Synthesis of Functionalized BODIPYs, BODIPY-Corrole, and BODIPY-Porphyrin Arrays with 1,2,3-Triazole Linkers Using the 4-Azido(tetrafluorophenyl)-BODIPY Building Block

Article abstract of DOI:10.1002/ejoc.201500413

The copper(I)-catalyzed 1,3-dipolar cycloaddition of 4-azido(tetrafluorophenyl)boron-dipyrrin (azido-BODIPY) with diverse terminal alkynes, varying from simple alkyl-substituted derivatives to alkynes with functional groups and carbohydrates, was successf

Full text of DOI:10.1002/ejoc.201500413

FULL PAPER
DOI: 10.1002/ejoc.201500413
Synthesis of Functionalized BODIPYs, BODIPY-Corrole, and BODIPY-
Porphyrin Arrays with 1,2,3-Triazole Linkers Using the
4-Azido(tetrafluorophenyl)-BODIPY Building Block
Hartwig R. A. Golf,[a,b] Anna M. Oltmanns,[a] Duc H. Trieu,[a] Hans-Ulrich Reissig,*[a] and
Arno Wiehe*[a,b]
Keywords: Porphyrinoids / Nucleophilic substitution / Click chemistry / Chromophores
The copper(I)-catalyzed 1,3-dipolar cycloaddition of 4-azido- linked array systems consisting of porphyrins and corroles
(tetrafluorophenyl)boron-dipyrrin (azido-BODIPY) with di-
verse terminal alkynes, varying from simple alkyl-substituted
derivatives to alkynes with functional groups and carbo-
hydrates, was successfully employed to obtain meso-func-
tionalized BODIPY derivatives through the 1,2,3-triazole
linkage. The scope of this reaction was extended to the prep-
aration of di- and trivalent BODIPY systems through the use
of appropriate alkynyl linkers. Moreover, the synthesis of hy-
droxyl- and pentafluorothio-(SF5)-substituted, 1,2,3-triazole-
as the central scaffold, in combination with a BODIPY, was
investigated. These covalently connected tetrapyrrole-
BODIPY arrays exemplify a versatile approach to the con-
struction of multichromophore systems: the combination of
1,3-dipolar cycloaddition and nucleophilic substitution on
pentafluorophenyl-substituted porphyrinoids. The systems
designed herein could serve in various light-harvesting ap-
plications and electron-transfer studies.
sis and functionalization of porphyrins is reasonably
straightforward, allowing a fine-tuning of their photophysi-
cal and redox properties through various modifications at
the meso- and β-pyrrole positions or complexation with a
broad variety of metal ions due to the flexible inner cavity
and the four ring-centered nitrogen donors. Regarding their
photophysical properties, free-base porphyrins exhibit ab-
sorption bands in the blue and red region around 400 to
800 nm of the visible light spectrum, characterized by a
strong Soret and four Q-bands. Metalloporphyrins, on the
other hand, exhibit a strong Soret and one or two Q-bands
in the same region. On their own, porphyrins and me-
talloporphyrins are not ideally suited for broad-band light-
harvesting arrays because of their lack of a significant op-
tical cross-section in the green light region of the visible
spectrum around 450 to 550 nm.[7]
Introduction
The rational design and synthesis of chromophore-based
energy-transfer array systems that mimic natural photosyn-
thetic processes for light-harvesting applications is a field
of ongoing interest. Porphyrin-based arrays have often been
employed because of their structural similarity to the natu-
rally occurring chlorophyll-based systems. In this regard,
several approaches towards multi-porphyrin arrays have
been presented as model compounds for artificial light-har-
vesting and energy-transfer processes in photosynthesis.[1]
Within such systems, photoinduced electron transfer and
high-energy charge-separated states can be observed.[2]
Porphyrins (Figure 1) are one of the most widely investi-
gated groups of tetrapyrrolic macrocycles; they are essential
for a range of biological processes and have found various
applications in many fields because of their abundant redox
and photochemical properties. They are being used in medi-
cine as photosensitizers for photodynamic therapy (PDT),[3]
as dyes for photoactive materials,[4] as catalysts,[5] and, as
mentioned above, for light-harvesting arrays.[6] The synthe-
[a] Institut für Chemie und Biochemie, Freie Universität Berlin,
Takustr. 3, 14195 Berlin, Germany
E-mail: hans.reissig@chemie.fu-berlin.de
http://www.bcp.fu-berlin.de/en/chemie/chemie/forschung/
OrgChem/reissig/index.html
Figure 1. Skeletons of porphyrin A, corrole B, and boron-dipyrrin
(BODIPY) C dyes.
[b] Biolitec Research GmbH,
Otto-Schott-Str. 15, 07745 Jena, Germany
E-mail: arno.wiehe@biolitec.de
http://www.biolitec.de
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500413.
Another class of chromophores with growing importance
are
4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes,
also
known as boron-centered dipyrrins or BODIPYs (Fig-
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Synthesis of Functionalized BODIPY Arrays
ure 1), which were reported for the first time by Treibs and ade. However, only very few examples of molecular chro-
Kreuzer in 1968.[8] Favorable properties such as high fluo- mophores based on a corrole–BODIPY conjugation are
rescence quantum yields, high molar absorption coeffi- known.[19] Such systems may not only be applied in light
cients, low intersystem crossing rates, a long lifetime after harvesting but may also find use in catalytic processes in-
excitation, and a high photostability are reasons why BOD- volving metals in high oxidation states.
IPYs are excellent dyes for a variety of applications in fields
Herein, we describe an approach towards BODIPY–tet-
such as organic-based photonics,[9] biological labeling,[10] rapyrrole conjugates by using an azido-functionalized
OLED-technology,[11] fluorescent probes for cell im- BODIPY and alkynyl-substituted tetrapyrroles through the
aging,[12] and artificial photosynthetic systems.[13] From the well-known copper(I)-catalyzed 1,3-dipolar cycloaddition
photophysical aspect, BODIPYs exhibit sharp absorption of azides with alkynes. This study includes the synthesis of
andemissioninthevisiblelightspectrumaround500 nm. The 1,2,3-triazole-linked arrays consisting of BODIPY and a
BODIPY scaffold is easily accessible from the dipyrrome- copper(III)corrole with hydrophilic hydroxyl and lipophilic
thane building block through a multistep, one-pot reac- pentafluorothio (SF5) substituents. Furthermore, the analo-
tion[14] and can be modified easily to fine-tune their optical gous synthesis of fluorophenyl-substituted BODIPY-
and electronic properties by structural modifications at the zinc(II) porphyrin arrays through 1,3-dipolar cycloaddition
meso- and pyrrole-positions. An exponential trend in the was also performed. The scope and reactivity of azido-
development of BODIPY chemistry can be observed be- BODIPY itself was investigated through its reaction with a
cause of their abundant applications and their outstanding range of terminal alkynes under copper(I) catalysis, leading
chemical and photophysical properties.
to meso-functionalized BODIPYs.
One way to increase the spectroscopic coverage and
hence the efficiency in synthetic light harvesting is the con-
junction of multiple chromophores that exhibit different ab-
sorption ranges. When comparing the complementary ab-
sorption spectra of porphyrins and BODIPYs, their link-
Results and Discussion
One of our main interests is the functionalization of tet-
age – either through covalent bonding or noncovalent inter- rapyrroles with alkoxides by nucleophilic aromatic substitu-
action – results in a desirable supplement towards enhanced tion on pentafluorophenyl-substituted systems.[20] Initially,
light-harvesting properties throughout a broad range in the we tried a synthetic approach towards multichromophoric
visible light spectrum between 400 and 700 nm. Hence, re- tetrapyrrole-BODIPY arrays by using a pentafluorophenyl
search on BODIPY–porphyrin conjugates has increased ex- (PFP)-substituted porphyrin, PFP-dipyrromethane (PFP-
ponentially in recent years; the first of such conjugates was DPM), as a precursor for BODIPYs, and diols as linkers.
reported by Lindsey in 1998 during a mixed condensation In theory, the DPM part of the final array system could
reaction performed during studies on light-harvesting com- be transformed into the corresponding BODIPY. However,
pounds.[15]
regardless of whether a PFP-substituted porphyrin was
Corroles, in contrast, are porphyrin-related analogues functionalized first with the diol and then conjugated with
with skeletons that are contracted by one meso-carbon, thus PFP-DPM or whether PFP-DPM was functionalized first
incorporating a direct pyrrole–pyrrole connection (Fig- and later reacted with a porphyrin by nucleophilic substitu-
ure 1). Regarding coordination chemistry, corroles act as tion, these protocols did not give the desired products, al-
tetradentate trianionic ligands, whereas porphyrins exhibit though a diol-linkage between two PFP-substituted por-
a diprotonic inner cavity. This unique feature of corroles phyrins has recently been described.[20a] Therefore, we de-
allows the stabilization of metal ions in unusually high oxid- cided to make use of the copper(I)-catalyzed 1,3-dipolar cy-
ation states such as iron(IV) or cobalt(IV) and cobalt(V).[16] cloaddition for the synthesis of the linked arrays.[22] The
For a long time, only a very limited number of reports on azido-functionalized BODIPY 3 was chosen as the 1,3-di-
applications for this class of macrocycles has appeared be- pole for the cycloaddition reaction because of its straight-
cause of the severe synthetic obstacles involved and because forward and convenient synthesis.[20b,21]
of the lack of efficient preparative procedures. As of 1999,
Azido-BODIPY 3 was synthesized over two steps start-
the groups of Gross,[17a] Paolesse,[17b] and Gryko[17c–17e] re- ing from pentafluorophenyl-dipyrromethane (PFP-DPM;
ported various straightforward methods towards direct cor- 1). Compound 1 was converted into PFP-BODIPY 2 by
role synthesis starting from readily available reagents; these the well-known three-step, one-pot protocol for BODIPYs
studies led to refocused attention on corrole chemistry that involving (1) oxidation by 2,3-dichloro-5,6-dicyano-1,4-
resulted in the development of a variety of transformations benzoquinone (DDQ), (2) proton abstraction with DIPEA
and applications such as oxidation[18a–18c] and reduc- and (3) by complexation with boron trifluoride–diethyl
tion[18d,18e] catalysis, corrole-based sensors,[18f–18i] and me- ether.[8] PFP-BODIPY 2 was then transformed into 3 in
dicinal applications.[18j–18l] Similar to porphyrins, corroles nearly quantitative yield by direct azidation reaction with
exhibit a characteristic absorbance with a sharp Soret band sodium azide in N,N-dimethylformamide (DMF)
around 400 nm and Q-bands in the range between 500 to (Scheme 1).[20b,21] This reaction can be carried out on a
600 nm.
gram scale because of the highly efficient and regioselective
Diverse array systems consisting of BODIPYs and por- azidation reaction at the para-position of the pentafluoro-
phyrins were reported and investigated during the last dec- phenyl substituent. The conceivable alternative direct azid-
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Table 1. Terminal alkynes investigated for the 1,3-dipolar cycload-
dition with azido-BODIPY 3.[a]
Scheme 1. Synthesis of azido-BODIPY 3 in two steps, starting from
PFP-DPM 1 via PFP-BODIPY 2.[21]
ation of DPM 1 with sodium azide followed by oxidation
to BODIPY 3 could not be realized.[20b]
In previous studies, we have investigated the functionali-
zation of 1 with alcohols and, further, the transformation
of such alkoxy-substituted DPMs into BODIPYs.[21] This
type of meso-functionalization allows the chromophore to
be modified with various functional groups with only mar-
ginal influence on the optical properties of the BODIPY
scaffold. The same should apply for any azide-alkyne click
products of BODIPY 3. To examine the reaction behavior
of 3 under copper(I)-catalyzed reaction conditions, we first
tried various reactions of 3 with terminal alkynes, resulting
in meso-functionalized 1,2,3-triazole-linked BODIPYs 4a–i
(Scheme 2, for alkynes see Table 1).
[a] Reactions were carried out under argon atmosphere. [b] Yield
of isolated product after purification. [c] See ref.[21]
duction of the azido group also occurred in part in the reac-
tions with two alkynyl-functionalized carbohydrates (entries
4 and 5). In a test reaction, BODIPY 3 was reacted under
identical reaction conditions used for the coupling with ter-
minal alkynes [copper(II) sulfate, sodium ascorbate,
DMSO, argon atmosphere] except that the alkyne was omit-
ted (Scheme 3). Within one hour, a nearly quantitative re-
duction of 3 to 5 was observed. Tentatively, this may be
explained by a redox reaction comprising the reduction of
the azido group to the amino group and, at the same time,
an oxidation of copper(I) to copper(II), which, in turn, is
reduced to copper(I) by sodium ascorbate.[24a,24b] In the
presence of DMSO as solvent, a mechanism operating via
a nitrene intermediate has also been discussed.[24d]
Scheme 2. Copper(I)-catalyzed 1,3-dipolar cycloaddition of
BODIPY 3 to alkynes (for substituents R of the alkyne see Table 1).
