Supramolecular assemblies of bay-substituted perylene diimides in solution and on a solid substrate

Article abstract of DOI:10.1039/c3ob41058g

Perylene diimides (PDIs) substituted with a terpyridine moiety at the bay-region have been synthesized. These building blocks were used to construct supramolecular complexes in chloroform. A dimer and a trimer were built via the bay-region complexation wi

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Supramolecular Assemblies of bay-Substituted Perylene Diimides in
Solution and on Solid Substrate
Essi Sariola-Leikas,*a Marja Niemi,a Helge Lemmetyinena and Alexander Efimova
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
Perylene diimides (PDIs) substituted with a terpyridine moiety at the bay-region have been synthesized.
These building blocks were used to construct supramolecular complexes in chloroform. A dimer and a
trimer were built via the bay-region complexation with zinc. The PDI compounds were further modified
to have silane anchors and PDI self-assembled monolayers (SAMs) were prepared on quartz substrate.
10 Complexation of metal ions was also done on the surface, and this was observed clearly in the absorption
spectrum. These studies on surface show possible progress towards supramolecular multilayer structures.
on a solid substrate (quartz). Siloxane anchors on PDIs are also
uncommon and to the best of our knowledge, no PDIs with a
50 silane anchor at the bay-region have been published before.16
Covalent attachment to the substrate was done in one step and
monomolecular layer formation was proved by absorption
measurements. Coordination with zinc(II) is a promising option
for layer-by-layer formation of supramolecular assemblies of
55 photoactive compounds.17 A supramolecular dimer and a trimer
were constructed in solution. Such tpy-PDI complexes, which are
connected through the bay-region, were prepared for the first
time. Furthermore, energy transfer from the middle PDI to the
side PDIs was observed in the PDI trimer with quantum yield
60 close to unity, eventhough the distance between the donor and the
acceptor is quite long.
Introduction
In recent years, considerable attention has been focused on
surface modification of solid substrates by forming highly
15 ordered organic films. One of the approaches to form ultrathin
films on the surface is immersing the substrate into a diluted
solution of an anchor-containing organic compound. The formed
films are referred to as self-assembled monolayers (SAMs).1
Silanes are one of the anchor group types, which form a strong
20 and stable covalent bond between the molecule and an oxide
surface.[2] Siloxane-containing compounds are rather difficult to
synthesize but they enable creating SAMs fast and easy.3-4
The use of a chelating ligand, such as a terpyridine, supports
the formation of supramolecular assemblies. Terpyridine ligands
25 are highly attractive terminal groups to be incorporated into
SAMs, since they can coordinate to a broad range of metals and
be substituted with many different functionalities.5 The three
nitrogen donors on each 2,2′:6′2″-terpyridine (tpy) interact
strongly with the metal ion. Most commonly used metals for this
30 purpose are zinc(II)6-7 and ruthenium(III)/(II)8. The terpyridine
moieties are widely used in metallo-supramolecular polymers,
where their role is significant.9
Perylene diimides (PDIs) are a unique class of chromophores,
which exhibit outstanding optical, electronic and physical
35 properties. Typically, PDIs are functionalized at the imide ring,
which restricts the interactions between chromophores and their
successive layers.10 On the other hand, introducing functional
groups in the bay-region (1,6,7,12-positions) modifies the
electronic and optical properties of PDIs and allows their fine
40 tuning.11-12 These dyes combined with the tpy units are powerful
building blocks for supramolecular organization and because of
their photoactive properties these units can be used for
optoelectronic applications.13-14
Results and Discussion
Synthesis
Borylation of bromophenylterpyridine was done according to
65 Scheme 1 with a moderate yield of 50% of tpy 1. Attempts to
improve the reaction efficiency by changing the base to NaOAc
and by using the catalyst PdCl2 and the ligand [dppf = 1,1′-
bis(diphenylphosphanyl)ferrocene] as separate reagents did not
increase the yield. Tpy 1 was used in a Suzuki coupling reaction
70 with 2-(benzyloxymethyl)pyrrolidine substituted PDI 2. The
synthesis of PDI 2 was done according to the procedure reported
earlier.18
Building block tpy-PDI
3
was synthesized from
regioisomerically pure 1,7-PDI 2 (Scheme 1).11 The reaction was
75 done in a toluene/water biphasic system with Pd catalyst. Product
3
was purified using automated low-pressure Combiflash
chromatograph on an alumina column. Silica columns could not
be used for the purification because of their excessive sorption of
terpyridyl-containing compounds.
In this paper we report syntheses of PDIs substituted with the
45 terpyridine moiety at the bay-region. Terpyridine moieties at the
bay-region in PDIs are extremely rare.15 We have also
synthesized PDIs with a silane anchor and prepared PDI SAMs
80
Deprotection of tpy-PDI 3 was performed using boron
tribromide (Scheme 2). Thus received PDI 4 was further modified
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25
Scheme 4 Synthetic route to pyr-PDI-Si(OEt)3 11.
Solution studies
PDIs 3 and 8 were used to construct supramolecular complexes in
solution. According to the literature, zinc ion forms complexes
Scheme 1 Borylation of tpy 1 and Suzuki coupling reaction of tpy-PDI 3.
30 with terpyridine under very mild conditions and the complexation
13
can be detected from their absorption spectra.7,
In our
experiments, zinc acetate did not give stable complexes.
Therefore, the counter ion was changed and zinc triflate
(Zn(OTf)2) was chosen. The complexes were prepared by
35 dissolving PDI (3 or 8) in CHCl3/CH3CN and adding zinc triflate
stock solution in the mixture. The reaction solution was stirred at
room temperature for 1h. Structures of the formed zinc
complexes Zn-3 and Zn-8 are presented in Figure 1.
A dimer (3-Zn-3) and a trimer (3-Zn-8) were also prepared
40 (Figure 1). The dimer was produced either from monomers Zn-3
and 3 (3-Zn-3a) or directly from PDI 3 (3-Zn-3b). Trimer 3-Zn-
8 was assembled in DMF because the solubility of Zn-8 in
chloroform-based solvents was poor.
Steady-state absorption was used as a quick method to prove
45 the formation of the complexes. Characteristic absorption bands
of tpy-PDI 3 appear between 550-750 nm and 400-500 nm
(Figure 2). Both the PDI core and the tpy unit absorb also at the
wavelengths below 350 nm. The 650 nm centered band is
characteristic for pyrrolidine substituted PDI.19 Distinct changes
50 in absorption were observed after complexation with zinc: an
increase of the absorption intensity between 300-350 nm and a
decrease and sharpening around 270 nm. These correspond to the
changes in the tpy unit absorption and thus indicate the formation
of the zinc complex.13
Scheme 2 Synthetic route to tpy-PDI-Si(OEt)3 6.
