An experimental and computational study on isomerically pure, soluble azaphthalocyanines and their complexes and boron azasubphthalocyanines of a varying number of aza units

Article abstract of DOI:10.1039/c8ob01705k

Herein, we present a series of isomerically pure, peripherally alkyl substituted, soluble and low aggregating azaphthalocyanines as well as their new, smaller hybrid homologues, azasubphthalocyanines. The focus lies on the effect of the systematically increasing number of aza building blocks [-N] replacing the non-peripheral [-CH] units and their influence on the physical and photophysical properties of these chromophores. The absolute and relative HOMO-LUMO energies of azaphthalocyanines were analyzed using UV-Vis and CV and compared to the density functional theory calculations (B3LYP, TD-DFT). The lowering of the HOMO level is revealed as the determining factor for the trend in the adsorption energies by electronic structure analysis. Crystals of substituted subphthalocyanines, N₂-Pc?H₂ and N₄-[Pc?Zn·H₂O], were obtained out of DCM. For the synthesis of the valuable tetramethyltetralin phthalocyanine building block a new highly efficient synthesis involving a nearly quantitative Co^II catalyzed aerobic autoxidation step is introduced replacing inefficient KMnO₄/pyridine as the oxidant.

Full text of DOI:10.1039/c8ob01705k

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Biomol. Chem., 2018, DOI: 10.1039/C8OB01705K.
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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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Journal Name
ARTICLE
Experimental and Computational Study of Isomerically Pure
Soluble Azaphthalocyanines and their Complexes and Boron
Azasubphthalocyanines of Varying Number of Aza Units
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
b
c
DOI: 10.1039/x0xx00000x
Martin Liebold , Eugen Sharikow , Elisabeth Seikel , Lukas Trombach , Klaus Harms , Petr Zimcik ,
c
b,*
a,*
Veronika Novakova , Ralf Tonner , and Jörg Sundermeyer
www.rsc.org/
Abstract: Herein, we present a series of isomerically pure, peripherally alkyl substituted, soluble and low aggregating
azaphthalocyanines as well as their new, smaller hybrid homologues, the azasubphthalocyanines. The focus lies on the
effect of the systematically increasing number of aza building blocks [-N=] replacing the non peripheral [-CH=] units and its
influence on physical and photophysical properties of these chromophores. The absolute and relative HOMO-LUMO
energies of azaphthalocyanines were analyzed using UV-Vis, CV and compared to density functional theory calculations
(B3LYP, TD-DFT). The lowering of the HOMO level is revealed as the determining factor for the trend in the adsorption
*
*
2 2 4 2
energies by electronic structure analysis. Crystals of substituted subphthalocyanine, N -Pc H and N -[Pc Zn∙H O] were
obtained out of DCM. For the synthesis of the valuable tetramethyltetraline phthalocyanine building block a new highly
II
efficient synthesis involving a nearly quantitative Co catalyzed aerobic autoxidation step is introduced replacing inefficient
4
KMnO /pyridine as oxidant.
1
3,14
nonperipheral ring substituents,
the solubility in common
Introduction
organic solvents is increased and aggregation decreased. In
current research, the investigation of [–CH=], [-N=] units is a
Phthalocyanines (Pc) and structurally related isosteric
octaazaphthalocyanines, in particular pyrazinoporphyrazines
1
5
4
hot topic. Recently, symmetrical A -type phthalocyanines
and naphthalocyanines as well as their aza-analogues were
investigated with respect to their singlet oxygen generation
(Ppz), probably became one of the technologically most
prominent classes of organic dyes. There are numerous
applications, including absorbers in dye sensitized solar cells
1
and photostability. A selective access to a class of meso
6
1
,2,3,4
substituted Pc derivatives, namely tetrabenzotriazaporphyrins
(
DSCs),
semiconductors in organic field effects transistors
1
7
5
OFETs), or photoconductors in laser printers. Traditionally,
6
(TBTAP), has been reported as well. Unfortunately, one tert-
butyl group at the peripheral position commonly used to gain
solubility of a Pc always leads to mixtures of up to four
(
7
8
they serve as dye ingredient in lacquers, paints, and plastics.
More recently, they are used as colour filters in liquid crystal
1
4
8
9
display, as fluorescent markers, as sensors or as sensitizers in
stereoisomers as a consequence of the cyclotetramerisation.
1
0
Commonly used two peripheral long n-alkyl or -OR, -SR
substituents per isoindoline unit lead to one stereoisomer,
however, it becomes difficult to get highly ordered crystalline
Pc phases. Linking two peripheral tert-butyl groups via a joint
C-C bond together leads to chromophores soluble enough for
photodynamic therapy (PDT). On one side, the characteristic
aggregation and -stacking of these 42 electron extended
ÜCKEL aromatic systems causes their optoelectronic materials
π
π
H
properties. On the other side, aggregation typically leads to
8
molecules completely insoluble in organic solvents. By
1
1
1,12
chromatography and H NMR spectroscopy, at the same time
introducing bulky axial metal ligands,
and/or peripheral or
sterically demanding enough to avoid intermolecular
1
deactivation paths of their excited state. Such a best
8
*
compromise phthalocyanine building block PDN
1
was first
reported by MIKHALENKO et al. (Fig. 1). Related symmetrical
-type Pc*MX complexes have a higher tendency to form
1
9
A
4
1
1
well-ordered and even single-crystalline phases. However,
*
the 8-step synthesis of Pc H
to followers, probably because a side chain oxidation of the
,1,4,4,5,6-hexamethyltetraline intermediate to the
corresponding o-dicarboxylic acid (Scheme 1) by KMnO in
pyridine was drastically limiting the overall yield of the
2
might not have looked appealing
1
4
1
9
ligand. Here, we report a much more attractive method and
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Journal Name
selective catalytic aerobic oxidation as replacement of this tetraline-6,7-dicarboxylic acid building block. So far this
synthesis step. It is suggested to call this sterically demanding stoichiometric oxidation was accomplished by treatment with
soluble and compact phthalocyanine derivative with 16 methyl large excess of potassium permanganate in hot pyridine. This
*
groups Pc H
2
, following the common terminology of prominent procedure is hampered with unreliable yields of 15-60% and
*
organometallic ligands Cp (C
5
H
5
) and Cp (C
5
Me
5
). The large amount of poisonous waste. Here we report a green
has been catalytic access to this key intermediate, which will promote
introduced by us only recently. The aim of this study is to drastically its future use in the synthesis of soluble, non-
apply the precursors PDN* ( ) and PyzDN*( ) to synthesize aggregating, isomerically pure phthalocyanines (Scheme 1).
and fully characterize a complete series of diaza-, tetraaza-,
*
corresponding soluble pyrazinoporphyrazine Ppz H
2
1
2
1
2
*
and hexaaza- N
x
-Pc M hybrid compounds as well as their
*
subphthalocyanine homologues Spc BCl, diaza-, tetraaza-, and
*
*
hexaaza-N
x
-[Spc BCl] (or [Sppz BCl] for n=6), respectively (Fig.
2 and 3). Despite of the fact, that a large number of lower-
symmetry phthalocyanines of A4-nBn-type and subphthalo-
cyanines of an A3-nBn-type is described in literature, only few of Scheme
1
.
New catalytic oxidation of 1,1,4,4,5,6-
2
0,21
such aza derivatives are systematically studied.
We were hexamethyltetraline to phthalic acid key building block.
interested in a systematic study of photophysical properties
and optoelectronic response upon stepwise substitution of Our protocol is similar to conditions used in the industrial
[–CH=] units by [–N=] units in these hybrid chromophores. In autoxidation of para-xylene to terephthalic acid with dioxygen
the following we correlate UV-Vis data with electro-analytically in the presence of cobalt acetate catalyst and a bromide
24
gained oxidation and reduction potentials measured by CV, promotor. The yield increases to 97%, the waste is negligible,
and compare these results with results of DFT calculations. water is formed as by-product. The product precipitated in
Density functional theory has been found to perform well for crystalline state, solvent glacial acid and even catalyst can be
2
2
the discussion of trends in excitation energies along a series,
although the derivation of accurate absolute excitation presence of acetic anhydride the isolated product is
fully recycled. With large excess of glacial acid or in the
23
energies needs more sophisticated methods. It was found corresponding phthalic anhydride, which saves even one
before, that the investigation of the HOMO-LUMO energy gap reaction step in the synthesis of PDN*
. The radical chain
mechanism induced by intermediate Co(OAc) is discussed in
1
2
2
can be a good indicator for the excitation energy observed.