The reaction of azido-BODIPY 3 and 1-heptyne in di-
methyl sulfoxide (DMSO) afforded triazole 4a within
30 min in good yield (Table 1, entry 1). The reaction with
propargyl alcohol led to the corresponding triazole 4b (en-
try 2) with lower yield (32%). Here, the formation of a side
product was observed in which the azido function of
BODIPY 3 underwent a reduction to give the amino-substi-
tuted BODIPY 5. Similar reactions of halogenated elec-
tron-deficient aromatic azides are known.[23,24] In case of
Scheme 3. Reduction of BODIPY 3 to amino-BODIPY 5 in the
presence of copper(II) sulfate and sodium ascorbate.
The reaction of 3 with di- and tri-ynes was then studied
propargylamine, no reaction to the desired product 4c could because such linkers can give access to multivalent
be observed (entry 3), and only 5 was isolated. Amino li- BODIPY systems (Table 1, entries 6–10).
gands may favor the reduction of the azide as previously
The BODIPY dimers (4f and 4g; Table 1, entries 6–7)
reported.[23] This could explain why, in this case, only and trimers (4h and 4i; entries 8–10) were obtained in ac-
amino-BODIPY 5 was isolated with 58% yield. The re- ceptable yields. The conditions for the synthesis of
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Synthesis of Functionalized BODIPY Arrays
BODIPY trimer 4i, which we recently published,[21] were perature revealed a very slow reaction resulting in only trace
investigated in more detail. The reaction of 3 with triethin- amounts of the conjugates 8a or 8b isolated after 24 h. In-
ylbenzene (entries 9–10) was performed in tetrahydrofuran creasing the amount of copper catalyst from 1.1 to
(THF) and DMSO. In THF, using 8.1 equiv. 3, heating was 1.5 equiv. increased the yield of product 8a slightly. How-
required (72 h) and the reaction was carried out in a seal- ever, a significant improvement of the reaction was achieved
able high-pressure tube to give 4i in 30% yield with only by heating the reaction mixture at 80 °C in a high-pressure
trace amounts of amino-BODIPY 5. In contrast, in DMSO, reaction tube with 1.5 equiv. copper(II) sulfate. Whereas the
with only 3 equiv. of 3, a higher yield (45%) of 4i was ob- formation of the amino-BODIPY side product 5 was ob-
tained and the reaction was complete within two hours. The served in very low yield (below 5%), conjugates 8a and 8b
use of an excess of azide (again 8.1 equiv. of 3) further in- were obtained in good yields of 44 and 58%, respectively.
creased the yield of the corresponding triazole derivative 4i
(68%; entry 10).
We then focused on the synthesis of more complex com-
pounds starting with A2B-corrole systems 6a–c. Corroles
6a–c were obtained by the standard procedure for corrole
synthesis of Gryko and co-workers,[17] involving first the
condensation of dipyrromethanes with pentafluorobenzal-
dehyde in a water/methanol mixture (1:1, v/v) under HCl
(37% aq) catalysis and followed by DDQ-mediated oxid-
ation in the second step. The introduction of the essential
alkynyl group for the 1,3-dipolar cycloaddition reaction was
carried out by nucleophilic substitution with propargyl
alcohol on the pentafluorophenyl substituent,[20a] while at
the same time – due to the basic reaction conditions – the
acetoxy protecting groups were also cleaved. This type of
two-step, one-pot functionalization has recently been de-
scribed for porphyrins.[20a] Applying the optimized reaction
conditions (KOH, DMSO, argon atmosphere, room temp.)
and a large excess of alcohol (30–50 equiv.) and KOH (15–
30 equiv.) on 6a–c, yielded the alkynyl-functionalized cor-
roles 7a–c (Scheme 4).
Scheme 5. Copper(I)-catalyzed 1,3-dipolar cycloadditions of
BODIPY 3 to alkynyl-functionalized A2B-corroles 8a/b.
We then investigated the synthesis of more lipophilic con-
jugates involving pentafluorothio substituents as counter-
part to the polar 3-hydroxy- and 4-hydroxy-substituted cor-
roles 7a/b and 8a/b. SF5-substituents are also of interest be-
cause of their strong electron-withdrawing effect, which will
influence the redox potential of the porphyrinoid in the
conjugate.[25] SF5-substituted A2B-corrole 7c was synthe-
sized analogously to 7a and 7b: (1) condensation of 3-
fluoro-5-(pentafluorothio)benzaldehyde with PFP-DPM 1
followed by DDQ-mediated oxidation and (2) nucleophilic
substitution with propargyl alcohol and KOH in DMSO,
as we previously described in detail.[25d] In this case, DMSO
was employed for the 1,3-dipolar cycloaddition, which re-
sulted in a significant reduction of the reaction time com-
pared to that with THF. The reaction of SF5-substituted
corrole 7c with BODIPY 3 thus yielded the corresponding
conjugate 8c within 15 min in 32% yield (Scheme 6),
whereas in THF a reaction time of 12 hours and heating at
80 °C in a high-pressure reaction tube were necessary to
Scheme 4. Nucleophilic substitution on A2B-corroles 6a–c with
propargyl alcohol.
The 1,3-dipolar cycloaddition reactions of free-base cor- obtain 8c with 19% yield (see Exp. Sect. for details). In
roles 7a and 7b with azido-BODIPY 3 were carried out in both cases, either THF or DMSO, azido-BODIPY 3 had
THF to obtain the corresponding copper(III)corrole- to be used in an excess of 1.5 equiv. because of the forma-
BODIPY conjugates 8a and 8b, respectively (Scheme 5). tion of amino-BODIPY 5 as a side product. When the reac-
Our first attempts to carry out the reaction at room tem- tion was instead performed with equimolar amounts of cor-
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role and azido-BODIPY 3, a decreased yield of 15% (in corrole 9, PFP-DPM 1 was condensed with 3-acetoxy-
THF) and 21% (in DMSO) was observed for 8c.
benzaldehyde and oxidized with DDQ. SF5-substituted cor-
role 10 was obtained by condensation of pentafluorobenzal-
dehyde with 3-fluoro-5-(pentafluorothio)phenyl dipyrrome-
thane followed by DDQ-mediated oxidation.[25d] In accord-
ance with the synthesis of alkynyl-functionalized corroles
7a/b, 9 and 10 were treated with propargyl alcohol (with
KOH in DMSO) to obtain the dialkynyl-substituted cor-
roles 11 and 12 with 70 and 81%[25d] yield, respectively
(Scheme 7).
Scheme 6. Copper(I)-catalyzed 1,3-dipolar cycloaddition of
BODIPY 3 with alkynyl-functionalized A2B-corrole 7c.
Scheme 7. Nucleophilic substitution on AB2-corroles 9 and 10 with
propargyl alcohol.
To construct array systems involving more than one
BODIPY, as described above for diethinylbenzene (Table 1,
The dialkynyl-functionalized corroles 11 and 12 were
entry 7), AB2-corroles with two available alkynyl groups subsequently treated with azido-BODIPY 3 (2.5 equiv.) in
were chosen as suitable precursors towards divalent cop- DMSO to afford BODIPY-copper(III)corrole conjugates 13
per(III)corrole-BODIPY conjugates. The 10-meso substitu- and 14 within 30 min with similar yields to those of the
ent was selected in analogy to corroles 8a (3-hydroxyphenyl) monovalent conjugates 8a and 8b (Scheme 8). Copper(II)
and 8c (3-fluoro-5-pentafluorothio). For the synthesis of sulfate pentahydrate had to be used in excess because part
Scheme 8. Copper(I)-catalyzed 1,3-dipolar cycloadditions of BODIPY 3 with alkynyl-functionalized AB2-corroles 11 and 12.
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Synthesis of Functionalized BODIPY Arrays
of the copper is complexed by the corrole during the reac- DPM 1 with 3-acetoxybenzaldehyde followed by DDQ-me-
tion. Corroles are trianionic ligands, therefore a “protec- diated oxidation yielding porphyrin 15, (2) nucleophilic flu-
tion” of the inner core of the corrole with zinc prior to the orine exchange in DMSO with KOH and propargyl alcohol
coupling reaction – as used for porphyrins (see below) – is in accordance with the method described above (at the same
not possible here. Again, when the synthesis of array 14 time deprotecting the phenolic OH groups), and (3) com-
was performed in THF in a pressure tube at 80 °C, 14 was plexation of the free-base porphyrin with zinc(II) acetate.
obtained in a yield of only 8%. We believe that the lower The tetraalkynyl-substituted A4-porphyin 18 was obtained
yields of the BODIPY-corrole conjugates (compared with likewise, except that the condensation step was carried
the BODIPY-porphyrin conjugates, see below) may be ex- out with pentafluorobenzaldehyde and pyrrole only
plained by a partial oxidative (copper-mediated) decompo- (Scheme 9).[20a,29]
sition of the corrole scaffold; this lower stability of corroles
is well known.[26] For the corrole-BODIPY conjugate 14,
unfortunately, the NMR spectra could not be analyzed be-
cause of line broadening. Problems with the NMR analysis
have also been reported for other corrole systems.[27] The
line broadening observed for 14 is probably due to a cop-
per-based redox equilibrium between the diamagnetic CuIII
-
corrole complex and its CuII cation radical, this equilibrium
being dependent on factors such as temperature and sol-
vent.[28]
In the next step, the central scaffold was changed and the
conjugation was extended to the porphyrins. Two examples
were chosen, a trans-A2B2- and an A4-substituted por-
phyrin with two and four pentafluorophenyl substituents,
respectively. The synthetic route towards 1,2,3-triazole-
linked zinc(II)porphyrin arrays requires at least one ad-
ditional step, which is the protection of the free-base por-
phyrin core with zinc(II) acetate to prevent an undesired
copper(II) insertion during the 1,3-dipolar cycloaddition.
Due to the paramagnetic nature of copper(II)-porphyrin
species, NMR characterization would otherwise be difficult.
Additionally, the copper(II) demetallation of porphyrin
complexes would require harsh reaction conditions (strong
acids, high temperatures), which, in turn, may decompose
the conjugate. Such difficulties do not emerge with zinc(II),
and the free-base porphyrin can be easily regenerated by
treatment of the zinc complex with dilute acid.
Scheme 9. Nucleophilic substitution with propargyl alcohol on
A2B2-trans-porphyrin 15 and A4-porphyrin 16 with subsequent
zinc(II) insertion.
The synthesis of dialkynyl-substituted A2B2-porphyrin
The copper(I)-catalyzed 1,3-dipolar cycloadditions of
17 was carried out in three steps: (1) Condensation of PFP- porphyrins 17 and 18 with azido-BODIPY 3 were then car-
Scheme 10. Copper(I)-catalyzed 1,3-dipolar cycloadditions of BODIPY 3 to trans-A2B2-substituted porphyrin 17 and A4-substituted
porphyrin 18.
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ried out again in THF in a pressure tube at 80 °C to obtain to complex conjugates involving tetrapyrroles and BODI-
the corresponding di- and tetravalent zinc(II)porphyrin- PYs. Such systems are being investigated for their interest-
BODIPY arrays 19 and 20 in yields of 64 and 60%, respec- ing photophysical properties and possible applications for
tively (Scheme 10).[30] For comparison, the click reaction example in light-harvesting and photomedicine.[34]
leading to the trans-A2B2-porphyrin-BODIPY conjugate 19
was also carried out in DMSO at room temperature with
the result of a significantly shorter reaction time of 15 min
and a minor increase in isolated yield (69%).
Experimental Section
General: Nomenclature and numbering (13C NMR) are in accord-
ance to IUPAC recommendations. Reactions were performed in
oven-dried flasks under inert argon atmosphere if not mentioned
otherwise. Solvents were distilled and dried by standard procedures.
