Modification of alkyne-functionalized asymmetric phthalocyanines by CuI-catalyzed azide-alkyne cycloaddition

Article abstract of DOI:10.1016/j.tet.2015.09.074

The use of asymmetric phthalocyanines (Pcs) as platforms for the preparation of several asymmetric hexatriazolyl-monohydroxyphthalocyanines via copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction was investigated. Asymmetric Pcs 5a and 5b were

Full text of DOI:10.1016/j.tet.2015.09.074

Accepted Manuscript
I
Modification of alkyne-functionalized asymmetric phthalocyanines by Cu -catalyzed
azide-alkyne cycloaddition
Xiaochun Chen, Chin-Wei Lu, Yiming Huang, Dominic V. McGrath
PII:
S0040-4020(15)30101-0
10.1016/j.tet.2015.09.074
TET 27171
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 August 2015
Revised Date: 29 September 2015
Accepted Date: 30 September 2015
Please cite this article as: Chen X, Lu C-W, Huang Y, McGrath DV, Modification of alkyne-functionalized
I
asymmetric phthalocyanines by Cu -catalyzed azide-alkyne cycloaddition, Tetrahedron (2015), doi:
10.1016/j.tet.2015.09.074.
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Modification of alkyne-functionalized
asymmetric phthalocyanines by CuI-
catalyzed azide-alkyne cycloaddition
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Xiaochun Chen, Chin-Wei Lu, Yiming Huang, Dominic V. McGrath
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721

1
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Tetrahedron
journal homepage: www.elsevier.com
Modification of alkyne-functionalized asymmetric phthalocyanines by CuI-catalyzed
azide-alkyne cycloaddition
Xiaochun Chen, Chin-Wei Lu, Yiming Huang, and Dominic V. McGrath*
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ 85721
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The use of asymmetric phthalocyanines (Pcs) as platforms for the preparation of several
asymmetric hexatriazolyl-monohydroxyphthalocyanines via copper(I)-catalyzed azide-alkyne
cycloaddition (CuAAC) reaction was investigated. Asymmetric Pcs 5a and 5b were prepared
through statistical macrocyclization of phthalonitriles (Pns) 1a and 2 to give PMB-protected 4a
and 4b which afforded asymmetric Pcs 5a and 5b after acidic cleavage. The “ROMP-Capture-
Release” method as a synthetic approach to prepare asymmetric Pc 5b was also evaluated. TIPS-
protection of the terminal alkynes was necessary to prevent cross-coupling during the ring-
opening metathesis polymerization (ROMP) step. Zinc Pc 5b was successfully used as a
scaffold for functional modification under CuAAC conditions using several azides bearing
hydrophobic, photo-crosslinkable, or electroactive moieties. Monitoring the CuAAC reaction by
both UV/Vis and FT-IR spectroscopies provided insight into the role of azide equivalent,
reaction time, and catalyst on reaction progress.
Available online
Keywords:
Phthalocyanine
Click Chemistry
Metathesis
Tetrapyrrolic Molecules
Cycloaddition
2009 Elsevier Ltd. All rights reserved
.
1. Introduction
demonstrated preparation of symmetric octaalkynyl Pcs as an
effective platform for Pc chromophore modification through
copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC)
reactions.19 Herein we report the synthesis of asymmetric
hexaalkynyl AB3 Pcs 5a and 5b and subsequent post-cyclization
modification with various azides to further demonstrate the utility
of Pc modification through the CuAAC reaction.21
Pcs are 18 π-electron tetrapyrrolic macrocycles that have been
applied in a number of advanced technologies including optical
limiting devices,1 photodynamic therapy (PDT),2 organic field-
effect transistors (OFETs),3 and organic photovoltaic (OPV)
devices.4 Due to their physical and chemical properties,5 effort
has been dedicated to the development of structurally diverse
Pcs. Of particular interest is the development of asymmetrically
substituted AB3 Pcs6 which can possess improved photodynamic
properties7 and unique second-order nonlinear optical effects.1d,8
Asymmetric AB3 Pcs containing active functional groups in the
odd quadrant such as hydroxy,9 amino,10 carboxylic acid,10a,11
isothiocyanate,12 azide,13 and alkyne14 serve as building blocks in
the design of Pc-based molecular systems.15 We have used
asymmetric AB3 Pcs as components of a model system to
investigate charge capture at oxide interfaces from typical OPV
donor materials.16
2. Results and Discussion
In seeking to use the CuAAC reaction as a means of
increasing structural diversity in asymmetric Pc chromophores,
we identified bis(alkynyl) Pn 1a,19a readily prepared from 4,5-
bis(4’-hydroxyphenoxy)phthalonitrile and commercially avail-
able 1-hexyn-6-ol through a Mitsunobu reaction, as a suitable
precursor. We have previously reported that macrocyclization of
1a under basic Linstead conditions afforded octaalkynyl ZnPc 3b
which possesses good solubility in common organic solvents
such as THF, DCM, acetone, and Et2O.19a Protection of the
terminal alkyne moieties was not necessary during the
macrocyclization reaction, providing a relatively simple way to
incorporate acetylenic moieties into a Pc scaffold.
