR
(b) article in press: S. Shao, et al., Metalloporphyrin nanoparticles: coordi-
nating diverse theranostic functions Coord. Chem. Rev. (2017) https://doi.org/
10.1016/j.ccr.2017.09.002.
(100 MHz, CDCl3)
d 169.6, 140.8, 135.6, 131.4, 128.8, 128.3, 125.5,
124.9, 121.6, 93.5, 89.9; HRMS (ESI): m/z calcd for C110H65Cu2N12
[MþH]þ 1679.4047, found 1679.4094.
[3] D. Kim, Multiporphyrin Arrays: Fundamentals and Applications, Pan Stanford,
Singapore, 2012.
[4] (a) R. Paolesse, R.K. Pandey, T.P. Forsyth, L. Jaquinod, K.R. Gerzevske,
D.J. Nurco, M.O. Senge, S. Licoccia, T. Boschi, K.M. Smith, J. Am. Chem. Soc. 118
(1996) 3869;
4.15. Triad 18
ꢀ ^
(b) R. Guilard, F. Jerome, C.P. Gros, J.-M. Barbe, Z. Ou, J. Shao, K.M.C.R. Kadish,
Acad. Sci. Ser. IIc: Chim. 4 (2001) 245;
A solution of 10-(4-bromophenyl)-5,15-diphenylcorrole-cop-
per(III) (3) (0.182 g, 0.273 mmol), 5,15-diethynl-10,20-diphe-
nylporphyrinato-zinc(II) (14) (0.050 g, 0.091 mmol), PdCl2(PPh3)2
(0.007 g, 0.0091 mmol) and CuI (0.002 g, 0.0091 mmol) in 7 mL of
Et3N and 5 mL of toluene was deoxygenated and stirred at 40 ꢀC
under N2 atmosphere. After 8 h, the mixture was cooled to room
temperature and H2O (10 mL) was added. The aqueous phase was
extracted with CH2Cl2 (3 ꢂ 10 mL). The solvent was removed under
reduced pressure. The crude product was purified by flash column
chromatography (CHCl3/hexanes 1:1) to provide 18 (64 mg, 40%) as
a purple solid: m.p.> 300 ꢀC; Rf: 0.80 (CHCl3/hexanes 1:1); IR (ATR,
(c) R. Guilard, F. Burdet, J.-M. Barbe, C.P. Gros, E. Espinosa, J. Shao, Z. Ou,
R. Zhan, K.M. Kadish, Inorg. Chem. 44 (2005) 3972;
(d) L. Flamigni, B. Ventura, M. Tasior, D.T. Gryko, Inorg. Chim. Acta. 360 (2007)
803;
(e) T.H. Ngo, F. Nastasi, F. Puntoriero, S. Campagna, W. Dehaen, W. Maes, Eur. J.
Org. Chem. (2012) 5605;
(f) T.H. Ngo, D. Zieba, W.A. Webre, G.N. Lim, P.A. Karr, S. Kord, S. Jin, K. Ariga,
M. Galli, S. Goldup, J.P. Hill, F. D'Souza, Chem. Eur. J. 22 (2016) 1301;
ꢀ
(g) V. Nikolaou, K. Karikis, Y. Farre, G. Charalambidis, F. Odobel,
A.G. Coutsolelos, Dalton Trans. 44 (2015) 13473;
(h) M. Murugavel, R.V.R. Reddy, J. Sankar, RSC Adv. 4 (2014) 13669;
(i) C. Chen, Y.-Z. Zhu, Q.-J. Fan, H.-B. Song, J.-Y. Zheng, Chem. Lett. 42 (2013)
936;
(j) S. Hiroto, I. Hisaki, H. Shinokubo, A. Osuka, Angew. Chem. Int. Ed. 44 (2005)
6763.
cmꢁ1
) n 3375, 3053, 2920, 2850, 1682, 1588, 1516, 1492, 1422, 1366,
1339, 1310, 1250, 1190, 1108, 1070, 1052, 1020, 1009, 982, 898, 874,
831, 811, 789, 758, 732, 707, 674; UV/Vis (CHCl3) lmax (log ε): 441
(4.59), 575 (3.76), 531 (3.65), 622 (3.90); 1H NMR (400 MHz, d8-
[5] (a) C.B. KC, G.N. Lim, F. D'Souza, Nanoscale 7 (2015) 6813;
(b) A.M.V.M. Pereira, A.R.M. Soares, A. Hausmann, M.G.P.M.S. Neves,
ꢀ
A.C. Tome, A.M.S. Silva, J.A.S. Cavaleiro, D.M. Guldi, T. Torres, Phys. Chem.