The reduced symmetry in protonated H Pc* or A B -type aza- the electronic supplement.
3
2
4-n n
H
atom abstraction occurs
3
exclusively at the benzylic sp CH bond. This type of side-chain
*
analogues N -Pc M should lead to splitting of the Q-band.
20
x
Knowing and predicting the trend in the HOMO-LUMO gap, oxidation can also be carried out in lower yield without
designing the absolute HOMO-LUMO energies, as well as bromide promotor, but higher amounts of [Co(OAc) ]∙4H O
2
2
2
5
adding a permanent dipole moment to these chromophores and methylethylketone are necessary.
and control their aggregation are fundamentals needed to
*
control level alignment at internal interface to wide band gap The azaphthalocyanines N -Pc H , shown in Fig. 2, were
x
2
1
,3,4
semiconductors such as TiO or ZnO.
2
Understanding exciton synthesized in a cyclotetramerization reaction following the
*
*
1 and PyzDN 2 in a
dynamics and exciton dissociation into mobile charges at ideal reliable protocol of reacting PDN
model heterojunctions is of fundamental importance, e.g. for suspension of lithium in n-octanol at 180 °C. After workup
optimizing DSSCs.
2
0
with phosphoric acid and washing with methanol the mixture
*
*
of the resulting four N
x
2 2
-Pc H 4a, 5a, 6a, and 7a, Pc H 3a, and
*
Ppz H
pentane/ethylacetate (PE/EE) 10:1
and PyzDN finally eluted using DCM. Using a 1:1 ratio of PDN
2
8a was separated via gradient column chromatography
Results and Discussion
*
ꢀ
2
1:1. Ppz H 8a could be
*
18,23,24
*
*
Synthesis. The respective dinitriles PDN
1
1
and
in this random co-cyclisation an overall yield of 39%
is the oxidation of of mixed (aza)phthalocyanines was obtained and separated by
,1,4,4,5,6-hexamethyltetraline to the 1,1,4,4-tetramethyl- middle pressure chromatography (MPLC) into six fractions:
1
2
2
*
have been described in literature. The overall yield limiting PyzDN 2
*
key step in the 8-step synthesis of PDN
1
1
2
| J. Name., 2012, 00, 1-3
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ARTICLE
*
12 shown in Fig. 3. [Spc BCl]
*
and [Sppz BCl] 12
Main
product
is
the
A
2
B
2
isomer
5a
(17%)
N
x
-[Spc*BCl]
9-
9
*
-Pc H
*
-Pc H
tetraazaphthalocyanine N
*
9%) and Ppz H
4
2
, followed by AB
3
N
6
2
7a was synthesized according to literature known procedures,
(
2
8a (9%). Minor product was the ABAB isomer using boron trichloride in a solvent such as toluene or
*
-Pc H
*
-Pc H
*
4a (3%) and Pc H
21
*
*
o-xylene. Compared to [Spc BCl] 9 with 13% yield, [Sppz BCl]
of N
4
2
6a (<1%) as well as A
3
B N
2
2
2
*
3a
(1%). Even by increasing the amount of PDN
1
, or by 12 could be obtained in surprisingly high yields of 35%.
*
-[Spc BCl] 10 and N
*
-[Spc BCl] 11 were obtained by using
increasing the temperature of the reaction, 5a was obtained as
main product.
N
2
4
*
*
K
OBAYASHI et al. reported about this both dinitriles PDN
1
and PyzDN
2
in a ratio 1:1. The ring
*
*
phenomenon, when different electron deficient phthalonitriles expansion was attempted with [Spc BCl]
9
, [Sppz BCl] 12, and
4
N -[Spc BCl] 11. Therefore, the isoindoline compound of
2
0
*
with different sterical demand were used. Due to the similar
steric bulk of both dinitriles, we assume a strong electronic PDN
influence in the reaction leading to a precyclisation of electron situ by introducing ammonia in a NaOMe/MeOH solution.
poor PyzDNs. A -Pc*H isomer 5a was differentiated from
ABAB isomer 6a by means of H NMR and UV/Vis To [Sppz BCl] 12, the isoindoline of
spectroscopy. the solution stirred at 120 °C for
After chromatographic isolation of the pure N -Pc*H , all zinc N -[Pc M]
*
*
*
1
, or PyzDN 2 in case of [Spc BCl] 9, was generated in
2
B
2
N
4
2
1
*
1
was added in DMSO and
h, yielding AB3
, reacting with the
, no ring expansion can be observed. A
Zn(hmds) ] (hmds = hexamethyldisilazane) or [Zn(OAc) ]∙2H O ring expansion is favoured, the more electron deficient the Spc
8
*
*
7
. In the case of [Spc BCl] 9
x
2
6
*
*
complexes Pcs, N -[Pc Zn] 3b-8b were obtained using isoindoline of PyzDN 2
x
[
2
2
2
as metallating agents. Attempts to purify mixtures of zinc is, the more electron rich the isoindoline compound is,
complexes by chromatography were of limited success. respectively. In the case of the insertion of isoindoline of in
, A B N -Pc H 5a was obtained. This verifies the
1
*
*
N -[Spc BCl]
9
4
2
2
4
2
In addition, we attempted to synthesize compounds 5a and 6a electronic influence of the pyrazine units upon
2
6
via KOBAYASHI ring expansion.
Following this synthetic cyclotetramerisation.
strategy, we synthesized a series of azasubphthalocyanines
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*
UV/Vis spectroscopy and CV. The synthesized N -Pc H have asymmetric broadening of the Q-band (Fig. 4). The strongest
x
2
been characterized by using UV/Vis spectroscopy and cyclic splitting was expected to be visible for ABAB type macrocycle
voltammetry (CV). Electronic absorption spectra of the 6a. In this case, however, seemingly one main Q-band was
compounds are displayed in Fig. SI-1-3 of the supporting detected. Closer inspection, however, revealed a shoulder at
information. The Q-band can be shifted from 450 nm to 701 nm as an indication of the split band. This small-intensity
710 nm. The following trend is observed: the higher the band at 701 nm was also detected in fluorescence excitation
number of inserted [-N=] atoms in the subphthalocyanine spectra (see electronic supplement, Fig. SI-1).
series (
type of
9
-
12), the more blue-shifted the Q-band within one
π-system. Measured in MeOH, at the high energy end Considering this small band, the splitting of the Q-band is then
we find the hexaazasubphthalocyanines (533 nm) followed by the strongest in the series of all studied Pcs in accordance with
2
tetraaza- (555 nm) and diazasubphthalocyanines (566 nm) and literature data for lower symmetrical Pcs. After insertion of a
7
*
finally the parent subphthalocyanine (575 nm). Measured in zinc atom, the lower symmetrical A
3 3 x
B and AB N -[Pc Zn] 4b
THF, the Same trend is observed for the phthalocyanine series and 7b showed a weak splitting of their Q-bands. This is caused
*
*
in the region [Ppz Zn] (640 nm) – Pc H
blue-shifted Q-band is observed for octaazaphthalocyanine, unperturbed Q-band was expectedly observed for both
followed by hexaaza-, followed by the A and ABAB isomers symmetrical 3b and 8b but also for A isomer 5b although
of tetraaza-, of diaza- and finally by the parent phthalocyanine. being of lower C2v symmetry. This observation is, however,
2 g
(710 nm): The most by the 1e orbitals, which are not degenerate anymore. Single
2
B
2
2 2
B
The studied Pc macrocycles were of lower symmetry either typical for adjacent isomers of A
2
2
B
2
7,28
type and has been
The UV/Vis spectra
due to the presence of the different number of pyrazine units reported several times in literature.
*
or due to presence of central hydrogens in N
reflected in the splitting of the Q-bands. In the metal-free computed excitation energies are listed. The optical values,
series N -Pc*H , the splitting occurred for all the macrocycles calculated by using UV/Vis spectroscopy, agree with the
x 2
-Pc H that was correlate with the measured CVs. In Table 1, the measured and
x
2
although, e.g. in case of 4a and 7a was only barely detectable determined redox excitation energies observed in CV
and in particular for the former one manifested only by measurements.