However, efficient production of Pc-based materials with
structural diversity, including AB3 asymmetry, still remains an
open challenge, especially for Pcs with sensitive substituents that
are not compatible with the conditions of cyclization of Pc
precursors. The copper(I)-catalyzed azide-alkyne cycloaddition
(CuAAC) reaction17 has proven useful for the synthesis of novel
materials,18 and has been demonstrated by us19 and others20 as
To use Pn 1a in the preparation of asymmetric AB3 Pcs, we
needed to choose a strategy for asymmetric Pc synthesis. The
preparation of asymmetrically substituted AB3 Pcs can be
achieved by solution phase statistical Linstead macrocyclization
between two different phthalonitriles or diiminoisoindolines.22
Ready availability of precursors makes the statistical macro-
cyclization often a more effective and direct than other
appropriate for Pc/Nc modification.
We have previously
Corresponding author. Tel.: +1 520 6264690; fax: +1 520 6218407
E-mail address: mcgrath@u.arizona.edu (D.V. McGrath)

2
Tetrahedron
We also evaluated the latter method, our previously reported
ACCEPTED MANUSCRIPT
RO
RO
CN
CN
“ROMP-Capture-Release” strategy9b to synthesize asymmetric
PMBO
CN
CN
LiBr or Zn(OAc)2
+
hexaalkynyl Pc 5a. This method employs solution phase
crossover-Linstead cyclization of a norbornyl-tagged Pn (A) with
a second Pn (B), followed by selective capture of asymmetric
norbornyl-tagged AB3 Pc under ROMP conditions and acidic
cleavage of the target asymmetric Pc from the ROMP polymer.
While this method was successfully developed for the synthesis
of an asymmetricAB3 Pc with alkyl substituents,9b the concern of
cross-coupling of free alkynes with the norbornyl tag during the
ROMP process remained. Enyne metathesis25 is well established
to occur with ruthenium-based metathesis catalysts,26 including
the cross-metathesis of terminal alkynes with norbornene
DBU, 1-pentanol
1a
2
OR
RO
RO
OR
RO
OR
RO
OR
N
N
M
N
N
N
N
N
N
N
N
N
N
N
N
M
N
N
+
detivatives.27 An unsuccessful attempt to ROMP
a
7-
OPMB
RO
OR
RO
oxanorbornene monomer with a pendant propargyl group was
RO
RO
OR
attributed to the competing enyne metathesis reaction.28 If
3a: M = H2
3b: M = Zn
4a: M = H2
4b: M = Zn
alkynes
undergo
ring-opening/ring-closing
metathesis
(ROM/RCM) with the norbornene moieties in the presence of
Grubbs’ catalyst, a protecting strategy can be employed to
prevent competing metathesis with the alkyne moiety.
OR
RO
RO
OR
N
To provide a comparison, preparation of two Pcs with free and
protected alkyne peripheries was conducted (Scheme 2) by
ROMP-Capture-Release through statistical macrocyclization of
norbornyl-tagged Pc 6 with both acetylenic Pn 1a and its TIPS-
protected analog 1b. When the mixture of Pcs 7a and 8a was
subjected to the previously established ROMP conditions,9b no
polymer precipitate was observed. Modified conditions were
also attempted, such as increasing the loading of crosslinker 9
and varying the reaction concentration and time, with similar
negative results. Conversely, when the mixture of TIPS-
protected Pcs 7b and 8b was subjected to the ROMP conditions
in the presence of crosslinker 9 the corresponding cross-linked
polymer was obtained after filtration and CH2Cl2 Soxhlet
extraction (Scheme 3). Treatment of the resulting ROMP
polymer 10 with 10% trifluoroacetic acid (TFA) in CH2Cl2
resulted in release of Pc 11. Deprotection of Pc 11 using an
excess of tetrabutylammonium fluoride (TBAF) afforded Pc 5a
in 7% overall yield from Pn 6.
N
N
N
N
10% TFA in CH2Cl2
M
N
N
N
OH
RO
RO
O
R =
5a: M = H2
5b: M = Zn
Scheme 1. Synthesis of asymmetric Pc 5a and 5b by statistical
macrocyclization followed by acidic cleavage.
approaches such as solid-phase synthetic methods23 and the “sub-
phthalocyanine” method.24 The challenge of statistical macro-
cyclization is that it inherently yields a mixture of Pc products
with minimal structural differences, making isolation of the
desired Pcs often challenging.
However, we have recently reported statistical cyclization
strategies but with modifications aimed at simplifying
purification. We have described the synthesis of asymmetric
AB3 Pcs via: (1) statistical macrocyclization using 4-
methoxybenzyl (PMB)-protected Pn16a to yield asymmetric AB3
Pcs with a unique phenolic quadrant that aids in isolation once
deprotected; and (2) a ROMP-Capture-Release9b strategy using a
norbornyl-tagged Pn, again leading to an asymmetric AB3 Pc
Despite the successful isolation of Pc 5a via the ROMP-
Capture-Release strategy, including successful prevention of
CN
RO
RO
CN
CN
DBU, LiBr
1-pentanol
O
CN
+
O
1a
1b
6
with a phenolic unique quadrant.
Both methods would
potentially serve to produce asymmetric AB3 Pcs with acetylenic
moieties for post-synthetic modification by the CuAAC reaction.
