Chromophores arranged as "magnetic meta atoms": Building blocks for molecular metamaterials

Article abstract of DOI:10.1021/jo4005662

Benzoperylenetriscarboximides were parallel arranged by stiff spacers where exciton interactions could be controlled by their distance. The most bathochromic electronic transition of the chromophores essentially exhibits only an electric component where a

Full text of DOI:10.1021/jo4005662

Article
pubs.acs.org/joc
Chromophores Arranged as “Magnetic Meta Atoms”: Building Blocks
for Molecular Metamaterials
Heinz Langhals* and Alexander Hofer
Department of Chemistry, LMU University of Munich, Butenandtstrasse 13, D-81377 Munich, Germany
S
* Supporting Information
ABSTRACT: Benzoperylenetriscarboximides were parallel arranged by stiff spacers where
exciton interactions could be controlled by their distance. The most bathochromic electronic
transition of the chromophores essentially exhibits only an electric component where an
orthogonal magnetic component was established by the distance-controlled interaction of
chromophores. Such arrangements were discussed as building blocks for molecular
metamaterials.
INTRODUCTION
■
Metamaterials1 are attracting more interest in science and
technology because special interactions with electromagnetic
waves can be expected. Such materials were created for
microwave radiation and allowed the generation of devices with
unusual properties, such as negative indices of refraction2 where
applications for camouflage3 are the most prominent. Unusual
optical properties can be expected from the creation of
metamaterials in the visible spectrum.
The orthogonal arrangement of the electric and magnetic
components of the interaction with electromagnetic radiation is
typical for metamaterials. This was realized for microwaves with
a periodically ordered framework of specially formed electric
conductors formally forming “magnetic meta atoms”. U-shaped
conductors were applied where two vertical lines of the U form
Figure 1. Left: U-shaped conductor for metamaterials. μe = electrical
dipole; μm = orthogonal magnetic dipole. Right: Transversal coupling
of two conductors and dielectric displacement current inducing a
magnetic moment for metamaterials.
electrical dipoles and the interlinking bow of the U a pathway
for the generation of an orthogonal magnetic component; see
Figure 1, left. A strong coupling between coplanar oriented
linear anti-operating oscillators4 would be an alternative where
the orthogonal magnetic component is induced by the
dielectric displacement current; see Figure 1, right.
π−π* transition in the visible region polarized along the
molecular long axis (Chart 1).9 As a consequence, the electric
component of light absorption dominates and parasitic
magnetic components become unimportant. We targeted to
introduce magnetic components by exciton interactions in
multichromophores composed of parallel arranged 1.
We tried to reduce the size of such components down to the
molecular scale by the exchange of the electric conductors with
conjugated π-systems where electrons are as mobile as in
metallic wires.5 The resonances of the metallic oscillators
become equivalent to the eigenvalues of the π-systems. The
transversal coupling according to Figure 1, right, corresponds to
a H arrangement of chromophores6 (compare exciton coupling
and Scheibe’s H-aggregates7). Suitable chromophores and
spacers are required as building blocks for such complex
structures.
RESULTS AND DISCUSSION
■
The solubility of complex multichromophores with basic
structures of 1 is expected to be very low and interferes with
UV/vis spectroscopic investigations. As a consequence, the
solubility-increasing 1-hexylheptyl substituent10 was attached to
We used benzoperylenetriscarboximides8 1 as resonating
components because there is only one very pure electronic
Received: March 18, 2013
© XXXX American Chemical Society
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caused by steric effects of the carbonyl groups; see Scheme 1.
Analogously, 1,4-diamino-2,3,5,6-tetramethylbenzene was al-
lowed to react with12 3 and further with 2 to form the
trichromophore 7 with a longer spacer with extra stiffness by
steric effects of the methyl groups. Perylenetetracarboxylic
bisanhydride (8) was similarly condensed with hydrazine for
the preparation13,14 of 9 with a long, bathochromically
absorbing aromatic spacer, and finally condensed with 1,4-
diamino-2,3,5,6-tetramethylbenzene to obtain the arrangement
12 with a very long spacer. Material 14 with a flexible spacer
was obtained in a similar way. As an alternative, the anhydride 2
was condensed with hydrazine and diaminotetramethylbenzene
to form the amino derivatives 15 and 16, respectively (Chart
2). A further condensation with naphthalene-1,8:4,5-tetra-
carboxylic bisanhydride (3) and perylene-3,4:9,10-tetra-
carboxylic bisanhydride (8) gave the corresponding trichromo-
phores in similar yields; however, preparation procedures and
purification proved to be more laborious.