*
*
*
*
*
*
Ppz H
2
(8a)
N
6
-Pc H
2
(7a)
N
4
-Pc H
2
(6a)
N
4
-Pc H
2
(5a)
N
2
-Pc H
2
(4a)
2
Pc H (3a)
E
E
E
E
ox / V
0.87
-1.05
-1.37
1.92
655
0.35
-1.47
-1.82
1.82
660
0.28
-1.47
-1.79
1.75
674
0.36
-1.37
-1.77
1.73
680
0.43
-1.23
-1.65
1.67
687
0.67
-0.97
-1.36
1.58
711
1
red / V
2
red / V
CV
g
b
/ V
c
max / nm
λ
optical
calc.
d
HOMO-LUMO
HOMO-LUMO
/ eV
1.89
1.52
1.59
1.87
1.44
1.56
1.85
1.36
1.52
1.82
1.41
1.46
1.80
1.35
1.45
1.74
1.35
1.37
/ eV
calc.
HOMO-(LUMO+1)
/ eV
4
| J. Name., 2012, 00, 1-3
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The computed Q-band positions give the right trend in Photophysical properties. Fluorescence emission spectra of all
comparison to experiments, although the absolute numbers derivatives were measured in THF or MeOH (Fig. 5). They
are around 100-130 nm smaller. The same conclusion holds for follow the same trends as the absorbance spectra. The higher
the HOMO-LUMO gap. It is found that the correlation is much the number of [-N=] units replacing [-CH=], the more blue-
better with the LUMO+1 orbital (DHL+1) which is depicted in shifted the maxima of the emission bands. Their shape
Figure SI-4 in the supporting information. A detailed discussion mirrored the absorbance Q-band with only small Stokes shifts
is given in the computational section. CV measurements were (6 – 26 nm) between absorbance and emission maximum.
carried out with an rhd-instruments setup, using a 2000
ꢀ
L
Position of the emission maximum can be finely tuned using
microcell in a glovebox. As working electrode a Pt electrode the proper composition of the macrocycle (Fig. 5) that can be
was used, a gold or Pt counter electrode as well as an Pt advantageously used in design of new fluorophores or
pseudo reference electrode. The compounds were measured photosensitizers with selected excitation and emission
in a 0.5 N [TBA]PF
6
in DCM solution using a 5 mmol solution of wavelength. Excitation spectra perfectly matched the
*
the N
.1 mmol Fc in DCM as reference. All measured N
one reversible oxidation process and two reversible reduction that the photophysical data were not affected by aggregation
x 2
-Pc H . All measurements have been carried out using a absorbance ones confirming that the compounds were in
*
0
x
2
-Pc H show monomeric form in the solution during measurements and
*
2
potentials, with exception for the Ppz H 8a, as shown in (Figs. SI-1-3). Exception from this observation was detected for
SI-8. In this case, no reversible redox process was observed. In the weakest fluorescent of 8a. In this case, the excitation
agreement with the Q-band position, as measured by UV/Vis spectrum was substantially different from the absorption one
spectroscopy, the energy gap was increasing with the number indicating that a different species (e.g. partially deprotonated
*
29
of pyrazine units in the
x
2
N -Pc H . The increasing electron on the central NH) is responsible for the fluorescence
deficiency of the aromatic system correlating with the emission. It might be connected with very weak fluorescent
1
increasing number of [-N=] is also seen in H NMR properties of 8a as suggested below that do not allow
spectroscopy. An expected low field shift of the aromatic detection of its signal. Consequently, the emission from the
protons, the methylene protons, as well as the methyl protons new species prevails even when present as very minor
by increasing the number of [-N=] can be observed. In component. In the zinc series N
summary, an almost linear trend could be observed in UV/Vis, fluorescence quantum yield (
ꢁ
CV and computational calculations. The origin of this trend is oxygen quantum yield ( = 0.56-0.73) for a particular
x
-[Pc*Zn], the sum of the
Φ
F
= 0.18-0.35) and singlet
Φ
analysed in the computational discussion part below.
compound, were relatively constant (Table 2, Fig. 6) reaching
values typically close to 0.9. The only difference between the
compounds in the series was in relative contribution of the
two processes.
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*
*
a
Table 2. Electronic and photophysical data of N
x
-Pc M in THF and N
x
-Spc BCl in MeOH. Absorption maximum (λmax), fluorescence
b
emission maximum (λ
F
), fluorescence lifetime (τ
F
), fluorescence quantum yield (Φ
F
), singlet oxygen quantum yield (Φ
ꢁ
). λexc = 371 nm
c
*
-[Pc M] and
or 634 nm. with [PcZn] (ΦF(THF) = 0.32, λexc = 598 nm) and rhodamin G6 (ΦF(EtOH) = 0.94, λexc = 490 nm) as reference for N
x
*
d
*
*
N
x
-[Spc BCl], respectively. with ZnPc (Φꢁ(THF) = 0.53) and bengal rose (Φꢁ(MeOH) = 0.76) as reference for N
x
x
-[Pc M] and N -[Spc BCl],
respectively.
b
c
d
λ
max (B-band) / nm
λ
max (Q-band) / nm
λ
F
/ nm
τ
F
/ ns
Φ
F
Φ
ꢁ
F ꢁ
Φ + Φ
Pc*H
2
3a
343
343
358
353
349
345
350
353
356
355
353
347
266
272
288
301
707, 673
686
711
5.52
3.45
1.62
1.79
0.42
0.33
0.14
0.16
0.06
0.03
0.31
0.25
0.35
0.18
0.27
0.30
0.18
0.21
0.23
0.19
0.16
0.14
0.07
0.10
0.04
0.05
0.59
0.63
0.56
0.73
0.62
0.57
0.65
0.62
0.64
0.69
0.58
0.47
0.21
0.26
0.10
0.08
0.90
0.88
0.91
0.91
0.89
0.87
0.82
0.82
0.87
0.87
N
N
N
N
N
2
4
4
6
8
-Pc*H
-Pc*H
-Pc*H
-Pc*H
2
2
2
2
4a
5a
6a
7a
692
684
674
664
658
689
686
667
687
663
642
587
577
567
546
678, 653
668, (701)
658, 643
652, 623
683
3.92 (26%), 0.63 (74%)
-*H
2
8a
2.15 (29 %), 0.36 (71%)
[Pc*Zn] 3b
3.31
2.69
3.08
1.98
2.69
2.98
2.04
2.19
2.85
2.98
N
N
N
N
N
2
4
4
6
8
-[Pc*Zn] 4b
-[Pc*Zn] 5b
-[Pc*Zn] 6b
-[Pc*Zn] 7b
-[Pc*Zn] 8b
679, 668
658
679, 651
648
633
[Spc*BCl] 9
575
N
N
2
4
-[Spc*BCl] 11
-[Spc*BCl] 12
566
555
[Sppz*BCl] 10
533
Different situation was observed in the metal-free series radiative relaxation pathway in a stepwise manner. In the
*
*
N -Pc H . The sum of the quantum yields was significantly N -[Spc BCl] series, the photophysical data resembled those
x
2
x
decreasing with the increasing number of aza-substitution with obtained for zinc derivatives (ΦF ~ 0.20, Φꢁ ~ 0.65) with sum of
compounds 7a and 8a being almost photophysically inactive ΦF and Φꢁ over 0.80 indicating that both these processes are
(from the point of view of ΦF and Φꢁ).
predominant in the relaxation of the excited states also in Spc
derivatives.
*
Figure 5. Normalized emission spectra of N -Pc Zn in THF Figure 6. Fluorescence quantum yields (
Φ
F
, full columns) and
, blank columns) for
x
-[Spc*BCl] in MeOH.
x
*
(
λexc = 598 nm) and N -Spc BCl in MeOH (λexc = 490 nm).
singlet oxygen quantum yields (
-[Pc*M] in THF and N
Φ
ꢁ
x
N
x
This interesting phenomenon does not have a clear
explanation at this moment but is fully consistent with recently The data are well comparable with the reported values of Spcs
2
9–31
32
reported photophysical data for some metal-free Ppzs.
presented series 3a
8a is, however, unique as the differences between fluorescence and singlet oxygen
photophysical data for metal-free derivatives are reported production were observed in dependence on the number of
The with different peripheral substitution.