RO
OR
OR
RO
RO
OR
RO
OR
Employing the former method, statistical macrocyclization of
1a and 4-methoxybenzyl (PMB)-protected Pn 216a (Pn 1a:2 = 3:1)
in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) as
a base and either LiBr or Zn(OAc)2 as metal template provided a
mixture of symmetric and asymmetric Pcs (Scheme 1). The crude
mixture was chromatographed to remove DBU and excess metal
salt from the Pc mixture. MALDI mass spectral analysis of the
resultant Pc mixtures revealed the presence of PMB-protected
A3B (4a/4b) and symmetric A4 (3a/3b) Pcs. Subjecting the
mixtures to PMB deprotection conditions yielded a mixture of
asymmetric free hydroxyl A3B (5a/5b) and symmetric A4 (3a/3b)
Pcs. Due to the increased polarity afforded by the unique
phenolic quadrant in the asymmetric Pcs, this mixture was easily
separable by flash chromatography to provide the desired
macrocycles 5a/5b in overall yields of 20 and 22% from Pn 2,
respectively.
N
N
NH
N
N
NH
O
N
N
N
N
+
N
HN
N
HN
N
N
RO
OR
O
RO
RO
RO
OR
7a
7b
8a
8b
O
a R =
TIPS
O
R =
b
Scheme 2. Statistical macrocyclization of Pns 1a, 1b, and 6.

3
ACCEPTED MANUSCRIPT
R
OR
RO
N
5b
N
RO
RO
OR
N
N
N
NH
9
N
N
7b + 8b
CH2Cl2, 40 °C
O
N
HN
N
N
1 mol %
NR
N
O
O
MesN
Cl
NMes
O
RO
O
HO
N
Ru
Cl
Ph
O
10
N
N
N
N
PCy3
Zn
N
N
n
N
O
O
O
O
O
O
OR
RO
RO
OR
OH
NR
RN
N
N
N
N
N
O
O
N
NH
13a-d
10% TFA in CH2Cl2
N
N
N
HN
N
N
N
N
N
N
N
RO
R
R
RO
TIPS
O
11 R =
R =
TBAF
THF
a
b
5b
O
R =
O
O
N
O
Scheme 3. ROMP-Capture-Release leading to asymmetric Pc 5a.
EtO2C
C6H13
C6H13
N
O
O
alkyne metathesis, the lengthy reaction route involving the
additional protection and deprotection resulted in low yields of
the desired asymmetric Pc. This hampered straightforward scale-
up to larger quantities of material. We relied on the statistical
macrocyclization using 4-methoxybenzyl (PMB)-protected Pn
for further preparation of 5a and 5b.
c
d
Scheme 4. Synthesis of Pc derivatives 13a-d by CuAAC.
UV/Vis absorption spectra exhibited a singlet Q-band ca. 685 nm
indicating the existence of metallated Pcs. Pc 13d showed
additional absorption peaks at 530 nm and 490 nm due to the
incorporation of the perylene diimide (PDI) chromophores.
With Pcs 5a and 5b in hand, we examined modification of the
periphery of the Pc chromophore with CuAAC chemistry.
Although we had previous success with insertion of copper into
non-metallated Pcs in the course of CuAAC reactions,19 we
observed incomplete metal-insertion in the CuAAC reactions of
Pc 5a and azides, characterized by both MS-MALDI and
UV/Vis. Samples isolated from these reactions contained a
mixture of both Cu-metallated and metal-free Pc. Metallation of
the modified Pc derivatives using various Cu(II) salts yielded
insufficient intercalation as well.
Observation of the CuAAC reactions indicated poor solubility
of the Cu complex. We anticipated that further utilization of the
CuAAC reaction on Pc 5b, particularly from Pcs bound to solid
support surfaces such as ITO and ZnO, would require fully
5b
We expected that Zn-metallated Pc 5b would prevent the
inherent Cu-insertion reaction in the modification of Pcs by
CuAAC and therefore allow the use of less CuI. Conditions
similar to those described in the previous literature were first
applied to reactions with azides 12a-c, CuI, and DIPEA in THF
(Scheme 4).19b Due to the poor solubility of 12d in THF, the
reaction towards 13d was carried out in CHCl3. Using a 10:1
ratio of azide to alkyne under these conditions, a reaction time at
ambient temperature of sixteen hours was sufficient to provide
hexatriazenyl Pcs 13a-d in yields of 24-44% from Pc 5b. Given
that each reaction represented the successful completion of 6
parallel azide-alkyne coupling reactions, these isolated yields
represent a range of 79-87% for the individual CuAAC reactions.
13a
13b
13c
13d
Pcs 13a-d were characterized by mass spectrometry,
combustion analysis and UV/Vis spectroscopy. UV/Vis
spectroscopic data was consistent with the chromophoric
structure of Pcs 13a-d relative to precursor Pc 5b (Figure 1). The
300
400
500
600
700
800
Wavelength (nm)
Figure 1. UV/Vis absorption of Pcs 5b and 13a-d in CHCl3.

4
Tetrahedron
ACCEPTED MANUSCRIPT
(a)
(b)
(b)
5b
5b
2.5
2
10 m
2 h
1 h
2 h
3 h
6 h
55 h
4 h
6 h
55 h
1.5
1
10 equiv.
3 equiv.
1 equiv.
0.5
0
0
40 80 120 160
Reaction Time (h)
450 550 650 750
Wavelength (nm)
450 550 650 750
Wavelength (nm)
Figure 3. (a) Maximum PDI absorbance normalized to Pc Q-band
intensity as a function of reaction time with CuI or Cu(PPh3)3Br as the
catalyst. (Inset) Digital image of isolated Pc mixture (~100 µM in
CHCl3) at different reaction times: (left to right) 1 h, 2 h, 3 h, 6 h, 50 h,
catalyzed by Cu(PPh3)3Br. (b) Normalized absorbance as a function of
reaction time with 1, 3, 10 equivalents of azide 12d relative to alkyne
moiety in 5b.