Chart 1. Benzoperylenetriscarboximides 1 and Anhydride 2
as Building Blocks for Synthesis
the nitrogen atoms of the six-membered ring carboximides
where the five-membered ring carboximide was used for the
interlinking between chromophores. The anhydride8 2 was a
good starting material for synthesis where 1 can be obtained by
the condensation with primary amines.
First, naphthalenetetracarboxylic anhydride (3) was con-
densed with hydrazine to form N,N′-diaminonaphthalene-
carboximide11 (4) as a reactive spacer and further condensed
with 2 to give the trichromophore 5 with parallel units of 1
Chiral derivatives of 1 were prepared in order to investigate
the importance of magnetic components for the electronic
transitions; compare ref 15. 2 was condensed with an excess of
diaminodimethylbiphenyl16 to prepare the monochromophore
17 with an axially chiral biphenyl at the periphery. The
condensation of the diamine with an excess of the anhydride
allowed the preparation of the chiral dyad 18 (Chart 3).
Scheme 1. Synthesis of the Arrangements 5, 7, 10, 12, and 14 (R = 1-Hexylheptyl): (i) N2H4·H2O, Imidazole; (ii) Quinoline
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Chart 2. Amino Intermediates 15 and 16
Figure 2. UV/vis absorption and fluorescence spectra in chloroform.
Dashed absorption (left) and fluorescence (right) spectra of 1. Dotted
lines: Absorption spectrum of N,N′-bis-1-methylpropylnaphthalene-
1,8:4,5-tetracarboxylic bisimide. Solid lines: Absorption (left) and
fluorescence (right) spectra of 5 (spacer 1).
The UV/vis absorption of 1 is strongly structured with a
maximum of about 470 nm where fluorescence is mirror-type;
see Figure 2, dashed line. The UV/vis spectra of the chiral dye
17 were examined for an estimation of electric (μe) and
parasitic magnetic (μm) components of the electronic transition
in the visible range.17 The absorption and fluorescence spectra
of 17 were essentially identical with the spectra of 1; see dashed
lines in the inset in Figure 3. The CD spectrum of 17
represents the baseline of the spectrometer and is an indication
that there is no significant parasitic magnetic component in the
electronic transition. As a consequence, the electronic transition
in the visible region is a very pure π−π* type with μe. Thus, no
interfering magnetic component of the electronic transition can
be expected. We tested the introduction of magnetic
components (μm) into the transition by means of exciton
interactions in the dyad 18 by the sandwich-like chiral
arrangement. The thus-induced magnetic component μm is
indicated by the strong CD effects with Δε of about −250,
where the negative CD effect is consistent with a (P) geometry
of 18; see Figure 3, solid line. The dihedral angle of the
biphenyl with regard to the nitrogen atoms in 18 is less than
90°, and the electric transition moment is parallel to the long
axis of the chromophore. The bonds to the five-ring nitrogen
atoms of the chromophores are orthogonal to the transition
moments. As a consequence, the angle between the transition
moments is more than 90° and is thus verified by the observed
negative CD effect.
Figure 3. UV/vis absorption (dashed on the left) and fluorescence
spectra (dashed on the right) of 18 and the CD spectrum (solid line)
in chloroform. Inset: Spectra of 17; the CD spectrum is essentially the
baseline.
Two parallel electric transition moments μe according to
Figure 1 are realized by the stiff arrangement of benzoperylene
chromophores 1 to form a H-type geometry in 5 with a
distance of about 22 Å (spacer 1). Exciton interactions cause a
perpendicular magnetic component μm; the consequences of
such interactions can be seen in the absorption spectrum in
Chart 3. Chiral benzoperylenetriscarboximide 17 and Chiral Dyad 18
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Figure 2 (solid line). The most bathochromic absorption of 5
(>400 nm) is more intense than that in 1; however, it does not
reach twice the intensity as would be expected from a simple
additive effect of the individual chromophores. Thus, the
exciton interaction is destructive to the efficiency of light
absorption. The individual bands are slightly hypsochromically
shifted, and the bandwidth is diminished. On the other hand, an
extraordinarily sharp absorption at 380 nm into a higher excited
state becomes dominant, partially overlaid by the naphthalene
biscarboximide; sharp resonances are typical for metamaterials
(see ref 18). Parallel oriented perylenecarboximides in
substituted xanthenes in positions 4 and 5 were previously
reported;19 however, there was no sharp hypsochromic
absorptions; the spectra resemble more of a skew-type
arrangement of chromophores.19 On the other hand, the
intensity of the sharp absorption of 5, ε = 162 000, exceeds the
sum of the absorption of the involved chromophores by far
(dotted and dashed lines in Figure 2). The high ε value may be
partially caused by the unusually low half-width of the line
where the integral represents the intensity of the transition. The
geometry of 5 corresponds to a perfect H arrangement of the
chromophores of 1 and should not exhibit fluorescence
Figure 5. UV/vis absorption and fluorescence spectra in chloroform.