No significant
-
*
only from the members lying on the edges of the N -Pc H
x
nitrogen atoms. The fluorescence emission properties were
2
series (i.e. only for x = 0 and x = 8). The trend observed on the complemented by the fluorescence lifetimes (Table 2).
Fig. 6 clearly indicated that the introduction of the nitrogens The fluorescence decays were characterized by mono-
into the Pc ring increases the feasibility of this unknown non- exponential curves for most of the studied compounds and
F
τ
6
| J. Name., 2012, 00, 1-3
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ARTICLE
*
*
values correlated well with the
F
Φ values (Fig. SI-4) further In addition to the [Spc BCl] 9, [Sppz BCl] was crystallised, but
validating the fluorescence data. Only in case of metal-free 7a because of the low quality of the crystal, an appropiate
and 8a, the decay curves were biexponential with increased discussion of the bond length is not possible, but in
*
contribution of the fast component. It supports the fact that comparison to [Spc BCl] information of the molecular
another relaxation pathway occurs by the metal-free arrangement in solid state can be obtained. The structure of
*
[Sppz BCl] is attached to the SI.
compounds as proposed above.
*
-Pc H
Crystal structure of [Spc*BCl],
*
-[Pc Zn
N
2
2
,
and
A
2
B
2
Table 3: Selected bond length (Å) and angles (°) of [Spc*BCl] 3 and
a
N
4
∙H
2
O]. Suitable crystals for X-Ray diffraction of [SpcBCl].
*
-Pc H
*
Spc BCl]
*
-[Pc Zn∙H
[
9, N
2
2
4a and A
2
B
2
N
4
2
O] 5b were
[
Spc*BCl] (3)
1.852(4)
1.480(3)
1.479(4)
1.480(3)
[SpcBCl]
1.863(7)
obtained from a saturated DCM-d
2
solution. Of all compounds,
B1-Cl1
B1-N1
B1-N3
B1-N5
selected crystallographic datas are collected in the supporting
9 crystallizes in the orthorombic crystal
*
system Cmc2 . The molecular structure of [Spc BCl]
1.466(8)
*
information. [Spc BCl]
1.468(5)
9
is shown
1
1.466(8)
in Fig. 7. Similar, to other literature known subphthalocyanines
N1-B1-Cl1, N3-B1-Cl1, N5-
B1-Cl1
112.2(2), 115.7(2),
112.2(2)
113.8(19, 112.8(1),
113.8(1)
*
the boron(III)-atom in the [Spc BCl]
tetrahedrally surrounded by one chlorine atom and three
nitrogen atom. The boron is out of plane to the -system.
These are the reasons why only three isoindoline units are
around the smaller boron atom, and causes the -system to
9 is almost perfect
N1-B1-N3, N3-B1-N5,
N1-B1-N5
105.4(2), 105.0(3),
105.4(2)
105.1(1), 105.3(0),
105.3(0)
π
⦡
Isoindoline
44.2
43.1-44.3
π
contract. In the crystal structure, the annulated methyl
substituted cyclohexene ring shows the typical twisted chair
conformation, which explains the multiplett of the methylene
*
The free ligand of N -[Pc H ] 4a was crystallized and a
2
2
monoclinic system with a P2 /c space group was determined.
1
Here, also the twisted-chair conformation of the methylene
ring is visible. The crystal structure is disorded, so in every
molecule the non-peripheral position is partly occupied by a
quarter [-N=] units and three quarters [-CH=], for the same
reason, each NH position is occupied with a factor of 0.5 as
shown in Fig. 8 in light blue. The molecular arrangement
differs from unsubstituted Pc, where a heringbone pattern is
typical.
1
group observed in H NMR spectroscopy (Fig. SI-6). The
isoindoline
characteristic bond lengths of the B-Cl and B-N
are
listed in Table 3, compared to the first literature known
3
3
[SpcBCl] by KIETAIBL.
Figure 7. Molecular structure of [Spc*BCl]
9 in crystal. Bond
distances and angles and the lattice structure are presented in
the SI.
With a bond length of B-Cl of 1.85 Å, it is within the expected
range, as well as all values found for C-C bonds in the aromatic
system and C-N bonds of pyrrole units. The bowl depth of
*
-Pc H
Figure 8. Molecular structure of N
2
2
4a in the crystal.
Corresponding C and N positions of pyrazine and benzene rings
are statistically 75:25 occupied. Bond distances and angles and
0
.56 Å, as a value for the position boron atom above the
3
the lattice structure are presented in the SI. Similar to the
*
previously reported strucutre of Pc H
3
inclined [-BN
3
-] plane is also comparable to [SpcBCl].
2
, in one unit cell the
molecules are orientated perpendicular to each other.
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ARTICLE
For the first time, a lower symmetrical, alkyl substituted experiment. The values for Pc*H
Journal Name
2
2
2
3a are comparable
22
*
-[Pc Zn∙H
N
4
2
O] was structurally characterized. In comparison although a smaller basis set was used before.
to known zinc phthalocyanines bearing water as axial ligand,
4
3
such as [PcZn∙H
2
O]∙2dmf, which is also stacked in a
herringbone fashion along the crystallographic b axis, in the
*
molecular packing of
4 2
N -[Pc Zn∙H O], the described
perpendicular orientation of the molecules is visible.
Furthermore, the axial water pulls the zinc out of the ligand
4
cavity [-MN -].
Figure 10. Orbital energies for HOMO (black), LUMO (red), and
*
2
*
Figure 9. Molecular arrangement of A2B N -[Pc Zn] 5b in
2
4
LUMO+1 (blue) for varying N-content of Pc H . Orbitals for
crystal.
2
Pc*H are depicted.
Corresponding C and N positions of pyrazine and benzene rings
are statistically 50:50 occupied. Bond distances and angles and
the molecular structure is presented in the SI.
We find – with few exceptions – two absorption energies for
the Q-bands as was found earlier for unsymmetric Pc
2
0
derivatives. The splitting is nevertheless very small and is not
relevant for the interpretation of experimental UV/Vis spectra
since the peaks observed are broader than the energy
differences computed here (Fig. 5). The absorption maxima
Computational Studies
The electronic structure of the compounds presented here are upon increase of the nitrogen content in going from Pc*H
further analysed with density-functional theory using the PBE to Ppz*H 8a are shifting to higher absorption energies,
and B3LYP exchange-correlation functionals and including independent of hydrogen or Zn being in the center. An
dispersion corrections (DFT-D3) for the structural optimization. exception is tautomer 5a which has a higher excitation energy
With the aim to derive trends with increasing nitrogen than 4a
2
3a
2
T
.
*
2
substitution, the series from [Pc M] to [Ppz*M] with M = H ,
Zn was investigated. All structures including regioisomers and Since this tautomer is much less stable than 5a, it will not be
tautomers are shown in Fig. SI-5 in the supporting information. observed in the experimental spectrum. The shift to higher
For 6a, two regioisomers A
are separated by only 5.6 kJ mol . Furthermore, for the substitution of the bridging carbon atom by nitrogen.
compounds 4a
5a and 7a, two tautomers are observed. Only Oscillator strengths are rather large and very similar for both
for the more favored regioisomer of 6a (A
), a significantly Q-bands. They do not change along the series of compounds
lower stability of one tautomer is found (
For all other compounds, an equilibrium of tautomers under The character of the Q-bands is in all cases dominated by the
2 2
B
and ABAB, were found which excitation energies here is stronger than what was found for
-1
20
,
2 2
B
-
1
ꢁ
E = 56.4 kJ mol ). investigated.