Figure 2. UV/Vis spectra of isolated products (~10 µM in CHCl3) from
the CuAAC reaction between 5b and 12d at different reaction times,
normalized to the Pc Q-band. (a) CuI and (b) Cu(PPh3)3Br were used as
catalysts, respectively.
soluble Cu sources such as Cu(PPh3)3Br,19a especially in flow-cell
configurations.16 We carried out the CuAAC reaction of azide
12d with both Cu(PPh3)3Br and CuI and monitored both by
UV/Vis characterization over approximately 60 hours (Figure 2).
Due to the large excess of azide, the quenched reaction mixture at
each time interval was subjected to flash column chromatography
to isolate the mixture of Pc species. UV/Vis spectra were
normalized to the absorbance of the Pc Q-band to illustrate the
relative increase of the PDI chromophore absorption, indicative
of the PDI to Pc ratio in the product mixture. The incorporation
of the PDI chromophore during the reaction was qualitatively
followed by monitoring the isolated products at 530 nm, an
optical window of Pcs. Upon normalization at the Pc Q-band, the
PDI absorbance arriving at a constant indicated that the CuAAC
reaction had reached completion.
Thin films of Pcs 5b, 13d, and PDI azide 12d were prepared
to investigate the nature of the Pc in the condensed state. Spin-
coated films on glass were fabricated from CHCl3 solutions (10
M). The resulting crack-free solid films were analyzed by
UV/Vis spectroscopy (Figure 4). Comparison of the solution
phase and condensed-phase spectra of Pc 5b revealed a
significant degree of aggregation in the thin film as evidenced by
the hypsochromically shifted component of the Q band at ca. 640
nm. Similarly, the condensed phase UV-Vis spectrum of PDI
azide 12d indicates extensive aggregation of the PDI
chromophores as evidenced by the greater intensity of the
vibronic band at ca. 490 nm relative to the fundamental transition
at ca. 550 nm.
The ratio of PDI absorbance to Pc Q-band reached 2.68 and
2.66 for CuI and Cu(PPh3)3Br catalyzed reactions, respectively.
A plot of the PDI absorbance maxima vs. reaction time (Figure
3a) indicates that both reactions reached this level of completion
after six hours under these reaction conditions. By visual
inspection of the reaction mixture at various time points, we
observed a clear progression of color as more PDIs are
incorporated on the Pc periphery (Figure 3a, inset). Monitoring
of the reaction by FT-IR also showed progress and confirmed
completion by the disappearance of characteristic terminal alkyne
absorptions of sp-hybridized C-H at 3291 cm-1 and the C≡C at
2119 cm-1 (Figure S11).
Interestingly, the UV-Vis spectrum of 13d reveals that while
the PDI chromophores in this conjugate remain aggregated, again
5b
13d
12d
The influence of azide equivalents on the modification of Pc
5b was also studied in a similar fashion. Keeping all other
reaction conditions constant (CuI, DIPEA, CHCl3), variation of
the azide equivalents (1, 3, 10 relative to alkyne residue) of 12d
was performed (Figure 3b). As expected, we observed that the
reaction progress was expedited with increased azide loading,
with ten equivalents showing a plateauing effect within six hours,
while three equivalents of azide likely afforded the product with
extended reaction times of longer than three days (Figure 3b).
The use of equimolar amounts of azide to free alkyne yielded a
PDI-Pc ratio of only 2.18, which is significantly lower than
observed with ten equivalents of azide (vide supra).
300
400
500
600
700
800
Wavelength (nm)
Figure 4. Condensed-phase UV/Vis spectra of 5b, 12d and 13d spin-
coated on glass.

5
chromatographed (SiO2, CH2Cl2: MeOH = 99:1). The green
evidenced by the relative intensities of the bands at 490 and 550
nm, the Pc chromophores appear to be in primarily unaggregated
form. This suggests that peripheral substitution with PDIs
through CuAAC chemistry can provide sufficient hindrance to
central Pc aggregation, presumably by steric interference.
However, we have previously observed varying degrees of
frustration of aggregation with varying substituents on the
periphery of Pc chromophores,19b,29 and in the case of 13d,
frustration of aggregation of the Pc cannot be merely the result of
steric interference of the PDI moieties alone. An analogous
compound to 13d with second generation benzyl arylene ether
dendrons, much bulkier substituents, in the same position as the
PDI moieties in 13d, exhibited Pc aggregation in the condensed
phase.19b We postulate that the strong aggregation tendency of
the PDI moieties, rather than their steric bulk alone, is a
contributing factor to preventing Pc aggregation, perhaps by
creating a tight shell around the Pc core of the compound.