5
Scheme 3 Synthesis of bis(substituted) tpy-PDI 8.
55 Table 1. Absorption and emission maxima of compounds 3 and 8 and
their zinc complexes in CHCl3.
to have a siloxane anchor. The hydrosilylation procedure was
similar to the one published earlier for other chromophores.4
Compounds 4, 5 and 6 were obtained with relatively high yields
Compound
3
Absorption, λmax (nm)
284, 442, 662
Emission, λmax (nm)
753
757
10 as indicated in Scheme 2.
Zn-3
288, 397, 438, 663
288, 402, 439, 666
288, 403, 442, 666
284, 556
Bis(substituted) tpy-PDI 8 (Scheme 3) was synthesized from
dibromo-PDI 7, which was pure 1,7-regioisomer.11 The reaction
conditions were similar to those described for PDI 3. However,
purification was not straightforward because of the minor amount
15 of mono-tpy-substituted PDI. Column separation did not provide
enough resolution, and the complete separation was achieved
only using preparative alumina TLC plates.
3-Zn-3a
3-Zn-3b
8
758
759
619
Zn-8
288, 338, 553
607
3-Zn-8
288, 389, 439, 666
603, 755
Small red-shift of the absorption maximum of the PDI unit
from 662 nm to 666 nm was observed during the complexation.
Also in the emission spectra a small shift of the maximum was
60 noticed (Figure 3). The two-fold increase in the molar
absorptivities (ε) were observed for the dimers (3-Zn-3a and 3-
Zn-3b). As expected, the dimers formed via different routes give
Bis-pyrrolidine PDI 11 with a siloxane anchor was also
prepared to compare the bonding densities of PDIs with different
20 substituents. Hydroxy-PDI 9 was prepared according to the
literature procedure.18 Syntheses of allyl PDI 10 and siloxane PDI
11 were similar as for the terpyridine PDIs. Purification of all
these compounds could be efficiently performed using silica gel.
The synthetic route is presented in Scheme 4.
identical absorption spectra (Figure 2). Table
1 presents
absorption and emission maxima of compounds 3 and 8 and their
65 complexes in solution.
2
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Fig. 1 Supramolecular complexes.
Fig. 3 Emission spectra of tpy-PDI 3 and its zinc complexes in CHCl3
(Exc: 630 nm).
5
Fig. 2 Absorption spectra of tpy-PDI 3 and its zinc complexes in CHCl3.
25
The emission spectra of bis(substituted) tpy-PDI 8 and its zinc
complexes are presented in Figure 5. As expected, the spectrum
of trimer 3-Zn-8 has two emission maxima at 603 nm and 755
nm, which correspond to PDI 8 and PDI 3, respectively.
Quenching of the fluorescence bands around 600 nm and 760 nm
Zn-complexation of compound 8 showed similar changes in
the absorption spectrum as that of compound 3, i.e. an increase of
the absorption around 340 nm and sharpening below 300 nm,
which are due to the formation of zinc tpy (Zn-8, Figure 4).
30 are seen in the trimer, whose emission spectrum is multiplied by
25 for comparison with the references. At the excitation
wavelength of 505 nm absorbance of PDI 3 is rather weak in
comparison to that of PDI 8, but still relatively strong emission
around 750 nm is observed for the trimer. This indicates that
35 energy transfer from the middle PDI to one of the side PDIs is the
reason for the quenching in the trimer.
Energy transfer from the middle PDI to the side PDI was
confirmed by time-resolved fluorescence measurements with the
time-correlated single photon counting method. Lifetimes of the
40 first singlet excited state of reference compounds PDI 8 and PDI
3 were determined as 8.3 ns and 1.57 ns, respectively (see
10 Remarkable blue shift was observed for the PDI band from
around 660 nm of 3 and Zn-3 to around 555 nm of 8 and Zn-8.
Such shift was expected for PDI 8 where there is no pyrrolidine
substituent. The low molar absorptivity of Zn-8 in Figure 4 can
not be considered accurate because of low solubility and
15 aggregation of the complex in CHCl3. When trimer 3-Zn-8 was
formed, bands similar as for 3 and Zn-3 were spotted and the
absorption maxima match well with the zinc complexes of PDI 3
and 8 (Table 1). Evidently the shoulder at about 570 nm
corresponds to the PDI moiety between the two tpy units (8), and
20 the maximum at about 665 nm to the PDI complexed with only
one tpy moiety (3).
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Fig. 6 Fluorescence decay-associated spectra of trimer 3-Zn-8 in CHCl3
Fig. 4 Absorption spectra of bis(substituted) tpy-PDI 8 and its zinc
complexes in CHCl3. The absorption spectrum of tpy-PDI 3 is shown for
comparison.
(Exc: 405 nm).
× 109 s-1 and the quantum yield of energy transfer can be
35 estimated from ϕenT = kenT / (kenT + kfl) as 0.99. Considering the
highly efficient energy transfer, it seems unreasonable that there
is significant emission around 600 nm in the steady state
fluorescence spectrum of the trimer (Figure 5). This can be
explained by the presence of ca. 4% (as derived from the
40 fluorescence quenching) of the highly emissive longer
oligomers13, residual 3-Zn-3 and trimer dissociated to its
components. Even a small amount of free PDI 8 will cause a
strong signal in the steady state spectrum due to the relatively
long lifetime of its singlet excited state.
45 NMR Characterization
The synthesized compounds were fully characterized by mass
spectrometry (see Experimental Section) and NMR spectroscopy
(see Supporting Information). All the products had good
solubility allowing the NMR measurements in CDCl3. The signal
50 assignments are based on two-dimensional NMR spectroscopy,
the heteronuclear single-quantum coherence (gHSQC) with
multiplicity editing and the homonuclear correlation spectroscopy
(COSY).
5
Fig. 5 Emission spectra of bis(substituted) tpy-PDI 8 and its zinc
complexes in CHCl3 (Exc: 505 nm).
Supporting Information). To distinguish between the different
emitting species in 3-Zn-8, fluorescence decays were collected
10 with a constant accumulation time (180 s) in the range 580-840
nm with 20 nm steps. The obtained decay curves were fitted
globally to obtain fluorescence decay component spectra (Figure
6). Three exponents were needed for a reasonable fit quality. The
fastest component (117 ps) follows the shape and position of the
15 fluorescence spectrum of PDI 8 at 600-700 nm. The negative
amplitude around 750 nm indicates a formation of fluorescence
and thus corresponds to energy transfer from the middle PDI to
the side PDI. The formed component shows clearly the spectrum
of PDI 3 (see Figure 6) centered at 750 nm and the lifetime (1.40
20 ns) is in agreement with the one measured for reference PDI 3
(1.57 ns). The final component with a lifetime of 7.89 ns is weak
in amplitude, but shows clearly the spectrum of PDI 8. The
lifetime is similar to that measured for reference PDI 8 and this
component can be assigned to a small amount of free PDI 8 in the
25 solution due to dissociation of the trimer.