-1
experimental conditions can be concluded (
For the Zn-substituted phthalocyanines, the two regioisomers energy differences in the absorption maxima of the Q-bands
ꢁ
E = 4.0 kJ mol ). HOMO→LUMO or the HOMO→LUMO+1 transiꢀon. The small
-1
5
b
and 6b show an energy difference of 1.6 kJ mol . Due to can therefore be understood by the close energetic proximity
the small energy differences, the analysis of the electronic of the LUMO and LUMO+1 orbital (Fig. 10). But even for the
structure was therefore carried out for all isomers described.
most symmetric molecules carrying hydrogen, the orbitals do
not have the same energy and therefore lead to different Q-
The absorption characteristics for all compounds as derived band energies. This is a consequence of the necessity to
from time-dependent density functional theory (TD-DFT) choose one tautomer in the computations. The resulting
computations are summarized in Table SI-1 in the supporting structure exhibits inequivalent nitrogen atoms in the ring,
information. The density functional used (B3LYP) has leading to the different orbital energies of LUMO and LUMO+1
previously been found to provide good agreement with
8
| J. Name., 2012, 00, 1-3
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ARTICLE
which are located either on the hydrogen-carrying or the the determining factor for the experimentally observed trend
hydrogen-free nitrogen atoms (orbital insets in Fig. 10).
in the excitation energies.
The dipole moment and polarizability
ꢀ
α are crucial quantities
for the application of phthalocyanines. Both values are listed in
Table SI-1 for the series of compounds investigated. The
observed dipole moment of up to 1.25 a.u. can easily be
rationalized by looking at the structure of the compounds
investigated. The N-substituted rings show higher electron
density and are thus always at the negative end of the dipole
moment vector. In case of more than one ring being N-
substituted, the direction of the dipole moment can be derived
from vector addition. The polarizability of the compounds is
also included and shows a slight increase upon substitution of
C-H groups by the more polarizable N atom. Every aza-
substituted ring adds approx. 23 a.u. to the isotropic
polarizability and the trend is irrespective of hydrogen or Zn
being in the center of the molecule.
Conclusions
We presented the first systematic study on the synthesis, the
spectroscopic, electroanalytical, photophysical, structural, and
computational analysis of three complete series of
Figure 11. Trend of experimental (black), TD-DFT (red), and
D
(blue) absorption maxima with linear regression curves for
H-L
*
Pc H .
*
azaphthalocyanines and azasubphthalocyanines: N -Pc H or
x
2
2
*
*
x x
N -[Pc Zn] (n = 0, 2, 4, 6, 8), and N -[Spc BCl] (n = 0, 2, 4, 6),
respectively.
In experiment, the tautomeric equilibrium will result in an
averaging of this difference and thus lead to only one, broader
excitation in addition to the usual broadening effects in UV/Vis
spectra.
4
Whereas non-aggregating soluble A -type phthalocyanines and
4
B -type pyrazinoporphyrazines (octaazaphthalocyanines) are
easily isolated in pure form and well-studied in literature, this
paper is dedicated to the unsymmetrical hybrid chromophores
The difference between frontier orbital energies
(ꢁHOMO/LUMO and ꢁHOMO/LUMO+1 in Table SI-1) gives
n n
of A4-nB and their A3-nB -sub-type. The effect of increasing
much higher values than the computed excitation energies due
to the missing orbital relaxation in this estimate. Nevertheless,
the trend is the same compared to the TD-DFT results:
increase of the gap with increased nitrogen content. The
comparison of experimental excitation energies and computed
number of [–CH=] units being stepwise substituted by [–N=]
units on photophysical (UV-Vis, fluorescence) and
electrochemical (CV) properties were correlated with the
results of computational calculations (TD-DFT). This study
offers insight to predict trends of the absolute HOMO and
LUMO levels and of the HOMO-LUMO gap, of the absolute
chromophore dipole moment and polarizability, and maybe
even of their singlet-oxygen versus fluorescence quantum yield
by chemical design. These are fundamental properties relevant
to applications of such chromophores as sensitizers in dye
ones from TD-DFT and the ꢁH-L approach is shown in Fig. 11.
The experimental trend of increasing excitation energies with
increasing nitrogen content is reproduced by both
computational approaches. But both approaches fail to
quantitatively reproduce the experimental slope and the
absolute excitation energies, while the more accurate TD-DFT
approach gives results in better agreement with experiment.
This indicates that both computational approaches are
appropriate for deriving trends in excitation energies for
substituted phthalocyanines but further improvement is
needed to achieve a quantitative agreement.
3
5
sensitized solar cells (DSSCs) , their injection of electrons into
3
6
a wide band gap inorganic semiconductor CB on the one
3
7
hand, or as singlet oxygen generators in PDT by energy
transfer on the other hand. All chromophores described herein
are suitable for organic molecular beam epitaxy, they can be
sublimed in HV without decomposition while parent
Since the frontier orbital gap is a suitable description for the
excitation energies, the question arises if the excitation energy
trend observed in the aza-substituted phthalocyanines is due
to a change in the energy levels of occupied or unoccupied
orbitals. The orbital energies for the lowest-energy structures
of the series of compounds investigated is shown in Fig. 10.
While LUMO and LUMO+1 show a similar slope, the occupied
HOMO shows a quicker decrease in energy upon nitrogen
substitution (larger slope). Thus, lowering the HOMO energy is
azaphthalocyanines, e.g. PpzH
without decomposition.
2
or [PpzZn], do not sublime
The synthesis of this class of weakly aggregating, soluble
*
*
x x
azaphthalocyanines, N -Pc M and N -[Spc BCl], has been
greatly improved by introducing a highly selective catalytic
aerobic oxidation of the 1,1,4,4,5,6-hexamethyltetraline to
corresponding phthalic acid key building block. With this
enhancement to prior art, we see a good chance that
hexadecamethyl-Pc (or short Pc*) chemistry will become
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Journal Name
similar popular among coordination chemists as pentamethyl- LTQ-FT spectrometer using dichloromethane/acetonitrile as
1
13
Cp (or short Cp*) chemistry became popular among solvent. H and C NMR spectra were recorded on a Bruker
organometallic chemists. Due to the rigid nature of this soluble AVII 300 MHz. X-ray diffraction (XRD) analyses was performed
and isomerically pure ligand class, insight into molecular and on a QUEST area detector system using Mo Kα radiation (λ=
lattice
structures
of
symmetrical
2,2,5,5- 71.073 pm) at 100 K.Stoe Quest software was used for
*
tetramethylcyclohexane substituted [Spc BCl] and Sppz integration and data reduction; structure solution and
*
Sppz BCl], as well as of lower symmetry N
*
-Pc H
[
2
2
and A
2
B
2
-
refinement was done with the WinGX program suite using
*
type N
time.
4
-[Pc Zn] was gained via single crystal XRD for the first BRUKER SAINT, XT V2014/1 and SHELX-2014/7. Molecular
graphics were produced with Diamond 4.0. The SQUEEZE
routine of the PLATON program package was used in these
Upon increasing number of [–N=] units replacing [–CH=] a cases to remove the corresponding delocalized electron
linear increase of the HOMO-LUMO gap and the excitation density from the data sets.
energies was observed. The optical HOMO-LUMO levels were Cyclovoltametric measurements were carried out with an rhd-
correlating with the potentials determined by CV. instruments setup, using a closed microcell in glovebox. As
Computational analysis gave the correct trend regarding the working electrode a Pt electrode was used, a gold or Pt
increase of excitation energies upon aza-substitution with counter electrode as well as an Ag reference electrode. The
ground state (DFT) and excited state (TD-DFT) methods compounds have been measured in a 0.5 M TBAF in DCM
*
-Pc H
although quantitative agreement needs refined methods. The solution using 5 mmol N
x
2
. All measurements have been
trend can be traced back to the HOMO energy rising quicker carried out using a 0.1 mmol Fc in DCM as reference.
than the LUMO and LUMO+1 energies. Transitions from the Synthesis of 1,1,4,4-tetramethyltetraline-6,7-dicarboxylic acid
2 2
HOMO into these two orbitals determines the Q-bands. The 0.05 g NaBr (486 ꢀmol), 125 mg [Co(OAc) ]∙4H O (502 ꢀmol),
trends in computed dipole moments and polarizabilities are in 3.00 g 1,1,4,4,6,7-hexamethyltetraline (13.9 mmol, 1 eq) were
line with the substitution patterns. Strong dipole moments are added in an autoclave. The autoclave was charged with 20 bar
observed for asymmetrically substituted N
x
-[Pc*M] molecules
2
O heated to 180 °C, 90 min. The pressure increased to 30 bar,
while polarizability increases with the increasing nitrogen dropped down to 20 bar. Autoclave was charged as often as
content. Both methods – frontier orbital gap and time- necessary, until the pressure stayed the same. Carboxylic acid
dependent density functional theory – provide the right trends was precipitated out of the solution and washed with water. A
but fails to reproduce the absolute values observed in second/third portion was yielded overnight, filtered, washed
experiment.
with water and finally dried in vacuum.