THF)
-H), 8.07 (d, J ¼ 6.5 Hz, 4H, Ph-H), 7.85 (br s, 2H, cor
2H, cor -H), 7.72e7.60 (m, 14H, Ph-H), 7.59e7.55 (m, 4H, cor
7.52e7.49 (m, 4H, cor -H), 7.49e7.45 (m, 8H, 4 cor -H, 4 Ph-H),
7.38e7.44 (m, 8H, Ph-H), 7.24 (br s, 4H, Ph-H), 7.15e7.10 (m, 4H,
Ph-H); 13C NMR (100 MHz, CDCl3)
169.7, 141.0, 140.8, 135.8, 128.4,
d
9.55 (d, J ¼ 4.6 Hz, 4H, porp
b
-H), 8.73 (d, J ¼ 4.5 Hz, 4H, porp
-H), 7.79 (s,
-H),
Chem. Phys. 13 (2011) 11858;
(c) A.R.M. Soares, V.M. Martinez-Diaz, A. Bruckner, A.M.V.M. Pereira,
b
b
ꢀ
ꢀ
J.P.C. Tome, C.M.A. Alonso, M.A.F. Faustino, M.G.P.M.S. Neves, A.C. Tome,
A.M.S. Silva, J.A.S. Cavaleiro, T. Torres, D.M. Guldi, Org. Lett. 9 (2007) 1557.
[6] Y. Inokuma, S. Hayashi, A. Osuka, Chem. Lett. 38 (2009) 206.
[7] (a) C.Y. Le, J.T. Hupp, Langmuir 26 (2010) 3760;
(b) C. Jiao, L. Zhu, J. Wu, Chem. Eur. J. 17 (2011) 6610;
(c) T.K. Khan, M. Ravikanth, Tetrahedron 68 (2012) 830;
(d) M.J. Leonardi, M.R. Topka, P.H. Dinolfo, Inorg. Chem. 51 (2012) 13114;
(e) B. Brizet, A. Eggenspiller, C.P. Gros, J.-M. Barbe, C. Goze, F. Denat,
P.D. Harvey, J. Org. Chem. 77 (2012) 3646;
b
b
b
b
d
128.2, 125.5, 96.8, 89.2; HRMS (ESI): m/z calcd for C110H63Cu2N12Zn
[MþH]þ 1741.3177, found 1741.2995.
(f) Q.-Q. Hu, Y.-Z. Zhu, S.-C. Zhang, Y.-Z. Tong, J.-Y. Zheng, Dalton Trans. 44
(2015) 15523.
4.16. Computational methods
[8] (a) T. Tanaka, N. Aratani, J.M. Lim, K.S. Kim, D. Kim, A. Osuka, Chem. Sci. 2
(2011) 1414;
Computational studies were performed using B3LYP [23] hybrid
functional in combination with the 6-311G(d,p) [24] basis set.
Vertical excitation energies were computed by means of time-
dependent density functional theory (TD-DFT) calculations based
on the optimized geometries. The lowest 100 vertical excitation
energy states were considered. All DFT and TD-DFT calculations in
this study were performed using the Gaussian 09 software [25]. For
the visualization of the optimized geometries and the molecular
orbitals, the GaussView [26] software was used. The Mulliken
Population Analysis (MPA) of the molecular orbitals was performed
using the GaussSum package [27].
(b) H. Mori, T. Tanaka, S. Lee, J.M. Lim, D. Kim, A. Osuka, J. Am. Chem. Soc. 137
(2015) 2097.