1
The assignment of H NMR peaks is complicated due to the
55 overlapping of the peaks and crowded aromatic and aliphatic
regions. Thus most of the signals are visible as multiplets.
However, the assignment for all the proton signals was
succesfully done. When comparing the aromatic regions of
compounds 3, 4, 5 and 6, some small changes of peak positions
60 are observed in the perylene core proton signals (7, 11, 14) and in
the signals of phenylene protons. In the spectrum of PDI 4 these
signals are distinguished better. In the spectra of PDIs 5 and 6,
the signal from proton 13 is shifted to lower field compared to the
other spectra. The aliphatic regions in the spectra are quite
65 consistent. In the spectrum of PDI 4, the signal from proton d is
moved to higher field when compared to the other spectra. In the
spectra of PDIs 5 and 6, the signal from proton e is deshielded (δ
4.66-4.41 ppm), which is due to changes in the anchor group. All
the characteristic proton signals such as hydroxyl group, terminal
70 double bond and silane protons, are observed easily from the
spectra of PDIs 4, 5 and 6, respectively. Positions of these signals
correspond well with values of previously studied
chromophores.4
The rate constant of energy transfer, kenT, in the trimer can be
calculated as kenT = k1 – kfl, where k1 is the rate constant of the
fastest process in the trimer (8.55 × 109 s-1) and kfl is the rate
constant of the fluorescence, which is obtained from the
30 measurement of PDI 8 (1.2 × 108 s-1). The calculated kenT = 8.43
4
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The symmetric structure of PDI 8 makes its spectrum quite
straightforward to resolve. Also the spectra of PDIs 10 and 11 are
simpler than those of the other PDIs because of the
30 shifted back to its old position (around 7.40 ppm) in the spectrum
of the dimer. These observations are similar with the results
found previously for a PDI with terpyridines at the imide
Fig. 9 Absorption spectra of pyr-PDI 10 on molar absorptivity (ε) scale
35
and PDI SAM 11 on quartz surface.
region.13
5 Fig. 7 The aromatic regions of 1H NMR spectra of tpy-PDI 3, Zn-3 and 3-
Zn-3. The marked signal (*) corresponds to protons 6″-H; the closest
protons to nitrogen atoms in terpyridine.
Complex Zn-8 was the only one measured in deuterated
methanol because of its low solubility in CDCl3. However,
similar shifting of signals from protons 5″-H and 6″-H are
40 observed when the spectra of bis(substituted) tpy-PDI 8 and Zn-8
are compared. The signal of protons 6″-H is deshielded from 8.70
to 8.95 ppm, and the signal of protons 5″-H is shifted from 7.40
to 7.95 ppm. Assignment of the aromatic region protons in the
spectrum of trimer 3-Zn-8 is too complex. The region is nearly
45 one big multiplet. Nevertheless, the integrals match well with the
number of protons.
Immobilization and Complexation
SAMs were prepared in a one-step process, where the reaction
vessel was loaded with a solution of siloxane PDI 6 or 11 in
50 distilled toluene and isopropyl amine under argon. Quartz plates
were precleaned according to the previously reported method.4
The cleaned plates were immersed in the solution, and the
reaction vessel was heated at 105 °C. After 2h, the plates were
sonicated on ultrasonic bath to remove residual physisorbed
55 compound. Absorption spectra of the SAMs were obtained by
subtracting the absorbance of the clean substrate from the
absorbance of the plate with the SAM. Considering the
absorption spectrum of the monolayer on the surface, the optical
densities in Figures 8 and 9 should be divided by two, because
60 layers are formed on both sides of the substrate.
The absorption spectrum of SAM 6 shows similar shape as
PDI 5 in solution (Figure 8). Even though absorptions of the
SAMs are low, the complexation with zinc triflate is nicely
observed from the spectrum of the plate. Complexation on the
65 surface was done by immersing the substrate with the SAM in the
salt solution for 1h. Same changes in the absorption spectrum are
seen as with complexation in chloroform: an increase of
absorption between 300-350 nm and a decrease around 270 nm.
An expected increase at 400 nm and 440 nm is also noticeable as
70 these bands are more intense in the complex form of PDI
(absorption spectrum of Zn-3). The PDI band of SAMs around
640 nm is slightly red-shifted upon complexation as was visible
also in the solution studies. The absorption maxima are collected
Fig. 8 Absorption spectra of tpy-PDI 5 and complex Zn-3 on molar
10
absorptivity (ε) scale and PDI SAM 6 on quartz surface.
uncomplicated substituent. Comparing 1H NMR spectra of
compounds 10 and 11, all the peaks in the aromatic region have
shifted a bit downfield in the spectrum of PDI 11. In the aliphatic
region, the signals from the terminal double bond have vanished
15 and the silane signals are visible in the spectrum of PDI 11. The
signal positions match well with the signals in the spectrum of
PDI 6.
Resolving the spectra of complexes (Zn-3, 3-Zn-3, Zn-8, 3-
Zn-8) is complicated but possible. The signals in the aliphatic
20 region correlate nicely with the uncomplex ones, though the
aromatic region signals are shifted. When comparing the spectra
of PDI 3 and complex Zn-3, it is clear that complexation has
occurred (Figure 7). Nearly all the peaks in the aromatic region
have moved in the spectrum of Zn-3. The closest protons to the
25 nitrogen atoms in the terpyridine moiety (5″-H, 6″-H) are shifted
to lower field from 7.35 and 8.75 ppm to 7.80 and 8.90 ppm,
respectively. When comparing the spectra of Zn-3 and dimer 3-
Zn-3, an extreme high-field shift of protons 6″-H is observed
(marked with * in Figure 7). The signal from protons 5″-H is
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in Table 2.
centred, and lock mass TOF correction was applied. Absorption
Bis-pyrrolidine PDI 11 was also attached on the surface. The 50 spectra were measured using Shimadzu UV-2501PC UV-Vis
absorption spectrum of SAM 11 imitates nicely the absorption of
pyr-PDI 10 (Figure 9). The absorption bands are broader in the
spectrum of the SAM but the band maxima correspond quite well
with pyr-PDI 10 in solution (Table 2).
Recording spectrometer and emission spectra were recorded by
Fluorolog Yobin Yvon-SPEX spectrofluorometer.