1
Yield: 97%. - H NMR (300 MHz, [D
The photophysical determination of fluorescence versus 2 H, COOH), 7.57 (s, 2 H, Ar-H), 1.66 (s, 4 H, CH
singlet oxygen quantum yield evidenced that a fast non- CH ) ppm. - MS (ESI(+), MeOH): m/z = 277.1436, cal. for
radiative relaxation pathway occurs for the metal-free +H : 277.1434. Additional information: Depending on
derivatives N -Pc*H and that the feasibility of this process the amount of glacial acid, the formation of the anhydride can
clearly increases with number of nitrogen atoms in the be observed, which is the product of the following step in the
6
]DMSO, 25 °C):
δ = 13.07 (s,
2
), 1.25 (s, 12 H,
2
C
16
H
20
O
4
1
x
2
*
*
*
macrocycle core. For the N
photophysical data revealed essentially 100% quantum yield as General procedure for N
sum of fluorescence quantum yields ( ) and singlet oxygen or as a mixture) were dissolved in 2 mL toluene per 5 mmol
quantum yields ), non-radiative decay paths are dinitril. Fresh boron trichloride solution (1 N in heptane or in o-
suppressed. Thus fine tuning of absorption and emission xylene, 1 eq) was added at once and then heated to 150 °C in a
x x
-[Spc BCl] and N -[Pc Zn] series, the synthesis of PN . An up-scaling of the reaction is possible.
*
x
-[Spc*BCl]: 1 eq PN 1 (or PyzDN* 2,
Φ
F
(Φ
ꢁ
maxima was demonstrated in these two series of dyes.
closed Schlenk tube. The yellowish solution turned into a deep
pink. After heating for 2-5 h the solution was added on a short
pluck of silica to remove insoluble byproducts. Spcs were
purified by a column chromatography with silica gel 60 Merck
and eluted with PE/EE 10:1.
Experimental Section
*
19
),
6,7-Dicyano-1,1,4,4-tetramethyltetraline (PN
1
5,5,8,8-
*
1
[
Spc BCl]: Yield: 13%. -
MHz, C , 25 °C): δ = 8.91 (s, 6 H, Ar-CH), 1.65-1.52 (m, 12 H,
CH ), 1.42 (s, 18 H, CH
MHz, [D ]DCM, 25 °C):
2 H, CH ), 1.66 (s, 18 H, CH
NMR (75 MHz, CDCl , 25 °C):
f
R (Tol/THF 30:1) = 0.27. - H NMR (300
tetramethyl-5,6,7,8-tetrahydro-chinoxaline-2,3-carbodinitrile
*
12,38
6 6
D
(
PyzDN
2),
and precursors were prepared according to
and were
1
2
3
),1.10 (s, 18 H, CH
3
) ppm. - H NMR (300
literature known procedures. The final dinitrils
1
2
2
δ
= 8.84 (s, 6 H, Ar-CH), 1.94-1.80 (m,
purified by using column chromatography or, if necessary,
sublimed before use. nOctanol was obtained from Merck,
dried according to standard methods and all reactions were
handled using standard SCHLENK techniques.
1
3
1
2
3
), 1.44 (s, 18 H, CH
3
) ppm. -
C
3
δ
= 150.0, 148.3, 130.0, 120.6,
3
2
7
3
5
C
5.5, 35.3, 32.6, 32.1, 30.1 ppm. - IR:ꢀ ꢁꢂ = 2959 (m), 2925 (m),
861 (m), 1729 (w), 1623 (w), 1466 (m), 1259 (m), 1088 (s),
The electronic UV/Vis spectra were recorded on an Avantes
AvaSpec-2048 spectrometer in a glovebox. IR spectra were
recorded on a Bruker Alpha FT-IR spectrometer with an ATR
measurement setup (diamond cell) in a glovebox using neat
samples. APCI-HR mass spectra were measured with a Finnigan
-
1
96 (s), 662 (m) cm . - UV/Vis (DCM):
18 (s), 267 (s) nm. - Fluorescence (DCM,
92 nm. - MS (APCI-HRMS(+)): m/z = 761.4247 [M+H] , cal. for
Cl +H: 761.4272.
λ
= 582 (s), 528 (sh),
λ
ex = 350 nm): λ =
+
48
H
54
B
1
1 6
N
1
0 | J. Name., 2012, 00, 1-3
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Journal Name
Sppz*BCl]: Yield: 35%. -
ARTICLE
1
(Tol/THF 30:1) = 0.35. - H NMR detected. - IR (ATR, 400-4000 cm ):ꢀ ꢁꢂ = 2956 (m), 2921 (s),
-1
[
R
f
(
300 MHz, CDCl
3
, 25 °C): δ = 1.94-2.07 (m, 12 H, CH
2
), 1.75 (s, 2855 (m), 1711 (w), 1688 (w), 1498 (m), 1301 (s), 1071 (s),
-1
1022 (m), 755 (s), 722 (m) cm . - UV/Vis (DCM):
13
1
8 H, CH
3
), 1.52 (s, 18 H, CH
3
) ppm. - C NMR (75 MHz, CDCl
3
,
λ =
MS (APCI-
2
5 °C): δ = 162.9, 146.2, 140.7, 39.3, 34.0, 30.2, 30.8 ppm. - IR: 687 (s), 619 (sh), 340 (s), 306 (s), 232 (s) nm.
+
= 2956 (m), 2922 (m), 2859 (m), 1708 (w), 1557 (m), 1454 (s), HRMS(+)): m/z = 957.5992 [M+H] , cal. for C62H N10+H:
72
-
ꢁꢂ
1
371 (s), 1356 (m), 1243 (vs), 1107 (s), 1045 (s), 798 (s), 733 957.6014.
-1
*
1
(
m) cm . - UV/Vis (DCM):
nm. - Fluorescence (DCM,
APCI-HRMS(+)): m/z
λ
= 534 (s), 489 (sh), 334 (m), 303 (s) ABAB N
ex = 350 nm): = 546 nm. - MS (CDCl
767.3964 [M+H] , cal. for (s, 8 H, CH
2 H, NH) ppm. C NMR (C
, 25 °C): δ = 36.5 ppm. - UV/Vis (DCM): λ = 672 (s), 642 (sh), 607 (s), 347
4
-Pc H
2
: Yield: <1%. -
R
f
(PE/EA 4:1) = 0.53. - H NMR
λ
λ
3
, 300 MHz): δ = 9.79 (s, 4 H, Ar-H), 2.22 (s, 8 H, CH
), 1.90 (s, 24 H, CH ), 1.85 (s, 24 H, CH ), -0.68 (s,
, 75 MHz): δ = 29.8, 33.0,
2
), 2.11
+
(
=
2
3
3
1
3
C
42
H
49
B
1
*
Cl
1
N
12+H: 767.3980.
6 6
D
1
N
4
-[Spc BCl]: Yield: 2%. - H NMR (300 MHz, CDCl
), 1.67 (s, 6 H, CH
), 1.36 (s, 6 H, CH ), 1.36 (s, cal. for C60
) ppm. - IR (ATR, 400-4000 cm ): ꢁꢂ
957 (m), 2869 (w), 1455 (m), 1253 (m), 1088 (s), 1020 (s), 797 MHz, CDCl
3
+
8
1
6
2
.76 (s, 2 H, ArCH), 1.76-1.48 (m, 12 H, CH
.65 (s, 6 H, CH ), 1.64 (s, 6 H, CH
H, CH ), 1.34 (s, 6 H, CH
2
3
), (s), 309 (s) nm. - MS (APCI-HRMS(+)): m/z = 959.5922 [M+H] ,
: 959.5919.