Solid lines: Absorption (left) and fluorescence (right) spectra of 10
(spacer 3). Dashed lines: Absorption (left) and fluorescence (right)
spectra of 1. Dotted lines: Absorption and fluorescence spectra of
N,N′-bis-1-hexylheptylperylene-3,4:9,10-tetracarboxylic bisimide.
components of 10 in this spectral region. The fluorescence of
the chromophore 1 in 10 is completely quenched, and efficient
energy transfer to the more bathochromically absorbing central
perylenebiscarboximide unit is observed as indicated by a
fluorescence quantum yield close to unity of the latter if the
former is excited at 436 nm. This is remarkable because electric
transition moments are orthogonal and the energy transfer
according to Forster’s concept. On the other hand, a broad
̈
bathochromically shifted fluorescence band with a quantum
yield of 0.2 is observed. We interpret these results as a
consequence of a relaxation of the excited state to intra-
molecular excimers with skew transition moments; compare ref
20.
forbidden by Forster’s theory; compare ref 21.
̈
The introduction of further tetramethylphenylene spacers in
12 (spacer 4) separates the two chromophores of 1 by 34 Å
(distance of the N−N connection lines of the six-membered
ring carboximides). Exciton interactions become weaker
because of the large distance; however, they are still present
as can be seen at the band at 375 nm (Figure 6). Energy
transfer proceeds as efficiently as in 10 so that a quantum
efficiency of close to unity is obtained.
The longer still stiff spacer in 7 separates the transition
moments to 30 Å. As a consequence, exciton interactions
become weaker and the UV/vis spectrum is more close to an
addition of the spectra of the involved chromophores (Figure
4). There is only a slight effect of diminishing the most
Figure 4. UV/vis absorption and fluorescence spectra in chloroform.
Solid lines: Absorption (left) and fluorescence (right) spectra of 7
(spacer 2). Dashed lines: Absorption (left) and fluorescence (right)
spectra of 1. Dotted lines: Absorption spectrum of N,N′-bis-1-
methylpropylnaphthalene-1,8:4,5-tetracarboxylic bisimide.
Figure 6. UV/vis absorption and fluorescence spectra in chloroform.
Solid lines: Absorption (left) and fluorescence (right) spectra of 12
(spacer 4). Dashed lines: Absorption (left) and fluorescence (right)
spectra of 1. Dotted lines: Absorption and fluorescence spectra of
N,N′-bis-1-hexylheptylperylene-3,4:9,10-tetracarboxylic bisimide.
bathochromic absorption. The sharp intense absorption at 380
nm still exists as the most intense absorption, but it exceeds
only slightly the band at 465 nm.
The perylenetetracarboxbismide in 10 forms a slightly
shorter spacer of 26 Å compared with the latter (spacer 3).
The absorption at 465 nm is still slightly diminished with
respect to the sum of the components (Figure 5). The apparent
absorption at 377 nm is much less pronounced than that for 5
and 7; however, it is essentially caused by exciton interactions
because light absorption is weak for all chromophoric
The introduction of the long, flexible spacer in 14 changes
the spectroscopic behavior fundamentally (spacer 5). The
exciton-induced band at 374 nm is still present; however, the
absorptivities are generally appreciably lowered (Figure 7). The
absorption at 464 nm of two chromophores is even lower than
that of a single chromophore, and similarly, the absorptivity of
the centrally linking perylenecarboximide is remarkably low,
where only 1/4 of the absorptivity of isolated chromophores is
D
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526 mg (95%) ochre solid, mp >300 °C; Rf (silica gel, chloroform)
0.00; MS (DEP/EI) m/z (%) 297.2 (15) [M+ + H], 296.2 (100) [M+],
294.2 (11), 281.2 (24), 267.2 (47), 266.2 (14), 252.2 (16), 238.2 (15),
181.1 (11).