ACCEPTED MANUSCRIPT
eluent was collected and concentrated under reduced pressure. A
solution of the resultant green residue, TFA (5 mL) and CH2Cl2
(50 mL) was stirred at room temperature under Ar for 4h. The
reaction mixture was washed with water (50 mL), aqueous
NaHCO3 (50 mL), and the organic layer was dried over MgSO4,
filtered, and evaporated. The crude product was purified by
column chromatography (SiO2, CH2Cl2: MeOH = 99:1) to give
1.2 g of Pc 5a (22% yield) as a green solid: 1H NMR (500 MHz,
CD2Cl2:DMSO-d6 = 95:5) δ (ppm) 9.85 (s, 1H), 8.30-7.90 (m,
8H), 7.44-7.26 (m, 13H), 7.06-6.93 (m, 12H), 4.06-3.99 (m,
12H), 2.38-2.29 (m, 12H), 2.11-2.07 (m, 6H), 2.01-1.95 (m,
12H), 1.85-1.77 (m, 12H); 13C NMR (125 MHz, CD2Cl2:DMSO-
d6 = 95:5) δ (ppm) 160.6, 156.0, 155.9, 155.8, 155.4, 151.63,
151.55, 151.4, 151.1, 151.0, 150.9, 150.5, 150.4, 149.7, 137.3,
132.5, 1324, 131.7, 130.7, 130.4, 127.0, 124.2, 121.1, 121.0,
120.3, 120.2, 120.0, 119.5, 119.2, 116.0, 115.9, 115.8, 113.5,
113.4, 112.7, 112.5, 111.4, 111.1, 108.1, 84.52, 84.49, 68.96,
68.95, 68.91, 68.90, 68.5, 68.2, 30.0, 28.92, 28.88, 25.60, 25.56,
18.59, 18.55; MS (MALDI) calcd for C104H91N8O13 [M+H]+: m/z
1659.67, found 1659.72. Anal. calcd for C104H90N8O13: C, 75.25;
H, 5.47; N, 6.75. Found: C, 75.00; H, 5.90; N, 6.44%
3. Conclusions
The modification of Pc peripheral substituents with CuAAC
chemistry was demonstrated on asymmetric Pc scaffold 5b.
Asymmetric Pc derivatives 13a-d were constructed from Pc 5b
and azides 12a-d under CuAAC conditions. The utility of using
the CuAAC reaction as a means to introduce various substituents
onto the periphery of the Pc chromophore holds much promise in
the preparation of multifunctional Pc derivatives. Modification
of the hydroxyl group in the unique quadrant of the Pc
chromophore will be the subject of future research.
4.2.2. 2,3,9,10,16,17-Hexa-(4'-(hex-5''-ynyloxy)phenoxy)-23-
hydroxyphthalocyanine (5a) by fluoride-deprotection of 11.
A
mixture of phthalonitrile 6 (400 mg, 1.12 mmol), phthalonitrile
1b (3.5 g, 4.4 mmol), DBU (836 mg, 5.50 mmol) and LiBr (47
mg, 0.55 mmol) in 40 mL 1-pentanol was refluxed under Ar for 8
h. The reaction mixture was allowed to cool to room temperature,
and poured into MeOH. The precipitate was filtered, washed with
MeOH, air dried and chromatographed on silica gel, eluting with
CH2Cl2: MeOH = 95:5. The green eluent was collected and
concentrated in vacuum. The resultant green residue and cross-
linker 9 (60 mg, 0.24 mmol) were dissolved in degassed CH2Cl2
(30 mL) under N2. To this solution was added [1,3-bis-(2,4,6-
trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethyl-
ene)(tricyclohexylphosphine)ruthenium (Grubbs’ 2nd generation
catalyst, 60 mg, 72 µmol), and the mixture was heated at 40 °C
for 12 h. CH2Cl2 (3 mL), MeCN (1.5 mL), and ethyl vinyl ether
(1.5 mL) were added sequentially. The mixture was heated at 40
°C for 1 h. The polymer was filtered and washed with CH2Cl2
(3×100 mL) and extracted with CH2Cl2 (Soxhlet) for 48 h. The
resulting Pc polymer was rinsed out of the thimble with CH2Cl2
and concentrated to 20 mL. 2 mL trifluoroacetic acid was added
to the suspension of polymer Pc, and the mixture was stirred at
room temperature under Ar for 1 h. The reaction mixture was
washed with water (20 mL), aqueous NaHCO3 (20 mL), and the
organic layer was dried over MgSO4, filtered, and evaporated.