Yield: 342 mg, 357 mmol, 17%. - H NMR (300
, 25 °C): δ = 9.56 (s, 2 H, Ar-H), 9.50 (s, 2 H, Ar-H),
2.20 (s, 8 H, CH ), 2.05 (s, 8 H, CH ), 1.91 (s, 24 H, CH ), 1.81 (s,
57 (s), 506 (sh), 330 (m), 296 (s) nm. - MS (APCI-HRMS(+)): 12 H, CH ), 1.80 (s, 12 H, CH ), -0.04 (s, 2 H, NH) ppm. -
NMR (75 MHz, C , 25 °C): δ = 162.4, 150.0, 149.6, 145.1,
, 25 °C): δ = 144.4, 135.2, 134.8, 122.7, 122.0, 39.4, 39.3, 36.1, 36.0, 35.2,
3
3
3
70 1
H N12+H
-1
*
1
3
3
=
2 2 4 2
A B N -Pc H :
3
-1
(s), 701 (m), 516 (m) cm .
-
UV/Vis (DCM):
λ
=
2
2
3
1
3
5
3
3
C
+
m/z = 765.4075 [M+H] , cal. for C44
H
51
B
1
Cl
-[Spc BCl]: Yield: 3%. - H NMR (300 MHz,CDCl
.87 (s, 2 H, ArCH), 8.78 (s, 2 H, ArCH), 1.73-1.50 (m, 12 H, 34.6, 34.5, 32.7, 32.7, 21.1, 30.8 ppm. - IR (ATR, 400-4000 cm
1
N
10+H: 765.4082.
6 6
D
*
1
N
2
3
-
8
1
CH
.36 (s, 6 H, CH
ATR, 400-4000 cm ): ꢁꢂ = 2960 (m), 2925 (w), 2861 (w), 1459 680 (s), 656 (s), 625 (sh), 348 (s), 232 (s) nm.
2
), 1.67 (s, 6 H, CH
3
), 1.42 (s, 6 H, CH
3
), 1.38 (s, 6 H, CH
) ppm. - IR 761 (m), 752 (m), 679 (s), 543 (w) cm . - UV/Vis (DCM):
MS (APCI-
w), 1259 (s), 1090 (s), 1016 (s), 791 (s), 695 (m) cm . - UV/Vis HRMS(+)): m/z = 959.5921 [M+H] , cal. for C60
DCM): = 572 (s), 519 (sh), 327 (m), 303 (s) nm. - MS (APCI- 959.5919.
3
),
):ꢀ ꢁꢂ = 2915 (m), 2857 (m), 1358 (s), 1328 (s), 1148 (s), 1128 (s),
-1
1
3
), 1.05 (s, 6 H, CH
3
), 1.03 (s, 6 H, CH
3
λ =
-1
(
(
(
-
-1
+
70
H N12+H:
λ
+
*
1
HRMS(+)): m/z = 763.4173 [M+H] , cal. for C46
H
53
B
1
Cl
1
N
8
+H:
N
6
-Pc H
CDCl , 25 °C): δ = 9.75 (s, 2 H, Ar-H), 2.22 (s, 4 H, CH
-[Spc BCl] are unstable towards light in solution and 12 H, CH ), 1.93 (s, 12 H, CH ), 1.91 (s, 12 H, CH ), 1.90 (s, 12 H,
), 1.83 (s, 12 H, CH ), -0.53 (s, 2 H, NH) ppm. - C NMR
-[Spc BCl] was observed (75 MHz, C , 25 °C): δ = 162.0, 139.1, 131.3, 134.1 (w), 132.9
(w), 132.9 (w), 131.3 (w), 127.1 (w), 123.1, 46.0, 41.3 (w), 39.7,
2
:
Yield: 178 mg, 185 mmol, 9%. - H NMR (300 MHz,
763.4177.
3
2
), 2.19 (s,
*
The N
x
2
3
3
1
13
should be kept in the dark under inert gas. In the H NMR N
X
-
CH
3
3
*
*
[Spc BCl] free dinitril of degredated N
X
6 6
D
which could not be separated.
Synthesis of N
x 2
-Pc*H 240 mg lithium was dissolved in 10 mL 39.3, 36.3, 34.5, 32.8, 31.8, 31.7, 31.1, 30.9, 30.8, 29.8, 29.5,
noctanol at 120 °C within 20 min. After cooling down to rt, 29.3, 29.2, 28.6, 28.1, 27.5, 27.5 ppm. - not all quartary atoms
*
*
1 (4.19 mmol, 2 eq) and 1.0 g PyzDN 2 (4.16 mmol, could be detected. - IR (ATR, 400-4000 cm ):ꢀ ꢁꢂ = 2957 (s), 2924
-1
1.0 g PN
2
eq) were added and stirred for 10 h at 180 °C. The solutions (s), 1727 (s), 1693 (w), 1511 (s), 1457 (m), 1411 (m), 1072 (m),
-1
had a change in color to deep green. After cooling down to rt, 1021 (s), 756 (w), 744 (m), 677 (s) cm . - UV/Vis (DCM):
00 mL MeOH and 3 mL H PO were added. The solution was 660 (s), 597 (sh), 343 (s), 234 (s) nm. - MS (APCI-HRMS(+)): m/z
further washed 3 x 100 mL with MeOH. The product mixture = 961.5825 [M+H] , cal. for C58
λ =
1
3
4
+
68
H N14+H: 961.5824.
(
1)
*
1
was separated using gradient column chromatography with
Ppz H
4a was eluted, CDCl , 25 °C): δ = 2.22 (s, 16 H, CH
6a was eluted. After (s, 2 H, NH) ppm. – UV/Vis (DCM): λ
2
: Yield: 174 mg, 181 mmol, 9%. - H NMR (300 MHz,
), 1.93 (s, 48 H, CH ), -1.02
= 655 (s), 621 (s), 576 (s),
2
-Pc*H 7a was eluted. 343 (s), 231 (s) nm. - MS (APCI-HRMS(+)): m/z = 963.5732
*
PE/EE 10:1
then the ABAB and A
changing the solvent to PE/EE 1:1 N
ꢀ
1:1. First, Pc H
2
3a and N
2
-Pc*H
2
3
2
2
2
B
2
N
4
-Pc*H 5a
2
,
6
*
+
Finally Ppz H
2
8a was eluted with DCM.
66
[M+H] , cal. for C56H N16+H: 963.5729.
(
1)
*
1
*
Pc H
CDCl , 25 °C):
8 H, CH ), -0.01 (s, 2 H, NH) ppm. - UV/Vis (DCM):
2
: Yield: 20 mg, 20.9 mmol, 1%. - H NMR (300 MHz, Additional Information (1): The characterization of the Pc H
2
*
3
δ
= 9.91 (s, 8 H, Ar-H), 1.79 (s, 16 H, CH
2
), 1.54 (s, and Ppz H
2
results of a separate synthesis; here the
4
7
2
3
λ
=
compounds only have been identified by APCI-HRMS and UV-
10 (s), 677 (s), 647 (sh), 615 (sh), 343 (s), 295 (sh), Vis spectroscopy.
31 (sh) nm. - MS (APCI-HRMS(+)): m/z = 955.6096 [M+H]+, Ring Expansion of a Spc
6 2 4 2
N -Pc*H and N -Pc*H could be
*
cal. for C64
H
75
N
8
+H: 955.6109.
Yield: 48 mg, 50.1 mmol, 3%. - H NMR (300 MHz, corresponding Spc [Sppz*BCl] or N
, 25 °C): = 9.69 (s, 2 H, Ar-H), 9.65 (s, 2 H, Ar-H), 9.42 (s, solution was stirred in DMSO at 120 °C, 8 h. After removing the
H, Ar-H), 2.19 (s, 4 H, CH ), 2.07 (s, 8 H, CH ), 2.04 (s, 4 H, solvent under reduced pressure the product was purified by
CH ), 1.90 (s, 12 H, CH ), 1.83 (s, 12 H, CH ), 1.81 (s, 12 H, CH ), column chromatography PE/EE 1:1.