THF and DMSO used for reactions were purchased from Sigma–
Aldrich and kept over molecular sieve. All liquid reagents were
added by using syringes. Purchased reagents were used as received
without further purification. All reactions were monitored by thin-
layer chromatography (TLC) analysis and detection was achieved
with a CAMAG variable UV detector (λ = 254/366 nm). Purifica-
tion was carried out by column chromatography on silica gel (60
M, 40–63 μm), yields refer to analytically pure samples. NMR spec-
tra were recorded with Bruker (AC 250, AC 500, AV 700) and
JEOL (ECX 400, ECP 500) instruments. Chemical shifts are re-
ported relative to TMS (1H: δ = 0.00 ppm), CDCl3 (1H: δ =
7.26 ppm, 13C: δ = 77.0 ppm) and [D6]acetone (1H: δ = 2.05 ppm,
13C: δ = 29.8 ppm). Integrals are in accordance with assignments;
coupling constants are given in Hz. All 13C spectra are proton-
decoupled. Multiplicity is indicated as follows: s (singlet), d (doub-
let), t (triplet), m (multiplet), mc (centered multiplet), dd (doublet
of doublets), br. s (broad singlet). For detailed peak assignments
2D spectra were measured (COSY 1H-1H, HMQC 1H-13C, and
A photophysical investigation of the compounds de-
scribed here was beyond the scope of this (synthetic) investi-
gation, but some preliminary observations were made. The
absorption as well as the fluorescence spectra of the mono-
valent BODIPYs 4a–e compared with the di- and the tri-
valent BODIPYs 4f–i do not differ significantly. More pro-
nounced differences were observed between the fluores-
cence spectra of the two porphyrin-BODIPY conjugates 19
and 20. Thus, it will be interesting to compare the photo-
physical properties of these conjugates with those of others
reported in the literature.[31]
Conclusions
The synthesis of meso-functionalized 1,2,3-triazole-
linked BODIPYs employing the copper(I)-catalyzed 1,3-di-
polar cycloaddition of azides with alkynes has been pre-
sented in the first part of this report. The azide component
4-azido(tetrafluorophenyl)-BODIPY 3 was chosen because
of its convenient and easy access from PFP-dipyrro-
methane. This azido-functionalized BODIPY served as the
crucial building block and was treated with various ter-
minal alkynes bearing functional groups, mainly hydroxy
substituents, allowing a fine tuning of the chemical proper-
ties and increasing the solubility of the resulting function-
alized triazoles in polar solvents. The examples presented
also render this azido-substituted BODIPY an ideal candi-
date for fluorescence labeling of diverse (bio)molecules with
the BODIPY fluorophore.[32] Multivalent BODIPY sys-
tems[33] were obtained with appropriate di- and tri-alkynes
as linkers.
In the second part of the report, more complex 1,2,3-
triazole-linked conjugates prepared from zinc(II)porphyrins
and copper(III)corroles in combination with the azido-
BODIPY as an antenna molecule have been described. The
free-base porphyrins required a precomplexation with zin-
c(II) acetate prior to conjugation with azido-BODIPY to
prevent undesired copper(II) coordination during the cyclo-
1
HMBC H-13C correlation experiments). For detailed assignments
of single carbon and/or proton positions see formulas in the Sup-
porting Information. The UV/Vis spectra were measured with a
SPECORD S300 VIS UV/-Visible spectrometer, from Analytic
Jena, Jena, Germany, using acetone, CH2Cl2, or methanol as sol-
vent and quartz cuvettes of 1 cm length. Fluorescence emission
spectra were recorded with a JASCO FP6500 spectrometer using
quartz cuvettes of 1 cm length and acetone as solvent. HRMS
analyses were performed with an Agilent 6210 ESI-TOF, Agilent
Technologies, Santa Clara, CA, USA and a Bruker Ultraflex II;
solvent flow rate was adjusted to 4 μL/min and spray voltage was
set to 4 kV. Drying gas flow rate was set to 15 psi (1 bar). All other
parameters were adjusted for a maximum abundance of the respec-
tive [M + H]+. (ESI-TOF = electrospray ionization – time of flight).
Reported melting points were measured with a Reichert Thermovar
apparatus. Compounds 2,[21] 3,[21] 7c,[25d] 8c,[25d] 10,[25d] 12,[25d]
16,[29] and 18[20a] were prepared according to reported procedures.
An additional procedure for preparing 8c is included in the experi-
mental section. The synthetic procedures and characterization data
of 3- and 4-(acetoxyphenyl)dipyrromethane used for the synthesis
of corroles 6a and 6b are included in the Supporting Information.
addition. Mono- and divalent copper(III)corrole-BODIPY 8-[2,3,5,6-Tetrafluoro-4-(4-pentyl-1H-1,2,3-triazole-1-yl)phenyl]-
BODIPY (4a): BODIPY 3 (100 mg, 0.26 mmol) was dissolved un-
der an argon atmosphere in anhydrous DMSO (2.0 mL). Heptyne
(0.07 mL, 0.53 mmol), sodium ascorbate (0.31 g, 1.58 mmol), and
CuSO4·5H2O (21.1 mg, 0.09 mmol) were added and the reaction
mixture was stirred for 30 min at room temp. After aqueous
workup, extraction with CH2Cl2 (4ϫ 50 mL), and drying over so-
dium sulfate, the crude product was evaporated to dryness and
purified by column chromatography (n-hexane/ethyl acetate, 3:1,
v/v) to obtain BODIPY 4a (89 mg, 71%) as a red powder; m.p.
arrays with hydrophilic hydroxy and highly lipophilic penta-
fluorothio substituents were synthesized in an analogous
way. A precomplexation with a metal ion is not required
for corroles because of the two-step, one-pot procedure em-
ployed, in which complexation of copper by the free-base
corrole takes place during the cycloaddition reaction. The
synthetic strategy presented here Ϫ the combination of the
copper(I)-catalyzed 1,3-dipolar cycloaddition and the nu-
cleophilic substitution on pentafluorophenyl-substituted
1
183 °C. H NMR (700 MHz, CDCl3): δ = 0.93 (t, J = 7.1 Hz, 2 H,
porphyrinoids Ϫ allows a simple building block approach ε-CH2), 1.36–1.45 (m, 4 H, γ-CH2, δ-CH2), 1.75–1.83 (m, 2 H, β-
4230
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 4224–4237

Synthesis of Functionalized BODIPY Arrays
CH2), 2.84–2.89 (m, α-CH2), 6.60 (d, J = 4.4 Hz, 2 H, 3,7-Hpyrrole),
6.89 (d, J = 4.4 Hz, 2 H, 2,8-Hpyrrole), 7.73 (s, 1 H, Htriazole), 8.01
(s, 2 H, 1,9-Hpyrrole) ppm. 13C NMR (176 MHz, CDCl3): δ = 13.9 142.2 (dd,
13 Hz, ArF-C), 120.2 (3,7-Cpyrrole), 126.2 (d, J = 15.2 Hz), 131.3
(2,8-Cpyrrole), 134.7 (4,6-Cpyrrole), 141.5 (d, J = 15.4 Hz, Ar-C),
1,2
1
J
= 255.5, 14.3 Hz, Ar-C), 144.66 (d, JC,F =
C,F
(ε-C), 22.3 (γ-C, δ-C), 25.4 (α-C), 28.7 (β-C), 31.3 (γ-C, δ-C), 113.7, 249.7 Hz, ArF-C), 147.3 (1,9-Cpyrrole) ppm. 19F NMR (376 MHz,
118.8, 120.0 (3,7-Cpyrrole), 122.8 (5-Ctriazole), 128.9, 130.4 (2,8- [D6]acetone): δ = –139.16 to –139.53 (m, 2 F, Ar-Fortho),
Cpyrrole), 134.5 (4,6-Cpyrrole), 140.8 (Ar-C), 142.2 (Ar-C), 143.7 (Ar- –144.43 (dd, J = 55.9, 29.7 Hz, 2 F, BF2), –147.06 to –147.32 (m,
C), 145.2 (Ar-C), 146.9 (1,9-Cpyrrole), 149.0 (4-Ctriazole) ppm. 19F
NMR (376 MHz, CDCl3): δ = –134.71 to –135.20 (m, 2 F, Ar-
Fortho), –143.82 to –144.27 (m, 2 F, Ar-Fmeta), –144.56 to –144.87
(dd, J = 55.9, 28.1 Hz, 2 F, BF2) ppm. HRMS (ESI-TOF): m/z
2 F, Ar-Fm e t a ) ppm. HRMS (ESI-TOF): m/z calcd. for
24H19BF6N5O6Na2 [M + 2Na+ – H+]+ 644.1128; found
+
C
644.1441. UV/Vis (acetone): λmax (log ε, Lmol–1 cm–1) = 490 (4.44),
514 (4.42) nm. Fluorescence emission (acetone): λmax = 541 nm at
λExcit = 470 nm.
calcd. for C22H19BF6N5 [M + H]+ 478.1632; found 478.1660;
+
calcd. for C22H18BF6N5Na+ [M + Na]+ 500.1452; found 500.1489;
calcd. for C22H18BF6N5K+ [M + K]+ 516.1191; found 516.1226.
UV/Vis (CH2Cl2): λmax (log ε, L mol–1 cm–1) = 489 (4.32), 520
(4.52) nm. Fluorescence emission (CH2Cl2): λmax = 545 nm at λExcit
= 470 nm.
8-[(2,3,5,6-Tetrafluoro-4-{4-[(tetra-O-acetyl-β-D-glucopyranosidyl)-
oxy]methyl}-1H-1,2,3-triazole-1-yl)phenyl]-BODIPY (4e): Prop-
argyl-tetra-O-acetyl-β-d-glucopyranoside (45.8 mg, 118 μmol), so-
dium ascorbate (16.7 mg, 79.0 μmol), and CuSO4·5H2O (3.95 mg,
15.8 μmol) were dissolved in anhydrous DMSO (1.0 mL). Then,
8-{2,3,5,6-Tetrafluoro-4-[4-(hydroxymethyl)-1H-1,2,3-triazol-1-yl]- BODIPY 3 (30.0 mg, 79.0 μmol) was added and the mixture was
phenyl}-BODIPY (4b): BODIPY 3 (30.0 mg, 0.08 mmol) was dis-
solved under argon atmosphere in anhydrous DMSO (1.0 mL),
propargyl alcohol (4.50 μL, 0.08 mmol), sodium ascorbate
(16.7 mg, 0.08 mmol), and CuSO4·5H2O (2.40 mg, 0.01 mmol) were
stirred for 30 min at room temp. After aqueous workup, extraction
with CH2Cl2 (4 ϫ 50 mL), and drying over sodium sulfate, the
crude product was evaporated to dryness and purified by column
chromatography (CH2Cl2/ethyl acetate, 7:1, v/v) and recrystallized
added and the mixture was stirred for 20 min at room temp. After (CH2Cl2/n-hexane) to obtain BODIPY 4e (8 mg, 13%) as red-green
1
aqueous workup, extraction with CH2Cl2 (4ϫ 50 mL), and drying
over sodium sulfate, the crude product was evaporated to dryness
and purified by column chromatography (n-hexane/ethyl acetate,
1:1, v/v) to obtain BODIPY 4b (11.2 mg, 32%) as a red-green solid;
crystals; m.p. 238 °C. H NMR (700 MHz, CDCl3): δ = 2.03 (s, 3
H, OCH3), 2.05 (s, 3 H, OCH3), 2.06 (s, 3 H, OCH3), 2.11 (s, 3 H,
OCH3), 3.80 (ddd, J = 10.0, 4.7, 2.4 Hz, 1 H, H-5ЈoseЈ), 4.21 (dd,
J = 12.4, 2.4 Hz, 1 H, H-6AЈoseЈ), 4.29 (dd, J = 12.4, 4.7 Hz, 1 H,
m.p. 202 °C. 1H NMR (700 MHz, CDCl3): δ = 2.30 (br. s, 1 H, H-6BЈoseЈ), 4.78 (d, J = 8.0 Hz, 1 H, H-1ЈoseЈ), 5.00 (d, J = 12.8,
OH), 5.01 (s, 2 H, OCH2), 6.64 (d, J = 4.2 Hz, 2 H, 3,7-Hpyrrole), 0.8 Hz, 1 H, H-4ЈoseЈ), 5.27 (t, J = 9.5 Hz, 1 H, H-2ЈoseЈ), 6.64 (d,
6.90 (d, J = 4.6 Hz, 2 H, 2,8-Hpyrrole), 8.00 (s, 1 H, Htriazole), 8.04
J = 4.4 Hz, 2 H, 3,7-Hpyrrole), 6.91 (d, J = 4.4 Hz, 2 H, 2,8-Hpyrrole),
7.98 (s, 1 H, Htriazole), 8.04 (s, 2 H, 1,9-Hpyrrole) ppm. 13C NMR
(176 MHz, CDCl3): δ = 20.5 (CH3), 30.9 (CH3), 61.7 (C-6ЈoseЈ),
63.0 (C-4ЈoseЈ), 71.2, 68.2, 72.0 (C-5ЈoseЈ), 72.6 (C-2ЈoseЈ), 100.5
(s, 2 H, 1,9-Hpyrrole) ppm. 13C NMR (176 MHz, CDCl3): δ = 30.9,
2
2
56.5 (C-OH), 114.3 (t, JC–F = 18.0 Hz, ArF-C), 118.5 (t, JC–F
=
13.0 Hz, ArF-C), 120.1 (3,7-Cpyrrole), 123.9 (5-Ctriazole), 128.6, 130.4
1,2
2
2
(2,8-Cpyrrole), 134.5 (4,6-Cpyrrole), 141.5 (dd,
J
= 261.0, (C-1ЈoseЈ), 114.3 (t, JC,F = 18.1 Hz, ArF-C), 118.4 (t, JC,F =
C,F
1,2
13.6 Hz, ArF-C), 144.5 (dd,
J
= 255.2, 12.5 Hz, ArF-C), 147.0
12.4 Hz, ArF-C), 120.1 (3,7-Cpyrrole), 125.0 (Ctriazole), 128.6, 130.4
C,F
(1,9-Cpyrrole), 148.3 (4-Ctriazole) ppm. 19F NMR (376 MHz, CDCl3): (2,8-Cpyrrole), 134.5 (4,6-Cpyrrole), 141.5 (dd,