The crude product was purified by column chromatography
(SiO2, CH2Cl2: MeOH = 95:5) to give Pc 11 (0.26 g, 10% yield)
as a green solid: 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) δ
(ppm) 9.96 (br s, 1H), 8.66 (br s, 1H), 8.48 (br s, 2H), 8.44 (br s,
1H), 8.36 (br s, 1H), 8.33 (br s, 1H), 8.27 (br s, 2H), 7.61 (d, J =
9 Hz, 1H), 7.38-7.34 (m, 4H), 7.28-7.25 (m, 8H), 7.05-7.03 (m,
4H), 6.99-6.94 (m, 8H), 4.06-3.99 (m, 12H), 2.47-2.40 (m, 12H),
2.08-2.01 (m, 12H), 1.87-1.79 (m, 12H), 1.13-1.09 (m, 126H);
13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) δ (ppm) 160.8,
158.5, 156.1, 155.98, 155.90, 155.86, 155.6, 151.7, 151.64,
151.60, 151.4, 151.19, 151.16, 151.1, 150.74, 150.66, 150.2,
150.1, 149.9, 137.5, 132.8, 132.7, 132.2, 130.9, 130.7, 127.2,
124.4, 120.9, 120.9, 120.2, 120.1, 119.62, 119.58, 119.4, 116.12,
116.07, 115.95, 115.89, 115.6, 113.8, 113.7, 113.1, 112.9, 111.9,
111.5, 110.9, 109.13, 109.06, 108.3, 80.9, 80.80, 80.76, 68.4,
68.3, 29.0, 26.1, 26.0, 20.1, 20.0, 18.9, 18.8, 18.2, 12.21, 12.20,
12.0, 11.9, 11.7, 11.6, 11.5. To a solution of Pc 11 (170 mg,
0.0650 mmol) in 15 mL THF was added TBAF (0.7 mL, 1.0 M
in THF, 0.7 mmol) in one portion. The reaction mixture was
stirred at room temperature for 8h and the reaction was quenched
by the addition of aqueous NH4Cl. The aqueous layer was
4. Experimental section
4.1. General aspects
All reactions were run under a nitrogen or argon atmosphere
unless otherwise noted. All chemicals were purchased from
commercial sources and used without further purification unless
otherwise noted. Compounds 1a,19a 1b,19a 2,16a 6,9b 9,30 12a-d31
were prepared according to the literature. DMSO was dried over
freshly activated 4 Å molecular sieves. Anhydrous CH2Cl2 was
distilled from CaH2 under argon. Anhydrous THF was distilled
from sodium and benzophenone under argon. Anhydrous THF
1
was distilled from sodium and benzophenone under argon. H
NMR spectra were recorded on a Bruker DRX-500 MHz or
AVIII-400 MHz spectrometer with 13C operating frequencies of
125 MHz or 100 MHz. 1H NMR spectra were obtained in CDCl3
or CD2Cl2:DMSO-d6 (95:5) and calibrated using residual CHCl3
(δ = 7.26 ppm) or CHDCl2 (δ = 5.32 ppm) as an internal
reference. 13C NMR spectra were obtained in CDCl3 or
CD2Cl2:DMSO-d6 (95:5) and calibrated using CDCl3 (δ = 77.0
ppm) or CD2Cl2 (δ = 53.8 ppm) as an internal reference. UV/Vis
spectroscopy was performed with a Shimadzu UV-2401PC
spectrometer. Mass spectra were obtained at the Mass
Spectrometry Facility, Department of Chemistry and
Biochemistry, University of Arizona. Elemental analysis were
obtained from NuMega Resonance Labs, Inc. Flash column
chromatography and TLC were performed using silica gel 60 and
Silica Gel 60 F254 plates respectively.
4.2. Experimental procedures and spectroscopic data
4.2.1. 2,3,9,10,16,17-Hexa-(4'-(hex-5''-ynyloxy)phenoxy)-23-
hydroxyphthalocyanine (5a) by statistical macrocyclization
followed by acidic cleavage. A mixture of phthalonitrile 2 (0.9 g,
3 mmol), phthalonitrile 1a (5.2 g, 10 mmol), DBU (2.0 g, 14
mmol) and LiBr (148 mg, 1.37 mmol) in 60 mL 1-pentanol were
refluxed under Ar for 8 h. The reaction mixture was allowed to
cool to RT and then poured into MeOH (150 mL). The
precipitate was filtered, washed with MeOH, air dried and then

6
Tetrahedron
extracted with DCM and the combined organic layers were
cyanine (13b). Following the procedure for Pc 13a, asymmetric
ACCEPTED MANUSCRIPT
washed with brine, dried over MgSO4, and concentrated under
vacuum. The crude product was purified by column
chromatography (SiO2, CH2Cl2: MeOH = 99:1) to yield Pc 5a (70
Pc 5b (50 mg, 0.030 mmol), 12b (281 mg, 1.74 mmol), dry
CHCl3 (10 mL), N,N-diisopropylethylamine (113 mg, 0.876
mmol) and Cu(PPh3)3Br (135 mg, 0.145 mmol) yielded Pc 13b
1
1
mg, 70%) as a green solid: H NMR (500 MHz, CD2Cl2:DMSO-
as a green solid (27 mg, 35%): H NMR (see Supplementary
d6 = 95:5) δ (ppm) 9.91 (br s, 1H), 8.18-7.72 (m, 8H), 7.36-7.25
(m, 12H), 7.03-6.93 (m, 12H), 4.00 (br s, 12H), 2.33 (br s, 12H),
2.14-2.10 (m, 6H), 1.96 (m, 12H), 1.78 (m, 12H); 13C NMR (125
MHz, CD2Cl2:DMSO-d6 = 95:5) δ (ppm) 160.5, 156.0, 155.83,
155.76, 155.71, 155.65, 155.42, 155.38, 151.7, 151.6, 151.5,
151.3, 151.0, 150.9, 150.8, 150.5, 150.4, 149.6, 149.5, 124.1,
121.2, 121.03, 120.98, 120.3, 120.1, 119.5, 119.0, 116.1, 115.9,
115.83, 115.76, 115.7, 113.4, 113.3, 112.6, 112.5, 111.3, 110.9,
107.9, 84.5, 69.1, 69.02, 68.97, 68.2, 68.1, 28.9, 28.8, 25.52,
25.49, 18.52, 18.48; MS (MALDI) calcd for C104H91N8O13
[M+H]+: m/z 1659.67, found 1659.69. Anal. calcd for
C104H90N8O13: C, 75.25; H, 5.47; N, 6.75. Found: C, 74.86; H,
5.87; N, 6.47%
data); MS (MALDI) calcd for C158H154N26O13Zn [M]+: m / z
2687.15, found 2687.16. Anal. calcd for C158H154N26O13Zn: C,
70.53; H, 5.77; N, 13.54. Found: C, 70.47; H, 6.14; N, 13.19.