.81 (s, 12 H, CH ), -0.07 (s, 2 H, NH) ppm. - C NMR (75 MHz, The N -/N -Pc*H could be identified by using H NMR, UV-Vis
, 25 °C): δ = 160.6, 149.8, 149.2, 148.6, 137.0, 133.0, spectroscopy and APCI-HRMS. All data correlated with the
obtained by inserting 1.1 eq isoindoline of PN
1 in the
*
1
N
2
-Pc H
2
:
4
-[Spc*BCl]. Therefore, the
CDCl
3
δ
2
2
2
2
3
3
3
1
3
1
1
3
6
4
2
6 6
C D
1
32.2, 122.2, 121.6, 39.1, 36.1, 36.1, 35.9, 35.4, 35.3, 34.7, ones described above.
2.9, 32.8, 32.7, 30.9 ppm. - not all quartary atoms could be
3
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
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Organic & Biomolecular Chemistry
Page 12 of 14
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DOI: 10.1039/C8OB01705K
ARTICLE
Journal Name
*
*
Synthesis of [N
x
-Pc Zn] 1 eq N
x
-Pc H
] was added at once. The The time-resolved fluorescence measurements were
solution was stirred for 30 min at 75 °C until the conversion to performed on FS5 fluorometer (Edinburgh Instruments) with
2
was dissolved in 2 mL values were corrected for the refractive indices of the solvents.
toluene/5 mmol Pc. 1.1 eq [Zn(hmds)
2
*
N
x
-[Pc Zn] was completed (NMR control). The solvent was picosecond pulsed diode lasers excitation at 371 nm (EPL-375,
evaporated as well as the rest of the HHMDS and [Zn(hmds) ] pulse width ~ 68 ps) and 634 nm (EPL-635, pulse width ~ 81
2
and finally washed out with Et
in vacuum.
2
O. The compounds were dried ps). The decay curves were fitted to exponential functions with
Fluoracle software (Edinburgh Instruments).
*
1
N
2
-[Pc Zn]: Yield: 80%. - H NMR (300 MHz, C
9.97 (s, 4 H, Ar-H), 9.94 (s, 2 H, Ar-H), 1.92 (s, 4 H, CH
), 1.80 (s, 12 H, CH ), 1.56 (s, 24 H, CH ), 1.46 (s, functional theory (DFT), using the PBE exchange-correlation
) ppm. - UV/Vis (DCM): = 675 (s), 613 (sh), 360 (s), functional together with the def2-TZVPP basis set for all
28 (s) nm. - Fluorescence (DCM, ex = 350 nm) = 697 nm. - elements adding a semiempirical dispersion correction term
6
D
6
, 25 °C): δ Computational details. Unconstrained structural optimizations
=
2
), 1.86 of the compounds investigated were carried out with density
4
0
(s, 12 H, CH
3
2
3
4
3
12 H, CH
3
λ
2
λ
λ
+
44
MS (APCI-HRMS(+)): m/z
10+H: 1019.5149.
=
1019.5139 [M+H] , cal. for (DFT-D3). Orbital energies were derived on this level. The
4
5
46
C
62
H
70
N
Gaussian09
optimizer together with Turbomole 6.5
*
1
47
ABAB N
MHz): δ = 9.96 (s, 4 H, Ar-H), 1.91 (s, 8 H, CH
CH ), 1.78 (s, 8 H, CH ), 1.45 (s, 25 H, CH ) ppm. - UV/Vis applied throughout. The excitation energies were derived from
DCM): λ = 687 (s), 657 (s), 631 (sh), 596 (sh), 357 (s) nm. - MS time-dependent DFT computations using B3LYP /def2-TZVPP
4
-[Pc Zn]: R (Tol/THF 20:1) = 0.63. - H NMR (C D , 300 energies and gradients was used. The resolution-of-identity
f
6
6
4
8
2
), 1.85 (s, 24 H, and the multipole accelerated RI-J approximation was
3
2
3
4
9
(
(
+
APCI-HRMS(+)): m/z
=
1021.5073 [M+H] , cal. for and the Tamm-Dancoff approximation as implemented in the
5
ORCA package. The RIJCOSX approximation was used.
0
C
60
H
68
N
12Zn
1
+H : 1021.5054.
1
*
-[Pc Zn]: Yield: 71%. - H NMR (300 MHz, C
1
A
2
B
2
N
4
6
D
6
, 25 °C): Polarizabilities and dipole moments were derived with
δ = 9.93 (s, 2 H, Ar-H), 9.91 (s, 2 H, Ar-H), 1.91 (s, 8 H, CH
.83 (s, 8 H, CH ), 1.78 (s, 24 H, CH ), 1.53 (s, 12 H, CH ), 1.43 XRD measurements: Data of the crystal structure
s, 12 H, CH ) ppm. - H NMR (300 MHz, [D ]DCM, 25 °C): determinations of 4a 5b, and have been deposited at the
.59 (s, 2 H, Ar-H), 9.56 (s, 2 H, Ar-H), 2.24 (s, 8 H, CH ), 2.08 (s, Cambridge Crystallographic Data Centre. The data have been
H, CH ), 1.93 (s, 12 H, CH ), 1.92 (s, 12 H, CH ), 1.83 (s, 12 H, assigned to the deposition numbers CCDC 1507498-1507500.
), 1.82 (s, 12 H, CH ) ppm. UV/Vis (DCM):
66 (s), 601 (sh), 361 (s) nm. Fluorescence (DCM,
50 nm)
2
), PBE/def2-TZVPP with ORCA.
1
2
3
3
1
(
3
2
δ
=
,
9
9
8
2
2
3
3
CH
3
3
-
λ
=
=
Further experimental and computational details are given in
the electronic supporting information.
6
3
-
λ
ex
λ
= 680 nm. - MS (APCI-HRMS(+)): m/z = 1021.5043
12+H: 1021.5054.
+
[M+H] , cal. for C60
H
68
N
*
1
N
6
-[Pc Zn]: Yield: 78%. - H NMR (300 MHz, C
.96 (s, 2 H, Ar-H), 1.89 (s, 12 H, CH ), 1.83 (s, 12 H, CH
s, 24 H, CH ), 1.76 (s, 4 H, CH ), 1.43 (s, 12 H, CH ) ppm. -
UV/Vis (DCM): 662 (s), 649 (s), 357 (s), 227 (s) nm.
Fluorescence (DCM, ex = 350 nm) = 673 nm. - MS (APCI-
HRMS(+)): m/z = 1023.4959 [M+H] , cal. for C58
023.4959.
6
D
6
, 25 °C):
δ =
Acknowledgements
9
2
3
), 1.79
(
3
2
3
This work was funded by DFG within SFB 1083. The singlet
oxygen study was supported by LOEWE Priority Program
SynChemBio. We also would like to thank J. Wallauer and rhd-
instruments for their advice in our CV measurements.
λ
=
-
λ
λ
+
66
H N14+H:
1
Photophysical measurements. The steady-state fluorescence
spectra were measured using an AMINCO-Bowman Series 2
luminescence spectrometer. For singlet oxygen and
fluorescence determination, the dye samples were purified by
preparative TLC on Merck aluminum sheets coated with silica
gel 60 F254 to ensure high purity. Both the
were determined by comparative methods
unsubstituted zinc phthalocyanine (ZnPc) as
Φ
ꢁ
and
Φ
F
values
using
3
9
a
reference
-[Pc*M]. The
-[Spc BCl] series were determined
F(EtOH) = 0.95 and bengal rose (
.76 ) as reference compounds and long-pass filter FGL455
instead of OG530 for determination. All of the experiments
were performed in triplicate, and the data represent the
means of the measurements (estimated error 10%). For
determination, the sample and reference were excited at 598
4
1
31
(
Φ
ꢁ
(THF)
=
0.53,
photophysical data for N
with rhodamin G6 (
Φ
F(THF)
= 0.32 ) for N
x
*
x
Φ
ꢁ(MeOH)
Φ =
4
2
0
Φ
ꢁ
±
Φ
F
*
x x
nm and 490 nm for N -[Pc*M] and N -[Spc BCl], respectively,
and the absorbance at the Q-band maximum was maintained
at less than 0.05 to avoid the inner filter effect. The emission
spectra were corrected for the instrument response. The
Φ
F
1
2 | J. Name., 2012, 00, 1-3
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Or gP al en ai sc e& d Bo i on mo to al ed cj uu ls at r mC ha re gmi ni ss try
View Article Online
DOI: 10.1039/C8OB01705K
Journal Name
ARTICLE
1
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