Fluorescence decays of the samples in the nanosecond and
sub-nanosecond time scales were measured using a time-
5
The absorption maximum provides a possibility to estimate the 55 correlated single photon counting (TCSPC) system (PicoQuant
mean molecular area (mma) of the PDI in the SAM. The mma
values were calculated assuming the same molar absorptivity (ε)
10 of compounds in SAMs as in solution (Table 2). This is true only
if the molecules are randomly oriented on the surface and if the
GmBH) consisting of PicoHarp 300 controller and PDL 800-B
driver. The samples were excited with the pulsed diode laser head
LDH-P-C-405B at 404 nm and fluorescence decays were
measured at the wavelength of maximum emission (620 nm and
chromophore-chromophore or chromophore-surface interactions 60 750 nm for PDI 8 and PDI 3, respectively). The signals were
are disregarded.20 The mma values are smaller than what one
could expect for perfect monolayers. This might be due to the
15 long linker, which allows chromophores to stack one over another
instead of forming an ideal monomolecular film. This hypothesis
detected with a micro channel plate photomultiplier tube
(Hamamatsu R2809U). The time resolution of the TCSPC
measurements was about 80 ps (FWHM of the instrument
response function). For trimer 3-Zn-8 the fluorescence decays
is supported by the complete fluorescence quenching of the films, 65 were measured in a range of wavelengths 580-840 nm with a 20
which is due to the aggregation of the PDI units. Evidently, a
more rigid tether is needed to improve the orientation of the
20 molecules in films, and this research is currently under way.
nm step and constant accumulation time of 180 s. The decays at
different wavelengths were fitted globally to obtain decay-
associated spectra.
Table 2. Absorption maxima and mean molecular areas (mma) of
samples.
4'-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-
70 2,2':6',2''-terpyridine (1)21
Sample
Solvent/
substrate
Absorption,
λmax (nm)
mmaa, (nm2)
4'-(4-Bromophenyl)-2,2':6',2''-terpyridine (100 mg, 0.26 mmol)
and KOAc (76 mg, 0.77 mmol) were dissolved in DMSO (5mL)
on ultrasonic bath. Bis(pinacolato)diboron (78 mg, 0.31 mmol)
and Pd(dppf)Cl2·CH2Cl2 (10 mg, 0.013 mmol) were added and
75 the reaction mixture was stirred at 80 °C under argon for 45 min.
The solution was diluted with CHCl3 and washed with a saturated
solution of EDTA (3 × 80 mL). The organic phase was
evaporated under reduced pressure. The crude product was
purified on Combiflash chromatograph using alumina column (12
80 g) eluting with hexane/EtOAc gradient (flow rate: 30 mL/min;
hexane (1 min), hexane to hexane/EtOAc 10:3.5 (5 min),
hexane/EtOAc 10:3.5 (3 min)). Product 1 was isolated as a white
solid (56 mg, 50%). δH(300 MHz; CDCl3; Me4Si): 1.39 (12H, s,
Me), 7.33-7.40 (2H, m, 5″-H), 7.89 (2H, td, J 7.8, 1.8, 4″-H),
85 7.92-7.98 (4H, m, phenylene-H), 8.68 (2H, d, J 7.9, 3″-H), 8.74
(2H, d, J 3.8, 6″-H), 8.75 (2H, s, 3′-H). δC(75 MHz; CDCl3 ;
Me4Si): 25.1 (CH3), 84.2 (C-dioxaborolane), 119.1 (C-3′), 121.6
(C-3″), 124.1 (C-5″), 126.8 (Co-phenylene), 135.6 (Cm-
phenylene), 137.1 (C-4″), 141.2 (Ci-phenylene), 149.4 (C-6″),
90 150.3 (C-4′), 156.2 (C-2′), 156.4 (C-2″); Cp-phenylene signal was
not observed. MS (ESI-TOF, CH3CN): m/z = 435.2223 [M+H]+
(calcd. for C27H26BN3O2 435.2233).
PDI 5
SAM 6
CHCl3
quartz
quartz
CHCl3
quartz
283, 412, 647
282, 640
1.01
0.89
SAM 6, Zn
PDI 10
291, 645
272, 434, 696
432, 680
SAM 11
0.96
a mma = ε/(NAA), where ε is molar absorptivity, NA is the Avogadro
constant and A is absorbance of the layer.
25 Experimental
Materials and instrumentations
All reagents and solvents (HPLC grade) were purchased from
Sigma-Aldrich Co., Tokyo Chemical Industry Co. or VWR
International. Unless otherwise mentioned, chemicals were used
30 as received. Dichloromethane was distilled over P2O5 and toluene
over sodium shots. Quartz plates were purchased from Finnish
Specialglass.
The monitoring of reactions was carried out by thin layer
chromatography (TLC), employing aluminum sheets precoated
35 with silica gel 60 F254 or aluminium oxide 60 F254 neutral
(Merck). The purification and isolation of the products was
performed by column chromatography on Silica 60 (mesh size
40-63 µm) or by flash chromatography using CombiFlash
5-(4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-12-(2-
((benzyloxy)methyl)pyrrolidin-1-yl)-2,9-dioctylanthra[2,1,9-
95 def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone (3)
Monobromo-PDI
2 [5-(2-((benzyloxy)methyl)pyrrolidin-1-yl)-
Companion (Teledyne ISCO).
1
12-bromo-2,9-dioctylanthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-
1,3,8,10(2H,9H)-tetraone]18 (110 mg, 0.12 mmol), compound 1
(60 mg, 0.14 mmol), tetrabutylammonium chloride (7 mg, 0.025
100 mmol) and Pd(dppf)Cl2·CH2Cl2 (10 mg, 0.012 mmol) were
dissolved in a two-phase mixture of toluene (5 mL) and 1M
K2CO3 (aq) (5 mL). The reaction mixture was stirred at 90 °C for
19 h. The organic phase was separated and washed with water (2
× 40 mL). The aqueous phase was extracted with toluene (2 × 10
105 mL) and the organic layers were combined and evaporated under
40
The H NMR spectra were measured on Varian Mercury 300
MHz spectrometer (Varian Inc.). All chemical shifts are given in
ppm relative to TMS as internal standard and the coupling
constants, J, are given in Hz. Mass spectra were recorded on high
resolution ESI-TOF LCT Permier XE mass spectrometer (Waters
45 Corp.). The sample of an analyte was dissolved in appropriate
solvent at concentration ca. 0.01 mg/mL and infused at 15
µL/min rate. The reference solution of Leucine Enkephaline (50
pg/mL) was infused simultaneously. The original spectra were
6
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Organic & Biomolecular Chemistry
reduced pressure. The product was purified on Combiflash
chromatograph using alumina column (12 g) eluting with
CHCl3/CH2Cl2 gradient (CHCl3/CH2Cl2 1:1 to CHCl3 (6 min)).