4.2.6. Zinc
oxoprop-1-en-1-yl)-phenoxy)
2,3,9,10,16,17-Hexa(4'-(4''-(1'''-(3-(4-(3-ethoxy-3-
propyl)-1H-1,2,3-triazol-4-yl)-
butoxy)phenoxy)-23-hydroxyphthalocyanine (13c). Following
the procedure for Pc 13a, asymmetric Pc 5b (20 mg, 0.012
mmol), 12c (200 mg, 0.726 mmol), dry CHCl3 (20 mL), N,N-
diisopropylethylamine (45 mg, 0.35 mmol) and Cu(PPh3)3Br (54
mg, 0.058 mmol) yielded Pc 13c as a green solid (17 mg, 44%):
1H NMR (see Supplementary data); MS (MALDI) calcd for
C188H191N26O31Zn [M+H]+: m / z 3372.35, found 3372.12. Anal.
calcd for C188H190N26O31Zn: C, 66.90; H, 5.67; N, 10.79. Found:
C, 66.84; H, 5.90; N, 10.51.
4.2.3. Zinc 2,3,9,10,16,17-hexa(4'-(hex-5''-ynyloxy)phenoxy)-23-
hydroxyphthalocyanine (5b). A mixture of phthalonitrile 2 (0.1 g,
0.4 mmol), phthalonitrile 1 (0.6 g, 1 mmol), DBU (0.2 g, 1
mmol) and Zn(OAc)2 (140 mg, 0.765 mmol) in 60 mL 1-pentanol
was refluxed under Ar for 8 h. The reaction mixture was allowed
to cool to RT, and poured in MeOH (150 mL). The precipitate
was filtered, washed with MeOH, air dried and then
chromatographed (SiO2, CH2Cl2: MeOH = 99:1). The green
eluent was collected and concentrated under reduced pressure. A
solution of the resultant green residue, TFA (2 mL) and CH2Cl2
(20 mL) was stirred at RT under Ar for 4h. The reaction mixture
was washed with water (50 mL), aqueous NaHCO3 (50 mL), and
the organic layer was dried over MgSO4, filtered, and evaporated.
The crude product was purified by column chromatography
(SiO2, CH2Cl2: MeOH = 99:1) to give Pc 5b (0.13 g, 20% yield)
as a green solid: 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) δ
(ppm) 9.77 (s, 1H), 8.80-8.40 (m, 8H), 7.51(d, J = 8 Hz, 1H),
7.36-7.35(m, 4H), 7.29-7.24 (m, 8H), 7.06-7.02(m, 4H), 6.98-
6.95 (m, 8H), 4.07-4.00 (m, 12H), 2.35-2.30 (m, 12H), 2.08-2.06
(m, 6H), 2.00-1.91 (m, 12H), 1.81-1.73 (m, 12H); 13C NMR (125
MHz, CD2Cl2:DMSO-d6 = 95:5) δ (ppm) 160.2, 156.0, 155.8,
155.60, 155.58, 155.52, 154.2, 153.3, 152.5, 151.8, 151.8,
151.64, 151.58, 151.2, 151.1, 151.0, 150.9, 150.5, 150.3, 149.9,
149.8141.0, 134.4, 134.3, 133.9, 130.7, 124.1, 120.8, 119.9,
119.8, 119.7, 119.6, 118.21, 116.0, 115.8, 113.74, 113.65, 113.5,
112.2, 112.0, 108.668.93, 68.87, 68.3, 68.23, 68.18, 30.0, 28.8,
25.5, 25.51, 25.47, 18.48, 18.45; MS (MALDI) calcd for
C104H88N8O13Zn [M]+: m/z 1720.58, found 1659.72. Anal. calcd
for C104H88N8O13Zn: C, 72.49; H, 5.15; N, 6.50. Found: C, 72.01;
H, 5.60; N, 6.51%
4.2.7. Compound 13d. Following the procedure for Pc 13a, a
mixture of asymmetric Pc 5b (21 mg, 0.012 mmol), 12d (493
mg, 0.752 mmol), dry CHCl3 (10 mL), N,N-
diisopropylethylamine (50 mg, 0.39 mmol) and CuI (13 mg,
0.068 mmol) was stirred at room temperature overnight. Af t er
wor k up t he cr ude solid was loaded t o column
chromatography and f ir st f lushed wit h 5% v/ v et hy l
acet at e in CH2Cl2 until excess 12d was completely removed
from the column. Then the product was eluted with 5% v/ v
MeOH in CH2Cl2 followed by recrystallization from
CHCl3/MeOH to give Pc 13d as a dark purple solid (24 mg,
1
35%): H NMR (see Supplementary data); MS (MALDI) calcd
for C344H335N38O37Zn [M+H]+: m / z 5653.48, found 5653.870.
Anal. calcd for C H N O Zn: C, 73.02; H, 5.95; N, 9.41. Found:
344
334
38
37
C, 73.02; H, 5.91; N, 9.08.
Acknowledgments
This work was supported by the National Science Foundation
(CHE-0719437) and the Center for Interface Science: Solar
Electric Materials (CIS:SEM), an Energy Frontier Research
Center funded by the U.S. Department of Energy, Office of
Science, Office of Basic Energy Sciences under Award Number
DE-SC0001084.