ꢀ
[9] (a) J.F.B. Barata, M.G.P.M.S. Neves, M.A.F. Faustino, A.C. Tome, J.A.S. Cavaleiro,
Chem. Rev. 117 (2017) 3192;
(b) R. Orlowski, D. Gryko, D.T. Gryko, Chem. Rev. 117 (2017) 3102;
(c) I. Aviv, Z. Gross, Chem. Commun. (2007) 1987.
[10] B. Temelli, O. Ozasik, D. Yüksel, Eur. J. Org. Chem. (2017) 4905.
[11] B. Temelli, H. Kalkan, Beilstein J. Org. Chem. 14 (2018) 187.
[12] B. Koszarna, D.T. Gryko, J. Org. Chem. 71 (2006) 3707.
[13] M. Murugavel, R.V.R. Reddy, D. Dey, J. Sankar, Chem. Eur. J. 21 (2015) 14280.
[14] I. Luobeznova, L. Simkhovich, I. Goldberg, Z. Gross, Eur. J. Inorg. Chem. 8
(2004) 1724.
~
[15] C. Brückner, R.P. Brinas, J.A. Krause Bauer, Inorg. Chem. 42 (2003) 4495.
[16] C.M. Lemon, M. Huynh, A.G. Maher, B.L. Anderson, E.D. Bloch, D.C. Powers,
D.G. Nocera, Angew. Chem. Int. Ed. 55 (2016) 2176.
[17] A.B. Alemayehu, L.K. Hansen, A. Ghosh, Inorg. Chem. 49 (2010) 7608.
[18] K. Pierloot, H. Zhao, S. Vancoillie, Inorg. Chem. 49 (2010) 10316.
[19] W. Sinha, M.G. Sommer, N. Deibel, F. Ehret, M. Bauer, B. Sarkar, S. Kar, Angew.
Chem. Int. Ed. 54 (2015) 13769.
[20] B.J. Littler, M.A. Miller, C.-H. Hung, R.W. Wagner, D.F. O'Shea, P.D. Boyle,
J.S. Lindsey, J. Org. Chem. 64 (1999) 1391.
[21] S.G. DiMagno, V.S.-Y. Lin, M.J. Therien, J. Org. Chem. 58 (1993) 5983.
[22] C. Liu, D.-M. Shen, Q.-Y. Chen, Chem. Commun. (2006) 770.
[23] (a) A.D. Becke, J. Chem. Phys. 98 (1993) 5648;
Acknowledgements
The authors thank Hacettepe University (BAP project 014 09 601
002-723) and The Scientific and Technological Research Council of
Turkey (project number: 115Z886) for financial support.
Appendix A. Supplementary data
(b) C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785.
[24] (a) A.D. McLean, G.S. Chandler, J. Chem. Phys. 72 (1980) 5639;
(b) K. Raghavachari, J.S. Binkley, R. Seeger, J.A. Pople, J. Chem. Phys. 72 (1980)
650;
Supplementary data associated with this article can be found in
the online version, at https://doi.org/10.1016/j.tet.2018.07.007.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
(c) A.J.H. Wachters, J. Chem. Phys. 52 (1970) 1033;
(d) P.J. Hay, J. Chem. Phys. 66 (1977) 4377.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb,
J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino,
G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven,
J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers,
K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand,
K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi,
References
[1] (a) L.R. Milgrom, The Colours of Life: an Introduction to the Chemistry of
Porphyrins and Related Compounds, Oxford University Press, New York, 1997;
(b) K.M. Kadish, K.M. Smith, R. Guilard, The Porphyrin Handbook, vols. 1e20,
Please cite this article in press as: B. Temelli, et al., Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT
calculations, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.07.007

B. Temelli et al. / Tetrahedron xxx (2018) 1e13
Gaussian, Inc., Wallingford CT, 2010.
13
N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi,
C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski,
G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas,
J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision C.01,
[26] R.D. Dennington II, T.A. Keith, J.M. Millam, GaussView, Semichem, Inc., Wall-
ingford, CT, 2008, 5.0.8. .
[27] N.M. O'Boyle, A.L. Tenderholt, K.M. Langner, J. Comput. Chem. 29 (2008) 839.
Please cite this article in press as: B. Temelli, et al., Ethynyl-bridged porphyrin-corrole dyads and triads: Synthesis, properties and DFT
calculations, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.07.007