J
= 259.3,
1,2
C,F
1
δ = –134.37 to –134.91 (m, 2 F, Ar-Fortho), –143.84 to –144.27 (m,
2 F, Ar-Fmeta), –144.67 (dd, J = 55.9, 27.9 Hz, 2 F, BF2) ppm.
HRMS (ESI-TOF): m/z calcd. for C18H11BF6N5O+ [M + H]+
14.6 Hz, ArF-C), 144.5 (d, JC,F = 255.7 Hz, ArF-C), 147.0 (1,9-
C
pyrrole), 169.4 (d, J = 9.5 Hz), 170.1 (C=O), 170.6 (C=O) ppm. 19
F
NMR (376 MHz, CDCl3): δ = –134.69 (mc, 2 F, Ar-Fortho), –144.15
438.0955; found 438.0987; calcd. for C18H10BF6N5NaO+ (mc, 2 F, Ar-Fmeta), –144.64 (dd, J = 55.9, 29.7 Hz, 2 F, BF2) ppm.
[M + Na]+ 460.0780; found 476.0827; calcd. for C18H10BF6N5KO+ HRMS (ESI-TOF): m/z calcd. for C32H29BF6N5O10 [M + H]+
+
+
[M + K]+ 476.0514; found 476.0555. UV/Vis (CH2Cl2): λmax (log ε, 768.1906; found 768.1944; calcd. for C32H28BF6N5NaO10 [M +
Lmol–1 cm–1) = 489 (4.41), 520 (4.66) nm. Fluorescence emission
Na]+ 790.1726; found 790.1760. UV/Vis (CH2Cl2): λmax (log ε,
Lmol–1 cm–1) = 489 (4.46), 520 (4.71) nm. Fluorescence emission
(CH2Cl2): λmax = 546 nm at λExcit = 470 nm.
(CH2Cl2): λmax = 545 nm at λExcit = 480 nm.
8-[2,3,5,6-Tetrafluoro-4-(4-{[(α-D-mannopyranosidyl)oxy]methyl}-
1H-1,2,3-triazole-1-yl)phenyl]-BODIPY (4d): Sodium ascorbate
(16.7 mg, 79.0 μmol), propargyl-α-d-mannopyranoside (25.9 mg,
8,8Ј-{[4,4Ј-(Butane-1,4-diyl)bis(1H-1,2,3-triazole-4,1-diyl)]bis-
(2,3,5,6-tetrafluoro-4,1-phenylene)}bis-BODIPY (4f): CuSO4·5H2O
118 μmol), and CuSO4·5H2O (3.95 mg, 15.8 μmol) were dissolved (33.0 mg, 0.13 mmol), sodium ascorbate (78.5 mg, 0.40 mmol), and
in anhydrous DMSO (1.0 mL) under an argon atmosphere, fol-
lowed by addition of BODIPY 3 (30.0 mg, 79.0 μmol) and stirring
for 30 min at room temp. After aqueous workup, extraction with
CH2Cl2 (4ϫ 50 mL), and drying over sodium sulfate, the crude
product was evaporated to dryness and purified by column
1,7-octadiyne (0.71 μL, 0.05 mmol) were dissolved under an argon
atmosphere in anhydrous DMSO (3.0 mL). Then, BODIPY 3
(50.0 mg, 0.13 mmol) was added and the mixture stirred for 60 min
at room temp. After aqueous workup, extraction with CH2Cl2 (4ϫ
50 mL), and drying over sodium sulfate, the crude product was
chromatography (CH2Cl2/MeOH, 9:1, v/v) to obtain triazole 4d evaporated to dryness and purified by column chromatography
(19.7 mg, 42%) as a red solid; m.p. 212 °C. 1H NMR (700 MHz,
[D6]acetone): δ = 3.61–3.68 (m, 1 H, H-5ЈoseЈ), 3.70–3.81 (m, 3 H,
(CH2Cl2/n-hexane, 3:1, v/v) to obtain BODIPY 4f (11 mg, 24%) as
a red solid; m.p. 187 °C. H NMR (700 MHz, CDCl3): δ = 1.93–
1
H-4ЈoseЈ, H-6aЈoseЈ, H-3ЈoseЈ), 3.83–3.89 (m, 2 H, H-2ЈoseЈ, OH- 2.04 (m, 4 H, α,αЈ-CH2), 2.99 (t, J = 6.5 Hz, 4 H, β,βЈ-CH2), 6.63
6ЈoseЈ), 4.83 (d, J = 12.5 Hz, 1 H, OH-4ЈoseЈ), 4.98 (d, J = 12.5 Hz, (d, J = 4.3 Hz, 4 H, 3,7-Hpyrrole), 6.89 (d, J = 4.3 Hz, 4 H, 2,8-
1 H, OH-2ЈoseЈ), 5.00 (d, J = 1.6 Hz, 1 H, H-1ЈoseЈ), 6.76 (d, J = Hpyrrole), 7.77 (s, 2 H, Htriazole), 8.04 (s, 4 H, 1,9-Hpyrrole) ppm. 13C
4.1 Hz, 2 H, 3,7-Hpyrrole), 7.36 (d, J = 4.3 Hz, 2 H, 2,8-Hpyrrole),
8.19 (s, 2 H, 1,9-Hpyrrole), 8.56 (s, 1 H, Htriazole) ppm. 13C NMR (t, JC,F = 18 Hz, ArF-C), 118.7 (t, JC,F = 12 Hz, ArF-C), 120.0
(176 MHz, [D6]acetone): δ = 59.4 (C-2ЈoseЈ), 62.0 (C-6ЈoseЈ), 67.9 (3,7-Cpyrrole), 122.9 (5-Ctriazole), 130.3 (2,8-Cpyrrole), 134.5 (4,6-
(C-4ЈoseЈ, C-6ЈoseЈ), 71.6 (C-4ЈoseЈ, C-6ЈoseЈ), 73.6 (C-5ЈoseЈ), 99.7 Cpyrrole), 141.5 (dd,
NMR (700 MHz, CDCl3): δ = 25.1 (α,αЈ-C), 28.5 (β,βЈ-C), 113.9
2
2
1,2
J
= 259.7, 14.6 Hz, ArF-C), 144.5 (dd,
C,F
2
2
1,2
(C-1ЈoseЈ), 113.6 (t, JC,F = 18.5 Hz, ArF-C), 118.7 (t, JC,F
=
J
= 255.1, 12.9 Hz, ArF-C), 147.0 (1,9-Cpyrrole), 148.4 (4-
C,F
Eur. J. Org. Chem. 2015, 4224–4237
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4231

H.-U. Reissig, A. Wiehe et al.
FULL PAPER
Ctriazole) ppm. 19F NMR (376 MHz, CDCl3): δ = –139.43 to
–140.04 (m, 4 F, Ar-Fortho), –144.71 (dd, J = 56.0, 28.0 Hz, 2 F,
BF2), –160.04 to –160.86 (m, 4 F, Ar-Fmeta) ppm. HRMS (ESI-
(4.82), 520 (5.16) nm. Fluorescence emission (CH2Cl2): λmax
549 nm at λExcit = 470 nm.
=
1,3,5-Tris{1-[4-(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)-
2,3,5,6-tetrafluorophenyl]-1,2,3-triazol-4-en}benzene (4i): Variant 2:
1,3,5-Triethynylbenzene (16.8 mg, 0.11 mmol) and BODIPY 3
(119 mg, 0.35 mmol) were dissolved under an argon atmosphere in
anhydrous DMSO (2.0 mL), CuSO4·5H2O (14.0 mg, 89.8 μmol),
and sodium ascorbate (47.5 mg, 0.23 mmol) were added and the
mixture was stirred for 120 min at room temp. The reaction mixture
was diluted with CH2Cl2, washed three times with water, and dried
with sodium sulfate. The crude product was evaporated to dryness
and purified by gradient column chromatography (acetone/n-hex-
ane, 1:2 to 2:3, v/v) and recrystallized (acetone/n-pentane) to obtain
4i (65 mg, 45%) as orange-red crystals. For variant 1 (THF, heat-
ing) and the optimized variant 3 and characterization data of 4i see
ref.[21]
+
TOF): m/z calcd. for C38H23B2F12N10 [M + H]+ 869.2096; found
869.2154; calcd. for C38H22B2F12N10Na+ [M + Na]+ 891.1921;
found 891.1984; calcd. for C38H22B2F12KN10 [M + K]+ 907.1660;
+
found 907.1719. UV/Vis (CH2Cl2): λmax (log ε, Lmol–1 cm–1) = 495
(4.56), 520 (4.84) nm. Fluorescence emission (CH2Cl2): λmax
543 nm at λExcit = 480 nm.
=
8,8Ј-[4,4Ј-(1,4-Phenylene)bis(1H-1,2,3-triazol-4,1-diyl)]bis(2,3,5,6-
tetrafluoro-4,1-phenylene)bis-BODIPY (4g): BODIPY 3 (100 mg,
0.26 mmol) was dissolved in anhydrous DMSO (2.0 mL) under an
argon atmosphere. Then, 1,4-diethynylbenzene (13.4 mg,
0.13 mmol), CuSO4·5H2O (65.0 mg, 0.26 mmol), and sodium as-
corbate (157 mg, 0.26 mmol) were added and the mixture was
stirred for 30 min at room temp. BODIPY 3 (50.0 mg, 0.13 mmol)
was added and the reaction mixture was stirred for 30 min at room
temp. After aqueous workup, extraction with CH2Cl2 (4ϫ 50 mL),
and drying over sodium sulfate, the crude product was evaporated
to dryness and purified by column chromatography (n-hexane/acet-
one, 3:2, v/v) to obtain BODIPY 4g (35 mg, 30%) as a red-green
8-(4-Amino-2,3,5,6-tetrafluorophenyl)-4,4-difluoro-4-bora-3a,4a-
diaza-s-indacene (5): BODIPY 3 (98 mg, 0.28 mmol) was dissolved
under an argon atmosphere in anhydrous DMSO (2.0 mL),
CuSO4·5H2O (65 mg, 0.26 mmol) and sodium ascorbate (43.0 mg,
0.21 mmol) were added and the mixture was stirred for 1 h at room
temp. After aqueous workup, extraction with CH2Cl2 and drying
over sodium sulfate, the crude product was evaporated to dryness
and purified by column chromatography (CH2Cl2/n-hexane, 3:1,
v/v) to give amino-BODIPY 5 (88 mg, 97 %) as orange-reddish
1
solid; m.p. 287 °C. H NMR (700 MHz, [D6]acetone): δ = 6.79 (d,
J = 4.4 Hz, 4 H, 3,7-Hpyrrole), 7.45 (d, J = 4.3 Hz, 4 H, 2,8-Hpyrrole),
8.32 (s, 4 H, 1,9-Hpyrrole), 8.21 (s, 4 H, HAryl), 9.30 (s, 2 H,
H
triazole) ppm. 13C NMR (176 MHz, [D6]acetone): δ = 113.4 (t,
2JC,F = 18.0 Hz, ArF-C), 121.1 (3,7-Cpyrrole), 124.6 (5-Ctriazole),
1
crystals; m.p. 224 °C. H NMR (700 MHz, CDCl3): δ = 4.39 (s, 2
126.8 (Ar-2,3,5,6-C-H), 130.0 (Ar-1,4-C-H), 118.4 (ArF-C), 132.3
1,2
H, NH2), 6.56 (dd, J = 4.2 Hz, 2 H, 3,7-Hpyrrole), 6.91 (d, J =
(2,8-Cpyrrole), 134.6 (4,6-Cpyrrole), 142.0 (dd,
J
= 255.0,
C,F
4.2 Hz, 2 H, 2,8-Hpyrrole), 7.95 (s, 2 H, 1,9-Hpyrrole) ppm. 13C NMR
1
14.0 Hz, ArF-C), 144.6 (d, JC,F = 241.3 Hz, ArF-C), 147.2 (4-
2
triazole), 148.4 (1,9-Cpyrrole) ppm. 19F NMR (376 MHz, [D6]acet-
(176 MHz, CDCl3): δ = 99.4 (t, JC,F = 18.1 Hz, ArF-Cipso), 119.1
C
2,3
(3,7-Cpyrrole), 128.6 (tt,
J
= 13.7, 3.8 Hz, ArF-Cpara), 130.8
C,F
one): δ = –138.32 (mc, 4 F, Ar-Fortho), –141.41 (dd, J = 57.2,
1,2
(2,8-Cpyrrole), 135.4 (5-Cmeso), 136.2 (dd,
J
= 241.1, 16.4 Hz,
C,F
29.1 Hz, 4 F, BF2), –145.82 (mc, 4 F, Ar-Fmeta) ppm. HRMS (ESI-
1,2
+
TOF): m/z calcd. for C41H20B2F12N9 [M + H]+ 888.1836; found
ArF-Cmeta), 144.3 (d,
J
= 247.1 Hz, ArF-Cortho), 145.4 (1,9-
C,F
C
pyrrole) ppm. 19F NMR (376 MHz, CDCl3): δ = –139.63 to
888.1826; calcd. for C41H19B2F12N9Na+ [M + Na]+ 910.1656;
found 910.1651; calcd. for C41H19B2F12KN9 [M + K]+ 926.1395;
+
–139.85 (m, 2 F, Ar-Fortho), –144.85 (dd, J = 57.1, 29.0 Hz, 2 F,
BF2), –160.34 to –160.51 (m, 2 F, Ar-Fmeta) ppm. HRMS (ESI-
TOF): m/z calcd. for C15H7BF6N3 [M – H]– 354.0643; found
354.0651. UV/Vis (CH2Cl2): λmax (log ε, Lmol–1 cm–1) = 485 (3.70),
516 (4.10) nm.