Supplementary data
Supplementary data associated with this article can be found
in the online version.
4.2.4. Zinc
2,3,9,10,16,17-Hexa(4'-(4''-(1'''-dodecyl-1
H-
1''',2''',3'''-triazol-4'''-yl)-butoxy)phenoxy)-23-hydroxyphthalo-
References and notes
cyanine (13a). Asymmetric Pc 5b (50 mg, 0.030 mmol) and 12a
(368 mg, 1.74 mmol) were dissolved in 20 mL dry THF before
N,N-diisopropylethylamine (45 mg, 0.35 mmol) and CuI (13 mg,
0.070 mmol) were added to the solution. The mixture was
degassed and backfilled with argon three times before stirring
overnight at room temperature. The reaction mixture was diluted
with CH2Cl2 followed by washing with 3x 100 mL 0.1 M EDTA,
3x 100 mL 1 M HCl, and 3x 100 mL brine. The organic layer
was concentrated and the crude product was purified by column
chromatography (SiO2, CH2Cl2: MeOH = 95:5), followed by
recrystallization (3x) from CH2Cl2/MeOH to give Pc 13a as a
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ACCEPTED MANUSCRIPT
Supporting Information
Modification of alkyne-functionalized asymmetric
phthalocyanines by CuI-catalyzed azide-alkyne cycloaddition
Xiaochun Chen, Chin-Wei Lu, Yiming Huang, and Dominic V. McGrath*
Department of Chemistry, University of Arizona, Tucson, AZ 85721
mcgrath@u.arizona.edu
Figure S1. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5a..................S2
Figure S3. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5b..................S3
Figure S4. 13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5b................S3
Figure S5. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 11..................S4
Figure S6. 13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 11. ...............S4
Figure S7. 1H NMR (400 MHz, CDCl3) spectrum of 13a. .......................................................S5
Figure S8. 1H NMR (400 MHz, CDCl3) spectrum of 13b........................................................S5
Figure S9. 1H NMR (400 MHz, CDCl3) spectrum of 13c.........................................................S6
Figure S10. 1H NMR (500 MHz, CDCl3:pyridine-d5 = 95:5) spectrum of 13d...............S6
Figure S11. FT-IR spectra of Pc 5b (top) and isolated 13d at the reaction time of six
hours (bottom) taken on a polyethylene card. ...........................................................................S7
S1

ACCEPTED MANUSCRIPT
OR
RO
RO
OR
N
N
N
NH
N
N
N
HN
OH
RO
RO
5a
O
R =
Figure S1. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5a.
OR
RO
RO
OR
N
N
N
NH
N
N
N
HN
OH
RO
RO
5a
O
R =
Figure S2. 13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5a.
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ACCEPTED MANUSCRIPT
OR
RO
RO
OR
N
N
N
N
N
Zn
N
N
N
OH
RO
RO
5b
O
R =
Figure S3. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5b.
OR
RO
RO
OR
N
N
N
N
N
Zn
N
N
N
OH
RO
RO
5b
O
R =
Figure S4. 13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 5b.
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ACCEPTED MANUSCRIPT
OR
RO
RO
OR
N
N
NH
N
N
N
N
HN
OH
RO
R =
RO
11
TIPS
O
Figure S5. 1H NMR (500 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 11.
OR
RO
RO
OR
N
N
NH
N
N
N
N
HN
OH
RO
R =
RO
11
TIPS
O
Figure S6. 13C NMR (125 MHz, CD2Cl2:DMSO-d6 = 95:5) spectrum of Pc 11.
S4

ACCEPTED MANUSCRIPT
R
R
N
N
N
N
N
N
O
O
N
N
N
N
R
R
N
N
O
O
O
O
O
O
N
N
N
N
N
N
N
Zn
N
OH
O
O
O
N
R
N
N
O
13a
R = C12H25
N
N
N
R
Figure S7. 1H NMR (400 MHz, CDCl3) spectrum of 13a.
R
R
N
N
N
N
N
N
O
O
N
N
N
N
R
R
N
N
O
O
O
O
O
O
N
N
N
N
N
N
N
Zn
N
OH
O
O
O
N
R
N
13b
N
O
R =
N
N
N
R
Figure S8. 1H NMR (400 MHz, CDCl3) spectrum of 13b.
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ACCEPTED MANUSCRIPT
R
R
N
N
N
N
N
N
O
O
N
N
N
N
R
R
N
N
O
O
O
O
O
O
N
N
N
N
N
N
N
Zn
N
OH
O
O
O
N
R
N
13c
N
O
EtO2C
R =
O
N
N
N
R
Figure S9. 1H NMR (400 MHz, CDCl3) spectrum of 13c.
R
R
N
N
N
N
N
N
O
O
N
N
N
N
R
R
N
N
O
O
O
O
O
O
N
N
N
N
N
N
N
Zn
N
OH
O
O
O
N
R
N
13d
N
O
R =
O
N
O
O
C6H13
C6H13
N
O
N
N
N
R
Figure S10. 1H NMR (500 MHz, CDCl3:pyridine-d5 = 95:5) spectrum of 13d.
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ACCEPTED MANUSCRIPT
Figure S11. FT-IR spectra of Pc 5b (top) and isolated 13d at the reaction time of six
hours (bottom) taken on a polyethylene card.
S7