Product 5 was crystallized on a watch glass and obtained as a
CHCl3/hexane gradient (flow rate: 30 mL/min; CHCl3/hexane 1:1 60 dark green solid (64 mg, 80%). UV-vis λmax(CHCl3)/nm 283
(6 min)). Product 3 was crystallized on a watch glass and
obtained as a dark green solid (108 mg, 78%). UV-vis
λmax(CHCl3)/nm 284 (ε/dm3 mol-1 cm-1 54740), 442 (9800) and
662 (23120). δH(300 MHz; CDCl3; Me4Si): 0.81-0.93 (6H, m, 22-
(ε/dm3 mol-1 cm-1 53130), 412 (9870) and 647 (24310). δH(300
MHz; CDCl3; Me4Si): 0.80-0.94 (6H, m, 22-H), 1.19-1.52 (20H,
m, 17-21-H), 1.62-1.85 (4H, m, 16-H), 1.86-2.11 (2H, m, b-H),
2.12-2.46 (2H, m, c-H), 3.22 (2H, d, J 6.7, COCH2), 3.40-3.75
5
H), 1.18-1.54 (20H, m, 17-21-H), 1.65-1.86 (4H, m, 16-H), 1.95- 65 (2H, m, a-H), 4.06-4.33 (4H, m, 15-H), 4.48-4.66 (2H, m, e-H),
2.15 (2H, m, b-H), 2.16-2.41 (2H, m, c-H), 3.43-3.77 (2H, m, a-
5.14-5.28 (2H, m, CH=CH2), 5.86-6.05 (1H, m, CH=CH2), 4.75
(1H, br s, d-H), 7.32-7.41 (2H, m, 5″-H), 7.77-7.84 (1H, m,
phenylene-H), 7.85-7.93 (5H, m, 4″-H, 13-H, phenylene-H), 7.98
(2H, d, J 8.2, 6-H, phenylene-H), 8.50-8.71 (5H, m, 3″-H, 7-H,
10 H), 3.77-4.11 (2H, m, e-H), 4.12-4.30 (4H, m, 15-H), 4.59-4.69
(2H, m, f-H), 4.69-4.80 (1H, m, d-H), 7.32-7.41 (7H, m, 5″-H, g-
H), 7.80 (1H, d, J 8.5, 13-H), 7.82-7.95 (5H, m, 4″-H, phenylene-
H), 8.00 (2H, d, J 8.2, 6-H, phenylene-H), 8.39-8.48 (1H, m, 14- 70 11-H, 14-H), 8.71-8.76 (2H, m, 6″-H), 8.78 (2H, s, 3′-H), 8.81
H), 8.62-8.67 (2H, m, 7-H, 11-H), 8.70 (2H, d, J 7.9, 3″-H), 8.73-
15 8.77 (2H, m, 6″-H), 8.80 (2H, s, 3′-H), 8.83 (1H, s, 4-H). MS
(ESI-TOF, CH3CN): m/z = 1111.5450 [M+H]+ (calcd. for
C73H70N6O5 1111.5486).
(1H, s, 4-H). MS (ESI-TOF, CH3CN): m/z = 1088.5270 [M]+
(calcd. for C70H68N6O6 1088.5200).
(1-(12-(4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-2,9-dioctyl-
1,3,8,10-tetraoxo-1,2,3,8,9,10-hexahydroanthra[2,1,9-
75 def:6,5,10-d'e'f']diisoquinolin-5-yl)pyrrolidin-2-yl)methyl 4-
(triethoxysilyl)butanoate (6)
5-(4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-12-(2-
(hydroxymethyl)pyrrolidin-1-yl)-2,9-dioctylanthra[2,1,9-
20 def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone (4)
All the glassware was dried in oven (150 °C, 2 h) before use. The
reaction flask was sealed with a septum, placed on an ice bath,
and kept under constant argon flow. Compound 5 (15 mg, 0.014
80 mmol) was dissolved in distilled toluene (1 mL) and added to the
flask. Triethoxysilane (0.46 mL, 2.5 mmol) and Karstedt catalyst
(platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
solution (Pt ~2%) in xylene; 17.2 μL, 2.07 μmol) were added, and
the mixture was stirred in cold under argon. After 10 min, argon
85 was removed and after 1 h the stirring was continued at room
temperature for 3 h more. The crude product was evaporated
under reduced pressure using a mechanical vacuum pump.
Purification was done on Combiflash chromatograph using an
alumina column (12 g, purged with argon) eluting with
90 CHCl3/EtOH gradient (flow rate: 30 mL/min; CHCl3 (0.5 min),
CHCl3/EtOH 10:1 (2 min)). Product 6 was obtained as a dark
green solid (13 mg, 76%). δH(300 MHz; CDCl3; Me4Si): 0.51-
0.71 (2H, m, COC2H4CH2Si), 0.82-0.92 (6H, m, 22-H), 1.13-1.49
(29H, m, 17-21-H, Si(OCH2CH3)3), 1.65-1.86 (6H, m, 16-H,
95 COCH2CH2CH2Si), 1.88-2.31 (4H, m, c-H, b-H), 2.33-2.53 (2H,
m, COCH2C2H4Si), 3.64-3.91 (8H, m, Si(OCH2CH3)3, a-H), 4.11-
4.31 (4H, m, 15-H), 4.41-4.64 (2H, m, e-H), 4.77 (1H, br s, d-H),
7.34-7.41 (2H, m, 5″-H), 7.78-7.83 (1H, m, phenylene-H), 7.85-
7.98 (5H, m, 4″-H, 13-H, phenylene-H), 8.03 (2H, d, J 8.2, 6-H,
100 phenylene-H), 8.52-8.72 (5H, m, 3″-H, 7-H, 11-H, 14-H), 8.72-
8.77 (2H, m, 6″-H), 8.80 (2H, s, 3′-H), 8.83 (1H, s, 4-H). MS
(ESI-TOF, CH3CN): m/z = 1253.6212 [M+H]+ (calcd. for
C76H84N6O9Si 1253.6147).