found 926.1403. UV/Vis (DMSO): λmax (log ε, Lmol–1 cm–1) = 490
(4.50), 519 (4.82) nm. Fluorescence emission (DMSO): λmax
554 nm at λExcit = 480 nm.
=
8,8Ј,8ЈЈ-({4,4Ј,4ЈЈ-[Nitrilotris(methylene)]tris(1H-1,2,3-triazol-1,4-
diyl)}tris(2,3,5,6-tetrafluoro-4,1-phenylene))tris-BODIPY (4h): 5,15-Bis(3-acetoxyphenyl)-10-(pentafluorophenyl)corrole (6a): 5-(3-
BODIPY 3 (100 mg, 0.26 mmol) was dissolved under an argon at-
mosphere in anhydrous DMSO (2.0 mL). Then, tris(propyn-2-yl)-
Acetoxyphenyl)dipyrromethane (1.08 g, 4.00 mmol) and penta-
fluorobenzaldehyde (0.24 mL, 2.00 mmol) were dissolved in meth-
amine (12.3 μL, 87.0 μmol), sodium ascorbate (156 mg, anol (200 mL). A mixture of distilled water (200 mL) and HCl
0.79 mmol), and CuSO4·5H2O (65.7 mg, 0.26 mmol) were added (36%, 10 mL) was added and the mixture was stirred for 1 h at
and the mixture was stirred for 40 min at room temp. After aque- room temp. After aqueous workup, extraction with CH2Cl2, drying
ous workup, extraction with CH2Cl2 (4ϫ 50 mL), and drying over
sodium sulfate, the crude product was evaporated to dryness and
purified by column chromatography (CH2Cl2/ethyl acetate, 5:1,
v/v) and recrystallized (CH2Cl2/n-hexane) to obtain triazole 4h
over sodium sulfate, and evaporation to dryness, the crude product
was dissolved in CH2Cl2 (1000 mL), DDQ (1.36 g, 6.00 mmol) was
added and the reaction mixture was stirred for 3 h at room temp.
After filtration through silica gel and evaporation to dryness, the
(44.8 mg, 40 %) as red-green crystals; m.p. 291 °C. 1H NMR crude reaction mixture was purified by column chromatography
(700 MHz, CDCl3): δ = 4.08 (s, 6 H, N-CH2), 6.68–6.57 (d, J = (CH2Cl2/n-hexane, 3:1, v/v) and recrystallized (CH2Cl2/n-pentane)
4.2 Hz, 6 H, 3,7-Hpyrrole), 6.89 (d, J = 4.4 Hz, 6 H, 2,8-Hpyrrole),
to give corrole 6a (178.0 mg, 12%) as purple crystals; m.p. 187 °C.
8.02 (s, 6 H, 1,9-Hpyrrole), 8.33 (s, 3 H, Htriazole) ppm. 13C NMR 1H NMR (700 MHz, [D6]acetone): δ = 2.39 (s, 6 H, CH3), 7.70–
(176 MHz, CDCl3): δ = 47.1 (N-CH2), 114.40 (t, J = 18.1 Hz), 7.31 (m, 2 H, Ar-Hpara), 7.97–7.76 (m, 2 H, Ar-H-2), 8.33–8.01 (m,
118.55 (t, J = 13.4 Hz), 120.1 (3,7-Cpyrrole), 126.4 (5-Ctriazole), 130.3
4 H, Ar-H-1 + Ar-H-3), 8.57–8.37 (m, 2 H, β-Hpyrrole), 8.75–8.59
1,2
(2,8-Cpyrrole), 134.5 (4,6-Cpyrrole), 141.58 (dd,
J
= 259.6, (m, 2 H, β-Hpyrrole), 9.11–8.80 (m, 4 H, β-Hpyrrole) ppm. 13C NMR
C,F
13.9 Hz, ArF-C), 144.2 (5-Ctriazole), 144.5 (d, 1JC,F = 254.9 Hz, ArF-
(176 MHz, [D6]acetone): δ = 20.1 (CH3), 90.8 (ArF-Cmeso), 115.4
C), 147.1 (1,9-Cpyrrole) ppm. 19F NMR (376 MHz, CDCl3): δ = (β-Cpyrrole), 116.8 (ArF-Cipso), 120.7 (Ar-Cpara), 124.7 (β-Cpyrrole),
–134.63 (mc, 6 F, Ar-Fortho), –144.14 (mc, 6 F, Ar-Fmeta), –144.69 128.3 (Ar-C-3), 128.9 (Ar-C-2), 130.9 (β-Cpyrrole), 132.2 (Ar-C-1),
(dd, J = 55.8, 28.0 Hz, 6 F, BF2) ppm. HRMS (ESI-TOF): m/z
135.2 (β-Cpyrrole), 137.8 (d, 1JC,F = 249.1 Hz, ArF-Cpara), 140.8 (Ar-
calcd. for C54H27B3F18N16Na+ [M + Na]+ 1297.2494; found
Cipso), 142.3 (ArF-Cmeta), 150.8 (Ar-C-OAc), 146.8 (d, JC,F
=
1
+
1297.2614; calcd. for C54H27B3F18KN16 [M + K]+ 1313.2233;
242.5 Hz, ArF-Cortho), 169.4 (C=O) ppm. 19F NMR (376 MHz,
found 1313.2359. UV/Vis (CH2Cl2): λmax (log ε, Lmol–1 cm–1): 489
[D6]acetone): δ = –140.07 (d, J = 23.8 Hz, 2 F, Ar-Fortho), –157.25
4232
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 4224–4237

Synthesis of Functionalized BODIPY Arrays
(t, J = 20.4 Hz, 2 F, Ar-Fpara), –165.02 to –165.53 (m, 2 F, Ar- dered KOH (85.4 mg, 1.52 mmol) was added and the reaction mix-
Fortho) ppm. HRMS (ESI-TOF): m/z calcd. for C41H26F4N4O4+ [M
ture was stirred for 1 h at room temp. After aqueous workup, ex-
+ H]+ 733.1869; found 733.1890; calcd. for C41H25F5N4NaO4 [M traction with ethyl acetate, and drying over sodium sulfate, the
+
+ Na]+ 755.1688; found 755.1712. UV/Vis (CH2Cl2): λmax (logε, crude product was purified by column chromatography (acetone/n-
Lmol–1 cm–1) = 412 (5.44), 568 (4.56), 611 (4.48) nm.
hexane, 2:3, v/v) and recrystallized (acetone/n-hexane) to obtain
alkynyl-functionalized corrole 7b (19.3 mg, 36%) as purple crystals;
m.p. 156 °C. 1H NMR (500 MHz, [D6]acetone): δ = 3.44 (t, J =
2.3 Hz, 1 H, CϵCH), 5.27 (d, J = 2.5 Hz, 2 H, OCH2), 7.41–7.26
(m, 4 H, Ar-Hmeta), 8.28–8.12 (m, 4 H, Ar-Hortho), 8.55–8.38 (m, 4
H, β-Hpyrrole), 9.01–8.79 (m, 4 H, β-Hpyrrole) ppm. 13C NMR
(176 MHz, [D6]acetone): δ = 62.1 (OCH2), 77.6 (CϵCH), 78.3
(CϵCH), 97.4 (ArF-Cmeso), 113.9 (ArF-Cipso), 115.2 (Ar-Cmeta),
117.2 (β-Cpyrrole), 121.3 (β-Cpyrrole), 124.0 (β-Cpyrrole), 128.5 (β-
5,15-Bis(4-acetoxyphenyl)-10-(pentafluorophenyl)corrole (6b): 5-(4-
Acetoxyphenyl)dipyrromethane (560 mg, 2.00 mmol) and penta-
fluorobenzaldehyde (0.12 mL, 1.00 mmol) were dissolved in meth-
anol (100 mL). A mixture of distilled water (100 mL) and HCl
(36%, 5 mL) was added and the mixture was stirred for 1 h at room
temp. After aqueous workup, extraction with CH2Cl2, drying over
sodium sulfate, and evaporation to dryness, the crude product was
dissolved in CH2Cl2 (500 mL), DDQ (676 mg, 3.00 mmol) was
added and the reaction mixture was stirred for 3 h at room temp.
After filtration through silica gel and evaporation to dryness, the
crude reaction mixture was purified by column chromatography
(CH2Cl2/n-hexane, 3:1, v/v) and recrystallized (CH2Cl2/n-pentane)
to obtain corrole 6b (220 mg, 30%) as purple crystals; m.p. 271 °C.
1H NMR (400 MHz, CDCl3): δ = 2.46 (s, 6 H, CH3), 7.67–7.43 (m,
4 H, Ar-Hmeta), 8.66–8.20 (m, 8 H, β-Hpyrrole + Ar-Hortho), 9.11–
8.79 (m, 4 H, β-Hpyrrole) ppm. 13C NMR (176 MHz, [D6]acetone): δ
= 20.0 (CH3), 90.4 (ArF-Cmeso), 115.4 (Ar-Cmeso), 116.9 (ArF-Cipso),
C
pyrrole), 131.0 (α-Cpyrrole), 135.2 (α-Cpyrrole), 136.1 (Ar-Cortho),
140.1 (α-Cpyrrole), 141.3 (α-Cpyrrole), 142.4 (ArF-Cmeta), 146.7 (d,
1JC,F = 234.9 Hz, ArF-Cortho), 157.6 (Ar-C-OH) ppm. 19F NMR
(376 MHz, [D6]acetone): δ = –141.85 (d, J = 22.4 Hz, 2 F, Ar-
Fortho), –157.49 to –157.87 (m, 2 F, Ar-Fmeta) ppm. HRMS (ESI-
+
TOF): m/z calcd. for C40H25F4N4O3 [M + H]+ 685.1857; found
685.1884. UV/Vis (CH2Cl2): λmax (log ε, Lmol–1 cm–1) = 414 (5.23),
581 (4.59), 608 (4.55), 650 (4.11) nm.