Compound 3 (98 mg, 0.09 mmol) was dissolved in dry CH2Cl2 (5
mL) and stirred in an ice bath under a drying tube for 1 h. BBr3
(1M solution in CH2Cl2; 105 μL, 0.105 mmol) was added in five
different portions with an interval of 30 min. The progress of the
25 reaction was closely monitored by TLC analysis. After complete
consumption of the starting material (4 h), the reaction was
quenched by addition of MeOH (10 mL). The reaction mixture
was washed with water (3 × 40 mL) and the organic phase was
evaporated under reduced pressure. The crude product was
30 purified on Combiflash chromatograph using alumina column (12
g) eluting with CHCl3 (flow rate: 30 mL/min). Product 4 was
isolated as a dark green solid (87 mg, 97%). δH(300 MHz; CDCl3;
Me4Si): 0.78-0.94 (6H, m, 22-H), 1.17-1.52 (20H, m, 17-21-H),
1.69-1.82 (4H, m, 16-H), 1.83-2.06 (2H, m, b-H), 2.06-2.42 (2H,
35 m, c-H), 2.89 (1H, br s, OH), 3.42-3.68 (2H, m, a-H), 3.78-4.08
(2H, m, e-H), 4.09-4.32 (4H, m, 15-H), 4.47-4.66 (1H, m, d-H),
7.32-7.41 (2H, m, 5″-H), 7.54 (1H, d, J 7.9, 13-H), 7.62-7.71
(2H, m, phenylene-H), 7.85-7.94 (3H, m, 4″-H, phenylene-H),
7.99 (2H, d, J 8.2, 6-H, phenylene-H), 8.33-8.39 (1H, m, 7-H),
40 8.48 (1H, s, 11-H), 8.54 (1H, d, J 7.9, 14-H), 8.65-8.70 (2H, m,
3″-H), 8.70-8.75 (2H, m, 6″-H), 8.77 (2H, s, 3′-H), 8.81 (1H, s, 4-
H). MS (ESI-TOF, CH3CN): m/z = 1021.5068 [M+H]+ (calcd. for
C66H64N6O5 1021.5016).
(1-(12-(4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-2,9-dioctyl-
45 1,3,8,10-tetraoxo-1,2,3,8,9,10-hexahydroanthra[2,1,9-
def:6,5,10-d'e'f']diisoquinolin-5-yl)pyrrolidin-2-yl)methyl
but-3-enoate (5)
5,12-bis(4-([2,2':6',2''-terpyridin]-4'-yl)phenyl)-2,9-
105 dioctylanthra[2,1,9-def:6,5,10-d'e'f']diisoquinoline-
1,3,8,10(2H,9H)-tetraone (8)
Compound 4 (75 mg, 0.073 mmol) was dissolved in CH2Cl2 (5
mL). DCC (30 mg, 0.15 mmol), DMAP (4 mg, 0.03 mmol) and
50 3-butenoic acid (12.5 μL, 0.15 mmol) were added to the solution,
and the mixture was stirred at room temperature for 3.5 h. The
solvent was evaporated under reduced pressure. The crude
1,7-Dibromo-PDI
def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone]11, 19 (50
mg, 0.06 mmol), compound (62 mg, 0.14 mmol),
7
[5,12-dibromo-2,9-dioctylanthra[2,1,9-
1
product was dissolved in a few milliliters of EtOAc, the flask was 110 tetrabutylammonium chloride (4 mg, 0.013 mmol) and
frozen under cold water and filtered through a cotton plug. This
55 procedure was done twice. The product was purified on
Combiflash chromatograph using alumina column (12 g) eluting
with CHCl3 (flow rate: 30 mL/min) and second purification using
Pd(dppf)Cl2·CH2Cl2 (11 mg, 0.013 mmol) were dissolved in a
two-phase mixture of toluene (5 mL) and 1M K2CO3 (aq) (5 mL).
The reaction mixture was stirred at 90 °C for 18 h. The organic
phase was separated and washed with water (2 × 30 mL). The
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aqueous phase was extracted with toluene (2 × 10 mL) and the
organic layers were combined and evaporated under reduced
(12 g, purged with argon) eluting with CHCl3/EtOH gradient
(flow rate: 30 mL/min; CHCl3 (0.5 min), CHCl3/EtOH 20:1 (2
pressure. The product was purified on preparative TLC plate 60 min)). Product 11 was obtained as a dark green solid (10 mg,
(aluminium oxide), eluent CH2Cl2/CHCl3 2:1. Product 8 was
obtained as the second fraction (Rf = 0.4 in CH2Cl2/CHCl3 2:1) as
a dark red solid (19 mg, 23%). UV-vis λmax(CHCl3)/nm 284
(ε/dm3 mol-1 cm-1 67790) and 556 (25610). δH(300 MHz; CDCl3;
56%). δH(300 MHz; CDCl3; Me4Si): 0.51-0.72 (2H, m,
COC2H4CH2Si), 0.81-0.92 (6H, m, 22-H), 1.12-1.50 (29H, m, 17-
5
21-H,
Si(OCH2CH3)3),
1.65-1.84
(6H,
m,
16-H,
COCH2CH2CH2Si), 1.86-2.41 (8H, m, c-H, b-H, i-H, j-H), 2.41-
Me4Si): 0.78-0.95 (6H, m, 22-H), 1.16-1.50 (20H, m, 17-21-H), 65 2.58 (2H, m, COCH2C2H4Si), 3.53-3.96 (12H, m, Si(OCH2CH3)3,
1.65-1.85 (4H, m, 16-H), 4.02-4.29 (4H, m, 15-H), 7.33-7.45
a-H, h-H, k-H), 4.21 (4H, t, J 7.5, 15-H), 4.36-4.77 (3H, m, d-H,
e-H), 7.66 (1H, d, J 7.9, 13-H), 8.12-8.27 (1H, m, 6-H), 8.31-8.55
(3H, m, 4-H, 7-H, 14-H), 8.59-8.72 (1H, m, 11-H). MS (ESI-
TOF, CH3CN): m/z = 1014.5597 [M]+ (calcd. for C59H78N4O9Si
10 (4H, m, 5″-H), 7.62 (2H, d, J 7.3, phenylene-H), 7.74 (2H, d, J
7.3, phenylene-H), 7.86-7.98 (6H, m, 4″-H, 6-H, 13-H), 8.01-8.11
(4H, m, phenylene-H), 8.15-8.26 (2H, m, 7-H, 14-H), 8.65-8.79
(10H, m, 3″-H, 6″-H, 4-H, 11-H), 8.80-8.87 (4H, m, 3′-H). MS 70 1014.5538).
(ESI-TOF, CHCl3/MeOH 10:15): m/z = 1229.5481 [M+H]+
15 (calcd. for C82H68N8O4 1229.5442).
Complexes
Zn(OTf)2-solution: zinc(II) trifluoromethanesulfonate (36 mg, 0.1
mmol) was dissolved in CHCl3/CH3CN 4:1 (10 mL) by
sonication.
75 Complex Zn-3
(1-(2,9-dioctyl-1,3,8,10-tetraoxo-12-(pyrrolidin-1-yl)-
1,2,3,8,9,10-hexahydroanthra[2,1,9-def:6,5,10-
d'e'f']diisoquinolin-5-yl)pyrrolidin-2-yl)methyl but-3-enoate
(10)
Compound
3 (10 mg, 0.009 mmol) was dissolved in
20 Pyrrolidine-PDI
9
[5-(2-(hydroxymethyl)pyrrolidin-1-yl)-2,9-
CHCl3/CH3CN 4:1 (5 mL) and Zn(OTf)2-solution (0.9 mL, 0.009
mmol) was added. The reaction mixture was stirred at room
temperature for 1h. The solvent was evaporated under reduced
80 pressure. Product Zn-3 was obtained as a dark green solid with
quantitative yield (13 mg). UV-vis λmax(CHCl3)/nm 288 (ε/dm3
mol-1 cm-1 49120), 397 (13250), 438 (11950) and 663 (21460).