BODIPY-CuIII-corrole Array (8a): A 25 mL high-pressure reaction
flask was loaded with CuSO4·5H2O (20.0 mg, 0.08 mmol), sodium
ascorbate (86.0 mg, 0.43 mmol), BODIPY 3 (30.0 mg, 78.7 μmol),
and 7a (50.0 mg, 73.0 μmol). The mixture was suspended in THF
(3.0 mL), heated to 80 °C and stirred for 24 h. After aqueous
workup, extraction with ethyl acetate, and drying over sodium sulf-
ate, the crude product was evaporated to dryness, purified by col-
umn chromatography (n-hexane/acetone, 3:2, v/v) and recrys-
tallized (acetone/n-pentane) to obtain array 8a (36.0 mg, 44%) as
a brown solid; m.p. Ͼ 300 °C. 1H NMR (700 MHz, CDCl3): δ =
5.61 (s, 2 H, OCH2), 6.59–6.55 (m, 2 H, 3,7-Hpyrrole), 6.88–6.83 (m,
2 H, 2,8-Hpyrrole), 6.99–6.95 (m, 2 H, Ar-H-6), 7.04 (d, J = 4.4 Hz,
2 H, β-Hpyrrole), 7.12–7.08 (m, 2 H, Ar-H-2), 7.17–7.12 (m, 2 H,
Ar-H-4), 7.26 (t, J = 7.8 Hz, 2 H, Ar-H-5), 7.35 (d, J = 3.4 Hz, 2
H, β-Hpyrrole), 7.66 (d, J = 4.1 Hz, 2 H, β-Hpyrrole), 7.85 (br. s, 2 H,
β-Hpyrrole), 7.97 (s, 2 H, 1,9-Hpyrrole), 8.23 (Htriazole) ppm. 13C NMR
121.5 (Ar-Cmeta), 125.7 (β-Cpyrrole), 127.9 (β-Cpyrrole), 135.5 (Ar-
1
C
ortho), 137.1 (ArF-Cpara), 138.5 (Ar-Cipso), 141.6 (d, JC,F
=
250.6 Hz, ArF-Cmeta), 146.8 (d, 1JC,F = 242.6 Hz, ArF-Cortho), 151.1
(Ar-Cpara), 169.1 (C=O) ppm. 19F NMR (376 MHz, CDCl3): δ =
–136.93 to –137.54 (m, 2 F, Ar-Fortho), –153.28 to –153.81 (m, 1 F,
Ar-Fpara), –161.90 to –162.47 (m, 2 F, Ar-Fmeta) ppm. HRMS (ESI-
TOF): m/z calcd. for C41H25F5N4NaO4 [M + Na]+ 755.1688;
+
found 755.1712. UV/Vis (CH2Cl2): λmax [log ε, Lmol–1 cm–1) = 413
(5.06), 574 (4.36), 599 (4.21), 651 (3.73) nm.
5,15-Bis(3-hydroxyphenyl)-10-[4-(2-propyn-1-oxy)tetrafluorophen-
yl]corrole (7a): Compound 6a (200 mg, 292.1 μmol) was dissolved
in anhydrous DMSO (5.0 mL) under an argon atmosphere, and
propargyl alcohol (1.0 mL, 17.28 mmol) was added. Freshly pow-
dered KOH (32.0 mg, 5.71 mmol) was added and the reaction mix-
ture was stirred for 1 h at room temp. After aqueous workup, ex-
traction with ethyl acetate, and drying over sodium sulfate, the
crude product was purified by column chromatography (acetone/n-
hexane, 2:3, v/v) and recrystallized (acetone/n-hexane) to obtain
alkynyl-functionalized corrole 7a (153.3 mg, 85%) as purple crys-
2
(176 MHz, CDCl3): δ = 67.2 (OCH2), 114.6 (t, JC,F = 18.0 Hz,
2
Ar1F-Cipso), 116.2 (Ar-C-6), 117.2 (Ar-C-2), 118.2 (t, JC,F
=
11.4 Hz, Ar2F-Cipso), 120.2 (3,7-Cpyrrole), 121.4 (β-Cpyrrole), 122.1
(Ar-C-4), 126.1 (5-Ctriazole), 126.8 (β-Cpyrrole), 129.4 (Ar-C-5), 130.5
(2,8-Cpyrrole), 134.5 (Ar2F-5-Cmeso), 134.6 (β-Cpyrrole), 143.7 (4-
Ctriazole), 136.6 (Ar1F-Cpara), 147.1 (1,9-Cpyrrole), 149.8 (Ar-Cipso),
156.7 (Ar-C-OH) ppm. 19F NMR (376 MHz, CDCl3): δ = –134.56
to –134.72 (m, 2 F, Ar2-Fortho), –138.83 to –139.47 (m, 2 F, Ar1-
Fortho), –144.05 to –144.19 (m, 2 F, Ar2-Fmeta), –144.66 (dd, J =
1
tals; m.p. 278 °C. H NMR (700 MHz, [D6]acetone): δ = 3.51–3.40
(m, 1 H, CϵCH), 5.30 (d, J = 2.4 Hz, 2 H, OCH2), 7.32–7.23 (m,
2 H, Ar-Hpara), 7.70 (t, J = 7.8 Hz, 2 H, Ar-H-2), 7.92–7.82 (m, 4
H, Ar-H-1 + Ar-H-3), 8.64–8.50 (m, 4 H, β-Hpyrrole), 8.99–8.89
(m, 2 H, β-Hpyrrole), 9.09–9.00 (m, 2 H, β-Hpyrrole) ppm. 13C NMR
(176 MHz, [D6]acetone): δ = 62.1 (OCH2), 77.6 (CϵCH), 78.3
(CϵCH), 91.1 (ArF-Cmeso), 114.7 (Ar-Cpara), 115.2 (β-Cpyrrole),
56.2, 28.1 Hz, 2 F, BF2), –155.42 to –155.65 (m, 2 F, Ar1-Fmeta
)
+
ppm. HRMS (ESI-TOF): m/z calcd. for C55H28BCuF10N9O3 [M
+ H]+ 1126.1539; found 1126.1454. UV/Vis (acetone): λmax (log ε,
Lmol–1 cm–1) = 407 (5.26), 514 (5.03) nm. Fluorescence emission
(acetone): λmax = 554 nm at λExcit = 350 and 500.
2
116.4 (t, JC,F = 20 Hz, ArF-Cipso), 116.9 (Ar-Cmeso), 121.5 (β-
Cpyrrole), 122.0 (Ar-C-3), 124.3 (β-Cpyrrole), 126.5 (Ar-C-1), 128.5
(β-Cpyrrole), 129.0 (Ar-C-2), 131.1 (α-Cpyrrole), 135.6 (α-Cpyrrole),
136.2 (ArF-Cpara), 140.3 (α-Cpyrrole), 141.0 (Ar-Cipso), 142.4 (α-
Cpyrrole), 142.5 (ArF-Cmeta), 146.8 (d, 1JC,F = 241.5 Hz, ArF-Cortho),
157.1 (Ar-C-OH) ppm. 19F NMR (376 MHz, [D6]acetone): δ =
–141.25 to –141.52 (m, 2 F, Ar-Fortho), –157.98 to –158.15 (m, 2 F,
BODIPY-CuIII-corrole Array (8b): A 25 mL high-pressure reaction
flask was loaded with CuSO4·5H2O (5.01 mg, 20.1 μmol), sodium
ascorbate (12.0 mg, 61.0 μmol), BODIPY 3 (8.0 mg, 21.9 μmol),
and 7b (10.0 mg, 15.5 μmol). The mixture was suspended in THF
(3.0 mL), heated to 80 °C, and stirred for 24 h. After aqueous
workup, extraction with ethyl acetate, and drying over sodium sulf-
ate, the crude product was evaporated to dryness, purified by col-
umn chromatography (n-hexane/acetone, 3:2, v/v) and recrys-
tallized (acetone/n-pentane) to obtain array 8b (10.2 mg,58%) as a
+
Ar-Fmeta) ppm. HRMS (ESI-TOF): m/z calcd. for C40H25F4N4O3
[M + H]+ 685.1857; found 685.1884. UV/Vis (CH2Cl2): λmax (log ε,
Lmol–1 cm–1) = 413 (3.99), 508 (3.85), 584 (3.41) nm.
5,15-Bis(4-hydroxyphenyl)-10-[4-(2-propyn-1-oxy)tetrafluorophen-
yl]corrole (7b): Compound 6b (57.0 mg, 77.8 μmol) was dissolved
in anhydrous DMSO (2.0 mL) under an argon atmosphere and
propargyl alcohol (0.36 mL, 6.22 mmol) was added. Freshly pow-
1
brown solid; m.p. Ͼ 300 °C. H NMR (700 MHz, [D6]acetone): δ
= 5.73 (s, 2 H, OCH2), 6.77–6.73 (m, 2 H, 3,7-Hpyrrole), 7.06 (d, J
= 8.4 Hz, 2 H, Ar-Hmeta), 7.38–7.28 (m, 2 H, 2,8-Hpyrrole), 7.48 (br.
Eur. J. Org. Chem. 2015, 4224–4237
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4233

H.-U. Reissig, A. Wiehe et al.
FULL PAPER
s, 4 H, β-Hpyrrole), 7.59 (d, J = 8.2 Hz, 2 H, Ar-Hortho), 7.66 (br. s,
2 H, β-Hpyrrole), 8.12 (br. s, 2 H, β-Hpyrrole), 8.18 (s, 2 H, 1,9-
–152.6 (t, J = 20.4 Hz, 2 F, Ar-Fpara), –161.5 (t, J = 19.3 Hz, 4 F,
+
Ar-Fmeta) ppm. HRMS (ESI-TOF): m/z calcd. for C39H19F10N4O2
Hpyrrole), 8.77 (s, 1 H, Htriazole), 8.80 (s, 2 H, Ar-OH) ppm. 13C [M + H]+ 765.1343; found 765.1340. UV/Vis (CH2Cl2): λmax (logε,
NMR (176 MHz, [D6]acetone): δ = 67.0 (OCH2), 109.9 (Ar-Cmeso),
Lmol–1 cm–1) = 412 (5.18), 579 (4.85), 628 (4.77) nm.
2
114.0 (t, JC–F = 18.5 Hz, Ar1F-Cipso), 115.3 (Ar-Cmeta), 118.5 (t,
10-(3-Hydroxyphenyl)-5,15-bis[4-(2-propyn-1-oxy)tetrafluorophen-
yl]corrole (11): Compound 9 (30.0 mg, 39.3 μmol) was dissolved
under an argon atmosphere in anhydrous DMSO (5 mL), then
propargyl alcohol (0.3 mL, 5.19 mmol) and freshly powdered KOH
(170 mg, 3.02 mmol) were added and the reaction mixture was
stirred for 30 min at room temp. After aqueous workup, extraction
with CH2Cl2, and drying over sodium sulfate, the crude product
was evaporated to dryness and purified by column chromatography
(n-hexane/acetone, 3:2, v/v) and recrystallized (CH2Cl2/n-hexane)
to obtain corrole 11 (21.8 mg, 70 %) as a purple powder; m.p.
2JC,F = 13.6 Hz, Ar2F-Cipso), 120.1 (3,7-Cpyrrole), 127.5 (5-Ctriazole),
128.1 (Ar-Cipso), 131.2 (2,8-Cpyrrole), 132.5 (Ar-Cortho), 134.7 (4,6-
2
1,2
C
pyrrole), 137.0 (t, JC,F = 17.2 Hz, Ar1F-Cpara), 141.9 (dd,
J
=
C,F
1,2
245.2, 12.2 Hz, ArF-Cmeta), 142.2 (dd,
J
= 245.9, 16.0 Hz, ArF-
C,F
= 250.3, 12.9 Hz, ArF-
C,F
1,2
C
meta), 143.1 (4-Ctriazole), 144.7 (dd,
J
Cortho), 147.3 (1,9-Cpyrrole), 158.8 (Ar-Cpara) ppm. 19F NMR
(
3
7
6
M
H z ,
[D6]acetone): δ = –139.11 to –139.32 (m, 2 F, Ar2-Fortho), –142.26
(dd, J = 23.1, 8.3 Hz, 2 F, Ar1-Fortho), –144.45 (dd, J = 55.7,
28.0 Hz, 2 F, BF2), –147.27 to –147.41 (m, 2 F, Ar2-Fmeta), –156.79
(dd, J = 23.0, 8.4 Hz, Ar1-Fmeta) ppm. HRMS (ESI-TOF): m/z
1
220 °C. H NMR (500 MHz, CDCl3): δ = 2.78 (t, J = 2.4 Hz, 2 H,
CϵCH), 5.17 (d, J = 2.4 Hz, 4 H, OCH2), 6.97 (d, J = 8.5 Hz, 1
H, Ar-Hpara), 7.42–7.34 (m, 1 H, Ar-H-3), 7.50 (t, J = 7.8 Hz, 1 H,
Ar-H-2), 7.68 (d, J = 6.0 Hz, 1 H, Ar-H-1), 8.61–8.53 (m, 2 H, β-
calcd. for C55H28BCuF10N9O3 [M + H]+ 1126.1539; found
+
1126.1454. UV/Vis (CH2Cl2): λmax (log ε, L mol–1 cm–1) = 379
(4.83), 398 (4.94), 406 (5.26), 514 (5.03) nm. UV/Vis (acetone): λmax
(log ε, Lmol–1 cm–1) = 406 (5.21), 514.5 (4.96) nm. Fluorescence
emission (acetone): λmax = 554 nm at λExcit = 350 and 500 nm.