δH(300 MHz; CDCl3; Me4Si): 0.76-0.95 (6H, m, 22-H), 1.19-1.51
(20H, m, 17-21-H), 1.63-1.83 (4H, m, 16-H), 1.95-2.08 (2H, m,
85 b-H), 2.12-2.38 (2H, m, c-H), 3.41-3.69 (2H, m, a-H), 3.74-4.10
(2H, m, e-H), 4.10-4.33 (4H, m, 15-H), 4.55-4.82 (3H, m, d-H, f-
H), 7.28-7.50 (5H, m, g-H), 7.62-7.73 (2H, m, 13-H, phenylene-
H), 7.74-7.82 (2H, m, 5″-H), 7.83-7.98 (2H, m, 6-H, phenylene-
H), 8.07-8.29 (4H, m, 4″-H, phenylene-H), 8.35-8.49 (2H, m, 7-
90 H, 14-H), 8.51-8.64 (4H, m, 3′-H, 3″-H, 4-H, 11-H), 8.72-8.81
(1H, m, 3″-H), 8.83-8.92 (2H, m, 6″-H), 8.96-9.05 (1H, m, 3′-H).
MS (ESI-TOF, CH3CN): m/z = 1323.4382 [M-OTf]+ (calcd. for
dioctyl-12-(pyrrolidin-1-yl)anthra[2,1,9-def:6,5,10-
d'e'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone]18 (30 mg, 0.04
mmol) was dissolved in CH2Cl2 (5 mL). DCC (16 mg, 0.08
mmol), DMAP (2 mg, 0.015 mmol) and 3-butenoic acid (6.5 μL,
25 0.08 mmol) were added to the solution, and the mixture was
stirred at room temperature for 20 h. The solvent was evaporated
under reduced pressure. The crude product was dissolved in a few
milliliters of EtOAc, the flask was frozen under cold water and
filtered through a cotton plug. This procedure was done twice.
30 The product was purified by column chromatography on Silica
60, eluting with CHCl3. Product 10 was obtained as a dark green
solid (32 mg, 99%). UV-vis λmax(CHCl3)/nm 272 (ε/dm3 mol-1
cm-1 17040), 434 (11230) and 696 (26120). δH(300 MHz; CDCl3;
Me4Si): 0.77-0.90 (6H, m, 22-H), 1.15-1.48 (20H, m, 17-21-H),
35 1.59-1.78 (4H, m, 16-H), 1.88-2.37 (8H, m, c-H, b-H, i-H, j-H),
3.19 (2H, d, J 6.2, COCH2), 3.48-3.98 (6H, m, a-H, h-H, k-H),
4.17 (4H, t, J 7.3, 15-H), 4.41-4.69 (3H, m, d-H, e-H), 5.07-5.25
(2H, m, CH=CH2), 5.80-6.03 (1H, m, CH=CH2), 7.44-7.57 (1H,
m, 13-H), 8.10 (1H, d, J 8.2, 6-H), 8.16-8.44 (3H, m, 4-H, 7-H,
40 14-H), 8.58 (1H, s, 11-H). MS (ESI-TOF, CHCl3/MeOH 10:15):
m/z = 850.4658 [M]+ (calcd. for C53H62N4O6 850.4669).
C74H70F3N6O8SZn 1323.4220).
Complex 3-Zn-3a
95 Compound
3 (10 mg, 0.009 mmol) was dissolved in
CHCl3/CH3CN 4:1 (5 mL) and complex Zn-3 (13 mg, 0.009
mmol) was added. The reaction mixture was stirred at room
temperature for 1h. The solvent was evaporated under reduced
pressure. Product 3-Zn-3a was obtained as a dark green solid
100 with quantitative yield (23 mg). UV-vis λmax(CHCl3)/nm 288
(ε/dm3 mol-1 cm-1 85990), 402 (25290), 439 (23650) and 666
(40230). δH(300 MHz; CDCl3; Me4Si): 0.75-0.92 (12H, m, 22-H),
1.17-1.50 (40H, m, 17-21-H), 1.61-1.82 (8H, m, 16-H), 1.91-2.07
(4H, m, b-H), 2.10-2.38 (4H, m, c-H), 3.38-3.67 (4H, m, a-H),
105 3.72-4.35 (12H, m, 15-H, e-H), 4.53-4.83 (6H, m, d-H, f-H),
7.30-7.51 (14H, m, 5″-H, g-H), 7.54-7.71 (4H, m, 13-H,
phenylene-H), 7.77-7.98 (8H, m, 6-H, 6″-H, phenylene-H), 8.00-
8.20 (8H, m, 4″-H, phenylene-H), 8.29-8.45 (4H, m, 7-H, 14-H),
8.46-8.64 (4H, m, 4-H, 11-H), 8.71-8.85 (4H, m, 3″-H), 8.94-9.08
110 (4H, m, 3′-H). MS (ESI-TOF, CH3CN): m/z = 2433.9680 [M-
OTf]+ (calcd. for C147H140F3N12O13SZn 2433.9626).
(1-(2,9-dioctyl-1,3,8,10-tetraoxo-12-(pyrrolidin-1-yl)-
1,2,3,8,9,10-hexahydroanthra[2,1,9-def:6,5,10-
d'e'f']diisoquinolin-5-yl)pyrrolidin-2-yl)methyl
4-
45 (triethoxysilyl)butanoate (11)
All the glassware was dried in oven (150 °C, 2 h) before use. The
reaction flask was sealed with a septum, placed on an ice bath,
and kept under constant argon flow. Compound 10 (15 mg, 0.018
mmol) was dissolved in distilled toluene (1 mL) and added to the
50 flask. Triethoxysilane (0.46 mL, 2.5 mmol) and Karstedt catalyst
(platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex
solution (Pt ~2%) in xylene; 7.3 μL, 0.88 μmol) were added, and
the mixture was stirred in cold under argon. After 10 min, the
stirring was continued at room temperature without constant
55 argon flow for 2 h. The crude product was evaporated under
reduced pressure using a mechanical vacuum pump. Purification
was done on Combiflash chromatograph using alumina column
Complex 3-Zn-3b
Compound
3 (10 mg, 0.009 mmol) was dissolved in
CHCl3/CH3CN 4:1 (5 mL) and Zn(OTf)2-solution (0.45 mL,
115 0.0045 mmol) was added. The reaction mixture was stirred at
8
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DOI: 10.1039/C3OB41058G
Page 9 of 10
Organic & Biomolecular Chemistry
room temperature for 1h. The solvent was evaporated under
ions. Zn-solution: zinc(II) trifluoromethanesulfonate (36 mg, 0.1
reduced pressure. Product 3-Zn-3b was obtained as a dark green 60 mmol) was dissolved in CHCl3/CH3CN 4:1 (10 mL) by
solid with quantitative yield (12 mg). UV-vis λmax(CHCl3)/nm
288 (ε/dm3 mol-1 cm-1 89130), 403 (26730), 442 (24770) and 666
(41100). δH(300 MHz; CDCl3; Me4Si): 0.77-0.90 (12H, m, 22-H),
1.16-1.50 (40H, m, 17-21-H), 1.62-1.83 (8H, m, 16-H), 1.94-2.08
sonication. For complexation the stock solution (3.6 mL) was
diluted with CHCl3/CH3CN 4:1 (20 mL). The plates with SAMs
were immersed in the salt solution and kept there for 1h. After an
appropriate time, the plates were washed with CHCl3/CH3CN 4:1,
5
(4H, m, b-H), 2.11-2.39 (4H, m, c-H), 3.40-3.68 (4H, m, a-H), 65 and the samples were dried in argon flow.
3.73-4.30 (12H, m, 15-H, e-H), 4.54-4.80 (6H, m, d-H, f-H),
7.28-7.51 (14H, m, 5″-H, g-H), 7.58-7.73 (4H, m, 13-H,
Conclusions
10 phenylene-H), 7.79-8.00 (8H, m, 6-H, 6″-H, phenylene-H), 8.01-
8.24 (8H, m, 4″-H, phenylene-H), 8.33-8.46 (4H, m, 7-H, 14-H),
8.50-8.64 (4H, m, 4-H, 11-H), 8.72-8.83 (4H, m, 3″-H), 8.96-9.07
(4H, m, 3′-H),. MS (ESI-TOF, CH3CN): m/z = 2433.9766 [M-
OTf]+ (calcd. for C147H140F3N12O13SZn 2433.9626).
15 Complex Zn-8
We have synthesized PDIs with terpyridine groups and silane
anchors at the bay-region. Both of these groups are rarely found
in this position of PDIs. Supramolecular dimer and trimer
70 structures were constructed from the monomers via the
terpyridine moieties and zinc ions. A trimer complex showed
efficient energy transfer from the middle PDI to the side PDIs.
The silane-containing PDIs were attached on the quartz substrate
and coordination of zinc was also done on the surface. Formation
75 of the complex was observed clearly in steady-state absorption
measurements. The molecular films were not obtained as perfect
monolayers, but demonstrate the potential to construct
supramolecular assemblies of PDI directly on a solid substrate.
This implies that attention should be paid on the surface-PDI
80 tether, and these studies are currently under way.
Compound
8 (10 mg, 0.008 mmol) was dissolved in
CHCl3/CH3CN 4:1 (5 mL) and Zn(OTf)2-solution (1.6 mL, 0.016
mmol) was added. The reaction mixture was stirred at room
temperature for 1h. The solvent was evaporated under reduced
20 pressure. Product Zn-8 was obtained as a dark red solid with
quantitative yield (16 mg). UV-vis λmax(CHCl3)/nm 288 (ε/dm3
mol-1 cm-1 47680), 338 (28780) and 553 (13980). δH(300 MHz;
CDCl3; Me4Si): 0.84-0.92 (6H, m, 22-H), 1.25-1.48 (20H, m, 17-
21-H), 1.70-1.88 (4H, m, 16-H), 3.97-4.36 (4H, m, 15-H), 7.70-
25 7.89 (5H, m, phenylene-H), 7.92-8.03 (5H, m, 5″-H, phenylene-
H), 8.18-8.49 (12H, m, 4″-H, 4-H, 6-H, 7-H, 11-H, 13-H, 14-H,
phenylene-H), 8.88-9.02 (8H, m, 3″-H, 6″-H), 9.11 (4H, s, 3′-H).
MS (ESI-TOF, CH3CN): m/z = 1803.2660 [M-OTf]+ (calcd. for
C85H68F9N8O13S3Zn2 1803.2507).
Acknowledgments
Graduate School of Tampere University of Technology and
Academy of Finland are greatly acknowledged for financial
support.
30 Complex 3-Zn-8
Complex Zn-8 (16 mg, 0.008 mmol) and compound 3 (20 mg,
0.018 mmol) were dissolved in DMF (7 mL). The reaction
mixture was stirred at room temperature for 2h. The solvent was
evaporated under reduced pressure using a mechanical vacuum
35 pump. Product 3-Zn-8 was obtained as a dark green solid with
quantitative yield (34 mg). UV-vis λmax(CHCl3)/nm 288 (ε/dm3
mol-1 cm-1 118050), 389 (42710), 439 (31690) and 666 (48620).
δH(300 MHz; CDCl3; Me4Si): 0.76-0.95 (18H, m, 22-H), 1.15-
1.52 (60H, m, 17-21-H), 1.62-1.83 (12H, m, 16-H), 1.93-2.08
40 (4H, m, b-H), 2.13-2.30 (4H, m, c-H), 3.41-3.68 (4H, m, a-H),
3.76-4.37 (16H, m, 15-H, e-H), 4.55-4.86 (6H, m, d-H, f-H),
7.29-7.51 (17H, m), 7.54-7.80 (11H, m), 7.82-8.00 (11H, m),
8.02-8.28 (15H, m), 8.31-8.67 (15H, m), 8.70-8.94 (9H, m), 8.96-
9.27 (6H, m). MS (ESI-TOF, CH3CN): m/z = 1937.6973 [M-
45 2(OTf)]2+ (calcd. for C230H206F6N20O20S2Zn2 1937.6901).
85 Notes and references
a Department of Chemistry and Bioengineering, Tampere University of
Technology, P.O. Box 541, 33101 Tampere, Finland. Fax: +358 3 364
1392; Tel: +358 40 198 1124; E-mail: essi.sariola-leikas@tut.fi
90 † Electronic Supplementary Information (ESI) available: Fluorescence
decays of PDI 8 and PDI 3. 1H NMR, 13C NMR and gHSQC NMR
spectra of compounds 1, 3-6, 8, 10 and 11. 1H NMR spectra of complexes
Zn-3, Zn-8, 3-Zn-3a, 3-Zn-3b and 3-Zn-8. Mass spectra of complexes 3-
Zn-3b and 3-Zn-8. See DOI: 10.1039/b000000x/
95
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Immobilization and complexation
Quartz plates were cleaned according to the process reported
earlier.4 The reaction vessel was cooled down after being in oven
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5
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