H
pyrrole), 8.67 (d, J = 4.7 Hz, 2 H, β-Hpyrrole), 8.71 (d, J = 4.7 Hz,
2 H, β-Hpyrrole), 9.12–9.04 (m, 2 H, β-Hpyrrole) ppm. 13C NMR
(176 MHz, CDCl3): δ = 61.9 (OCH2), 77.2 (C=CH), 77.6 (C=CH),
97.7 (ArF-Cmeso), 112.6 (Ar-Cmeso), 113.5 (ArF-Cipso), 114.6 (Ar-
Cpara), 117.2 (β-Cpyrrole), 121.5 (Ar-C-3), 121.7 (β-Cpyrrole), 125.8
BODIPY-CuIII-corrole Array (8c). Variant 1: A 25 mL high-pres-
sure reaction flask was loaded with CuSO4·5H2O (20.0 mg,
0.08 mmol), sodium ascorbate (75.0 mg, 0.38 mmol), BODIPY 3 (β-Cpyrrole), 127.5 (Ar-C-1), 127.6 (β-Cpyrrole), 128.3 (Ar-C-2), 131.1
(36.0 mg, 95.6 μmol), and 7c (60.0 mg, 63.7 μmol). The mixture
was suspended in THF (1.5 mL), heated to 80 °C, and stirred for
12 h. After aqueous workup, extraction with ethyl acetate, and dry-
ing over sodium sulfate, the crude product was evaporated to dry-
ness, purified by column chromatography (CH2Cl2) and recrys-
tallized [CH2Cl2/(MeOH/H2O, 9:1, v/v)] to obtain array 8c
(17.2 mg, 19%) as a brown solid.
(α-Cpyrrole), 135.3 (α-Cpyrrole), 136.2 (ArF-Cpara), 140.1 (α-Cpyrrole),
1,2
141.2 (α-Cpyrrole), 141.8 (dd,
J
= 252.6, 17.5 Hz, ArF-Cmeta),
C,F
146.1 (d, JC,F = 249.1 Hz, ArF-Cortho), 154.2 (Ar-C-OH) ppm. 19F
1
NMR (471 MHz, CDCl3): δ = –134.93 (d, J = 8.8 Hz, 4 F, Ar-
F
ortho), –139.12 to –139.43 (m, 4 F, Ar-Fmeta) ppm. HRMS (ESI-
+
TOF): m/z calcd. for C43H23F8N4O3 [M + H]+ 795.1637; found
795.1680. UV/Vis (CH2Cl2): λmax (logε, Lmol–1 cm–1) = 412 (5.23),
568 (4.53), 613 (4.35) nm.
Variant 2: All reagents with initial weight as described for variant
1 were suspended in DMSO (2 mL) and stirred for 15 min at room
temp. After workup and purification as described above, conjugate
8c (28 mg, 32%) was obtained as a brown powder. For detailed
characterization data of 8c see ref.[25d]
BODIPY-CuIII-corrole Array 13: CuSO4·5H2O (47.0 mg,
0.19 mmol), sodium ascorbate (149 mg, 0.76 mmol), BODIPY 3
(60.0 mg, 0.16 mmol), and 11 (50.0 mg, 62 μmol) were suspended
in DMSO (2.0 mL) and stirred for 15 min at room temp. After
aqueous workup, extraction with CH2Cl2, and drying over sodium
sulfate, the crude product was evaporated to dryness, purified by
column chromatography (n-hexane/ethyl acetate, 10:9, v/v) and
recrystallized (CH2Cl2/n-pentane) to obtain array 13 (47 mg, 50%)
as dark-green crystals; m.p. Ͼ 300 °C. 1H NMR (700 MHz, [D6]-
acetone): δ = 5.73 (s, 4 H, OCH2), 6.77 (d, J = 3.6 Hz, 4 H, 3,7-
Hpyrrole), 7.09–7.03 (m, 4 H, Ar-H), 7.36 (d, J = 4.1 Hz, 4 H, 2,8-
Hpyrrole), 8.20 (s, 4 H, 1,9-Hpyrrole), 8.65 (s, 1 H, Ar-OH), 8.79 (s, 2
5,15-Bis(pentafluorophenyl)-10-(3-acetoxyphenyl)corrole (9): A sin-
gle-necked 250 mL flask was loaded with methanol (50 mL), penta-
fluorophenyl dipyrromethane 1 (312 mg, 1.00 mmol), and 3-
acetoxybenzaldehyde (0.07 mL, 0.50 mmol). Subsequently, a solu-
tion of HCl (36%, 2.5 mL) in water (50 mL) was added and the
reaction mixture was stirred at room temp. for 1 h. After aqueous
workup, extraction with CH2Cl2 and drying over sodium sulfate,
the CH2Cl2 containing solution was concentrated to 250 mL, DDQ
(338 mg, 1.50 mmol) was added and the reaction mixture stirred
for 3 h at room temp. After filtration through silica gel, purification
by column chromatography (CH2Cl2/n-hexane, 2:1, v/v) and
recrystallization (CH2Cl2/n-pentane), corrole 9 (171.8 mg, 45 %)
H, Htriazole) ppm. β-Hpyrrole signals could not be detected. 13C
NMR (176 MHz, [D6]acetone): δ = 67.0 (OCH2), 113.9 (t, JC,F
2
=
17.8 Hz, Ar1F-Cipso), 116.2 (Ar-C), 118.5 (Ar2F-Cipso), 120.2 (3,7-
Cpyrrole), 121.7 (Ar-C), 127.6 (5-Ctriazole), 129.2 (Ar-C), 129.5 (Ar-
C), 131.3 (2,8-Cpyrrole), 134.7 (4,6-Cpyrrole), 137.1 (Ar1F-Cpara),
141.4 (ArF-Cmeta), 142.7 (ArF-Cmeta), 143.0 (4-Ctriazole), 144.7 (d, J
= 244.9 Hz, ArF-Cortho), 147.4 (1,9-Cpyrrole), 157.4 (Ar-C-OH) ppm.
19F NMR (376 MHz, [D6]acetone): δ = –139.17 (mc, 4 F, BODIPY-
Ar-Fortho), –141.20 (mc, 4 F, corrole-Ar-Fortho), - 44.52 (dd, J = 55.4,
27.7 Hz, 4 F, BF2), –147.31 (mc, 4 F, BODIPY-Ar-Fmeta), –156.58
(mc, 4 F, corrole-Ar-Fmeta) ppm. HRMS (ESI-TOF): m/z calcd. for
C73H31B2CuF20N14O3+ [M + H]+ 1616.1866; found 1616.1655. UV/
Vis (acetone): λmax (log ε, Lmol–1 cm–1) = 402 (5.26), 489 (4.99),
514.5 (5.23) nm. Fluorescence emission (acetone): λmax = 557 nm
at λExcit = 350 and 470 nm.
1
was obtained as purple crystals; m.p. 275 °C. H NMR (700 MHz,
CDCl3): δ = 2.39 (s, 3 H, CH3), 7.51 (ddd, J = 8.3, 2.3, 1.1 Hz, 1
H, Ar-Hpara), 7.79 (t, J = 7.9 Hz, 1 H, Ar-H-2), 7.97 (t, J = 2.0 Hz,
1 H, Ar-H-3), 8.10–8.07 (m, 1 H, Ar-H-1), 8.64–8.56 (m, 2 H, β-
Hpyrrole), 8.78 (d, J = 4.5 Hz, 2 H, β-Hpyrrole), 8.80 (d, J = 4.6 Hz, 2
H, β-Hpyrrole), 9.09 (d, J = 4.1 Hz, 2 H, β-Hpyrrole) ppm. 13C NMR
(176 MHz, CDCl3): δ = 21.2 (CH3), 112.1 (Ar-Cmeso), 114.0 (t, J =
18.0 Hz, ArF-Cipso), 117.5 (β-Cpyrrole), 121.0 (Ar-Cpara), 121.6 (β-
Cpyrrole), 125.7 (β-Cpyrrole), 127.8 (β-Cpyrrole), 128.0 (Ar-C-3), 128.2
(Ar-C-2), 131.3 (α-Cpyrrole), 132.3 (Ar-C-1), 135.3 (α-Cpyrrole), 137.9
1,2
(dt,
J
= 251.4, 12.0 Hz, ArF-Cpara), 140.7 (α-Cpyrrole), 141.8 (d,
C,F
1JC,F = 256.1 Hz, ArF-Cmeta), 142.6 (Ar-Cipso), 146.1 (d, JC,F
=
BODIPY-CuIII-corrole Array 14: CuSO4·5H2O (34 mg, 0.14 mmol),
1
246.3 Hz, ArF-Cortho), 149.8 (COAc), 169.6 (C=O) ppm. 19F NMR sodium ascorbate (128 mg, 0.65 mmol), BODIPY 3 (123 mg,
(376 MHz, CDCl3): δ = –137.7 (d, J = 17.2 Hz, 4 F, Ar-Fortho),
4234
0.32 mmol), and 10-[3-fluoro-5-(pentafluorothio)]-5,15-bis[4-(2-
www.eurjoc.org
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 4224–4237

Synthesis of Functionalized BODIPY Arrays
propyn-1-oxy)tetrafluorophenyl]corrole (12; 100 mg, 0.10 mmol)
were suspended in DMSO (2.0 mL) and stirred for 15 min at room
temp. After aqueous workup, extraction with CH2Cl2, and drying
over sodium sulfate, the crude product was evaporated to dryness,
Ar-H), 7.62–7.66 (m, 2 H, Ar-H), 7.72–7.78 (m, 4 H, Ar-H), 8.78
(s, 2 H, Ar-OH), 9.05–9.08 (m, 8 H, β-Hpyrrole) ppm. 13C NMR
(176 MHz, [D6]acetone): δ = 62.2 (OCH2), 77.6 (CϵCH), 78.4
(CϵCH), 103.2 (ArF-Cmeso), 114.6 (Ar-C), 114.7 (Ar-C), 116.9 (t,
purified by column chromatography (CH2Cl2/ethyl acetate, 98:2, J = 20.3 Hz, ArF-Cipso), 121.5 (Ar-C), 121.9 (Ar-C), 122.0 (Ar-C),
v/v) and recrystallized [CH2Cl2/(MeOH/H2O, 9:1, v/v)] to obtain
array 14 (85 mg, 45 %) as dark-brown crystals; m.p. Ͼ 300 °C.
HRMS (ESI-TOF): m/z calcd. for C73H29B2CuF26N14O2S+ [M]+
1744.1386; found 1744.2034. C73H30B2CuF26N14O2S+ [M + H]+
1745.1458; found 1745.2004. UV/Vis (CH2Cl2): λmax (log ε,
Lmol–1 cm–1) = 408.5 (4.89), 486 (3.96), 514.5 (5.24) nm. Fluores-
cence emission (acetone): λmax = 543 nm at λExcit = 350 and
400 nm.
126.4 (Ar-C), 127.4 (Ar-C), 130.3 (β-Cpyrrole), 133.0 (β-Cpyrrole),
136.6 (t, J = 12.8 Hz, ArF-Cpara), 141.6 (dd, J = 247.0, 15.8 Hz,
ArF-Cmeta), 143.9 (Ar-Cipso), 146.7 (d, J = 241.4 Hz, ArF-Cpara),
149.5 (α-Cpyrrole), 150.6 (α-Cpyrrole), 155.6 (Ar-C-OH), 155.7 (Ar-
C-OH) ppm. 19F NMR (376 MHz, [D6]acetone): δ = –141.07 to
–141.37 (m, 4 F, Ar-Fmeta), –158.08 to –158.32 (m, 2 F, Ar-
F
ortho) ppm. HRMS (ESI-TOF): m/z calcd. for C50H24F8N4O4Zn+
[M + H]+ 961.1034; found 961.0973. UV/Vis (acetone): λmax (log ε,
Lmol–1 cm–1) = 415 (5.29), 545.5 (4.19) nm.
5,15-Bis(3-acetoxyphenyl)-10,20-bis(pentafluorophenyl)porphyrin
(15): Anhydrous CH2Cl2 (500 mL) was placed in a three-necked
flask equipped with a magnetic stirrer and argon gas inlet. After
3-acetoxybenzaldehyde (0.38 mL, 2.00 mmol) and pentafluoro-
phenyl-dipyrromethane 1 (625 mg, 2.00 mmol) were added, the
flask was shielded from ambient light. Trifluoroacetic acid (77 μL,
1.00 mmol) was added and the reaction mixture was stirred at room
temp. for 18 h. DDQ (0.70 g, 0.30 mmol) suspended in anhydrous
CH2Cl2 (50 mL) was added and the mixture was stirred for 2 h.
Triethylamine (0.7 mL, 5.00 mmol) was added and, after 15 min,
the mixture was filtered through silica and the solvent was evapo-
rated. After column chromatography (CH2Cl2/ethyl acetate, 99:1,
v/v) and recrystallization (CH2Cl2/n-hexane) the product (130 mg,
28 %) was obtained as purple crystals; m.p. 283 °C. 1H NMR
(400 MHz, [D6]acetone): δ = –2.88 (s, 2 H, NH), 2.40 (s, 6 H, CH3),
7.55–7.60 (m, 2 H, Ar-H-6), 7.79 (t, J = 7.9 Hz, 2 H, Ar-H-5),
7.96–8.01 (m, 2 H, Ar-H-2), 8.06–8.13 (m, 2 H, Ar-H-4), 8.84 (d,
J = 4.4 Hz, 4 H, 2,8,12,18-β-Hpyrrole), 9.03 (d, J = 4.6 Hz, 4 H,
3,7,13,17-β-Hpyrrole) ppm. 13C NMR (126 MHz, [D6]acetone): δ =
21.3 (CH3), 102.4 (ArF-Cipso), 116.4 (ArF-Cipso), 120.2 (ArF-Cmeso),
121.5 (Ar-C-6), 127.9 (Ar-C-5), 128.1 (Ar-C-2), 132.3 (Ar-C-4),
142.5 (Ar-Cipso), 145.6 (ArF-Cmeta), 147.6 (ArF-Cortho), 149.4 (Ar-
C-3), 169.7 (C=O) ppm. 19F NMR (376 MHz, [D6]acetone): δ =
–136.28 to –137.16 (m, 4 F, Ar-Fmeta), –152.02 (t, J = 21.3 Hz, 2 F,
Ar-Fpara), –161.30 to –162.23 (m, 2 F, Ar-Fortho) ppm. HRMS (ESI-
BODIPY-ZnII-porphyrin Array 19. Variant 1: A 25 mL high-pres-
sure reaction flask was loaded with CuSO4·5H2O (12.7 mg,
50.9 μmol), sodium ascorbate (47.0 mg, 0.24 mmol), BODIPY 3
(122 mg, 0.32 mmol), and zinc porphyrin 17 (77.0 mg, 80.2 μmol).
The mixture was suspended in THF (3.0 mL), heated to 80 °C, and
stirred for 24 h. After aqueous workup, extraction with ethyl acet-
ate, and drying over sodium sulfate, the crude product was evapo-
rated to dryness, purified by column chromatography (n-hexane/
acetone, 3:2, v/v) and recrystallized (acetone/n-pentane) to obtain
array 19 (89 mg, 64%) as reddish pink powder; m.p. Ͼ 310 °C.
Variant 2: As described for variant 1, all reactants were suspended
in DMSO (2 mL) and stirred for 15 min at room temp. Workup
and purification was carried out in accordance to variant 1, yield
1
96 mg (69%). H NMR (700 MHz, [D6]acetone): δ = 5.92 (s, 4 H,
OCH2), 6.78 (d, J = 4.3 Hz, 4 H, 3,7-Hpyrrole), 7.31 (ddd, J = 8.4,
2.5, 1.0 Hz, 2 H, Ar-H), 7.39 (d, J = 4.4 Hz, 4 H, 2,8-Cpyrrole),
7.57–7.61 (m, 2 H, Ar-H), 7.70–7.72 (m, 2 H, Ar-H), 7.75 (s, 2 H,
Ar-H), 8.22 (s, 4 H, 1,9-Cpyrrole), 8.83 (s, 2 H, Ar-OH), 8.96 (s, 2 H,
H
triazole), 9.04 (d, J = 4.5 Hz, 4 H, β-Hpyrrole), 9.06 (d, J = 4.6 Hz, 4
H, β-Hpyrrole) ppm. 13C NMR (176 MHz, [D6]acetone): δ = 67.1
2
(OCH2), 103.1 (ArF-Cmeso), 114.0 (t, JC,F = 18.4 Hz, ArF-Cipso),
2
2
114.7 (Ar-C), 116.9 (t, JC,F = 20.3 Hz, ArF-Cipso), 118.6 (t, JC,F
= 13.9 Hz, BODIPY-ArF-Cpara), 120.2 (3,7-Cpyrrole), 121.5 (Ar-C),
122.0 (Ar-C), 126.4 (Ar-C), 127.4 (Ar-C), 127.7 (5-Ctriazole), 129.2
TOF): m/z calcd. for C48H25F10N4O4 [M + H]+ 911.1711; found
+
911.1719. UV/Vis (CH2Cl2): λmax (log ε, L mol–1 cm–1) = 415.5
(5.19), 510 (4.04), 543 (3.38), 588.5 (3.29), 645 (3.12) nm.
(5-Cmeso), 130.3 (β-Cpyrrole), 131.3 (2,8-Cpyrrole), 132.9 (β-
2
C
pyrrole), 134.7 (4,6-Cpyrrole), 137.0 (t, JC,F = 12.5 Hz, porphyrin-
2,3
ArF-Cpara), 141.7 (dd,
(dd,
(Ar-C), 144.8 (ddt,
J
= 246.8, 15.5 Hz, ArF-Cmeta), 142.3
= 255.3, 16.3 Hz, ArF-Cmeta), 143.3 (4-Ctriazole), 143.9
C,F
{5,15-Bis(3-hydroxyphenyl)-10,20-bis[4-(2-propyn-1-oxy)tetra-
fluorophenyl]porphyrinato}zinc(II) (17): Compound 15 (200 mg,
0.21 mmol) was dissolved in anhydrous DMSO (3.0 mL) under an
argon atmosphere, KOH (130 mg, 2.31 mmol) and propargyl
alcohol (0.67 mL, 12.1 mmol) were added and the reaction mixture
was stirred at room temp. for 25 min. After aqueous workup, ex-
traction with ethyl acetate, and drying over sodium sulfate, the
crude product was evaporated to dryness, purified by column
chromatography (CH2Cl2/MeOH, 95:5, v/v) and recrystallized
(CH2Cl2/n-hexane) to obtain bis(3-hydroxyphenyl)-10,20-bis[4-(2-
propyn-1-oxy)tetrafluorophenyl]porphyrin (165 mg, 83%) as pur-
ple solid; m.p. 278 °C. The alkynyl-substituted porphyrin was then
dissolved in a mixture of CH2Cl2/MeOH (4:1, v/v, 100 mL).
Zinc(II) acetate (5.0 g, 22.7 mmol) and sodium acetate (300 mg,
3.56 mmol) were added and the reaction mixture was stirred at
room temp. for 2 h. After aqueous workup, extraction with ethyl
acetate, and drying over sodium sulfate, the crude product was
evaporated to dryness, purified by column chromatography
(CH2Cl2/MeOH, 95:5, v/v) and recrystallized (CH2Cl2/n-hexane) to
2,3
J
C,F
2,3,4
J
= 249.9, 13.5, 4.8 Hz, ArF-Cortho), 146.8
C,F
2
(d, JC,F = 245.2 Hz, ArF-Cortho), 147.4 (1,9-Cpyrrole), 149.5 (α-
Cpyrrole), 150.6 (α-Cpyrrole), 155.6 (Ar-C-OH) ppm. 19F NMR
(376 MHz, [D6]acetone): δ = –139.04 to –139.24 (m, 4 F, BODIPY-
Ar-Fortho), –141.02 to –141.19 (m, 4 F, porphyrin-Ar-Fortho),
–144.44 (dd, J = 56.0, 27.5 Hz, BF2), –147.14 to –147.32 (m, 4
F, BODIPY-Ar-Fmeta), –158.07 to –158.32 (m, 4 F, porphyrin-Ar-
F m e t a ) p p m . H R M S ( E S I - T O F ) : m / z c a l c d . f o r
C80H37B2F20N14O4Zn+ [M + H]+ 1723.2275; found 1723.2171.
C80H37B2F20N14NaO4Zn+ [M + Na + H]+ 1746.2024; found
1746.2026. UV/Vis (acetone): λmax (log ε, L mol–1 cm–1) = 420
(5.11), 514 (4.41) nm. Fluorescence emission (acetone): λmax = 543,
603, 650 nm at λExcit = 355 and 500 nm.
BODIPY-ZnII-porphyrin Array 20: {Tetrakis[4-(propargyloxy)-
2,3,5,6-tetrafluorophenyl]porphyrinato}zinc(II) (18; 29.6 mg,
26.4 μmol), BODIPY 3 (60.5 mg, 158 μmol), CuSO4·5H2O (8.4 mg,
33.6 μmol), and sodium ascorbate (31.4 mg, 158 μmol) were dis-
solved in THF (3.0 mL) in a high-pressure tube. Upon sealing, the
obtain zinc complex 17 (173 mg, 98 %) as a pink powder; m.p.
1
203 °C. H NMR (700 MHz, [D6]acetone): δ = 3.50 (t, J = 2.4 Hz, reaction mixture was heated to 80 °C and stirred for 24 h overnight.
2 H, CϵCH), 5.34 (d, J = 2.4 Hz, 4 H, OCH2), 7.32–7.36 (m, 2 H, After aqueous workup, extraction with ethyl acetate, and drying
Eur. J. Org. Chem. 2015, 4224–4237
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
4235

H.-U. Reissig, A. Wiehe et al.
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over sodium sulfate, the crude product was evaporated to dryness,
purified by column chromatography (n-hexane/acetone, 2:3, v/v)
and recrystallized [CH2Cl2/(MeOH/H2O, 8:2, v/v)] to obtain array
20 (43 mg, 60 %) as pink crystals; m.p. Ͼ 310 °C. 1H NMR
(700 MHz, [D6]acetone): δ = 5.91 (s, 8 H, OCH2), 6.77 (d, J =
4.3 Hz, 8 H, 3,7-Hpyrrole), 7.38 (d, J = 4.3 Hz, 8 H, 2,8-Cpyrrole),
8.20 (s, 8 H, 1,9-Cpyrrole), 8.95 (s, 4 H, Htriazole), 9.21 (s, 8 H, β-
[6]
H
pyrrole) ppm. 13C NMR (176 MHz, [D6]acetone): δ = 67.2 (OCH2),
2
2
104.3 (ArF-Cmeso), 114.0 (t, JC,F = 18.6 Hz), 116.1 (t, JC,F
18.6 Hz, ArF-Cipso), 118.6 (tt,
=
2,3
J
= 12.9, 2.9 Hz, BODIPY-ArF-
C,F
Cpara), 120.2 (3,7-Cpyrrole), 127.7 (C=CHtriazole), 129.2 (5-Cmeso),
131.3 (2,8-Cpyrrole), 132.0 (β-Cpyrrole), 134.7 (4,6-Cpyrrole), 137.4 (t,
[7]
[8]
2,3
2JC,F = 12.5 Hz, porphyrin-ArF-Cpara), 141.72 (dd,
J
= 248.1,
C,F
2,3
15.5 Hz, ArF-Cmeta), 142.37 (dd,
J
= 255.0, 15.6 Hz, ArF-
C,F
2,3
Cmeta), 143.3 (C=CHtriazole), 144.81 (dd,
J
= 250.3, 13.4 Hz,
C,F
2
ArF-Cortho), 146.8 (d, JC,F = 247.2 Hz, ArF-Cortho), 147.4 (1,9-
C
pyrrole), 150.3 (α-Cpyrrole) ppm. 19F NMR (376 MHz, [D6]acetone):
δ = –139.01 to –139.24 (m, 8 F, BODIPY-Ar-Fortho), –141.01 to
–141.31 (m, 8 F, porphyrin-Ar-Fortho), –144.40 (dd, J = 55.8,
27.9 Hz, 8 F, BF2), –147.00 to –147.28 (m, 8 F, BODIPY-Ar-Fmeta),
–157.76 to –158.05 (m, 8 F, porphyrin-Ar-Fmeta) ppm. HRMS (ESI-
TOF): m/z calcd. for C116H44B4F40N24O4NaZn+ [M + Na]+
2727.2900; found 2727.2894. UV/Vis (acetone): λmax (log ε,
Lmol–1 cm–1) = 417 (5.39), 514.5 (4.22) nm. Fluorescence emission
(acetone): λmax = 546, 590, 643 nm at λExcit = 350 and 450 nm.
See ref.[8c] and: S. Suzuki, M. Kozaki, K. Nozaki, K. Okada,
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Financial support by the Deutsche Forschungsgemeinschaft
(DFG), Graduate School 1582 – Fluorine as a Key Element – and
by the Bundesministeriums für Bildung und Forschung (BMBF)
(EuroNanoMed Project “Target-PDT”, FKZ: 13N11032, Biolitec
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Received: March 30, 2015
Published Online: May 27, 2015
Eur. J. Org. Chem. 2015, 4224–4237
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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