2,7-Bis-(4-amino-2,3,5,6-tetramethylphenyl)benzo[lmn][3,8]-
phenanthrolin-1,3,6,8-tetraone (6, Spacer 2). Isochromeno[6,5,4-
def ]isochromen-1,3,6,8-tetraone (3, 2.00 g, 7.46 mmol) was dissolved
in melt imidazole (10 g), treated with 2,3,5,6-tetramethylbenzene-1,4-
diamine (3.06 g, 18.6 mmol), stirred at 110 °C for 17 h, allowed to
cool, precipitated with 2 M aqueous HCl (500 mL), collected by
vacuum filtration (D4 glass filter), washed with 2 M aqueous HCl and
distilled water, and dried at 110 °C for 16 h: Yield 4.2 g (98%) ochre
solid, mp >300 °C; MS (MALDI, anthracene) m/z: 560.4 [M+].
Figure 7. UV/vis absorption and fluorescence spectra in chloroform.
Solid lines: Absorption (left) and fluorescence (right) spectra of 14
(spacer 5). Dashed lines: Absorption (left) and fluorescence (right)
spectra of 1. Dotted lines: Absorption and fluorescence spectra of
N,N′-bis-1-hexylheptylperylene-3,4:9,10-tetracarboxylic bisimide.
reached. Both line type and absorptivity remain unchanged if
the solution of 14 is diluted. We interpret this result as a
consequence of internal aggregation-like interaction of the
involved chromophores. The second hypsochromic vibronic
band of the central unit is as well amplified as the mirror-type
fluorescent band. Such effects and diminished absorptivity are
typical for H-type aggregation of chromophores. Moreover, the
fluorescence quantum yield of 75% is still high, however, it is
appreciably lower than for 7 or 10; this is a further indicator for
H-type arrangements of chromophores.
Finally, multichromophoric systems with orthogonal electric
and magnetic transition moments such as 5, 7, 10, and 12 have
to be regularly arranged in space to obtain macroscopic optical
metamaterials. This may be successful by the application of
liquid crystals.
2,9-Diaminoanthra[2,1,9-def;6,5,10-d′e′f′]diisoquinolin-1,3,8,10-
tetraone (9, Spacer 3). Perylene-3,4:9,10-tetracarboxylic bisanhydride
(8, 1.00 g, 2.55 mmol) and imidazole (5 g) were heated at 100 °C,
treated with hydrazine hydrate (417 mg, 0.013 mmol), stirred at 100
°C for 5 h, allowed to cool, precipitated with 2 M aqueous HCl (300
mL), collected by vacuum filtration (D4 glass filter), washed with 2 M
aqueous HCl and distilled water, and dried at 110 °C for 16 h: Yield
̃
1.05 g (95%) red solid, mp >300 °C; IR (ATR: ν = 3258.6 (w), 1733.0
(w), 1699.7 (vs), 1662.2 (s), 1633.2 (w), 1593.8 (s), 1575.8 (m),
1558.2 (m), 1505.5 (w), 1456.3 (w), 1436.3 (w), 1417.1 (w), 1401.4
(m), 1368.2 (m), 1253.9 (m), 1174.3 (m), 1123.7 (w), 976.4 (w),
959.2 (w), 901.6 (w), 805.7 (vs), 798.0 (w), 791.7 (w), 747.9 (w),
733.5 (vs), 663.7 cm−1 (w); MS (DEP/EI) m/z (%) 420.1 (12) [M+],
97.1 (12), 83.1 (12), 69.1 (27), 67.1 (11), 57.1 (19), 56.1 (12), 55.1
(20), 44.0 (100), 43.0 (24), 41.0 (26); HRMS (FAB+, quadrupole,
C24H12N4O4) calcd m/z 420.0859, found m/z 420.0863, Δ = −0.0004.
CONCLUSIONS
■
Molecular components for metamaterials in the visible region
can be constructed by a stiff arrangement of parallel oriented
chromophores with dominating π−π* transitions. Exciton
interactions introduce orthogonal magnetic components
controlled by the intramolecular distance; the smallest spacer
in H-shaped arrangements given in compound 5 seems to be
the most promising candidate for metamaterials. Flexible
spacers cause a more complex behavior where intramolecular
aggregation-like interaction is observed. A combination of
various chromophores allows intramolecular energy transfer
processes, although the electronic transition moments are
orthogonally arranged.
2,9-Bis-(4-amino-2,3,5,6-tetramethylphenyl)anthra[2,1,9-
def;6,5,10-d′e′f′]diisoquinolin-1,3,8,10-tetraone (11, Spacer 4).
Perylene-3,4:9,10-tetracarboxylic bisanhydride (8, 1.00 g, 2.55 mmol)
in imidazole (10 g) was heated at 140 °C, treated with 2,3,5,6-
tetramethylbenzene-1,4-diamine (2.10 g, 12.8 mmol), stirred at 140 °C
for 4 h, allowed to cool, precipitated with 2 M aqueous HCl (300 mL),
collected by vacuum filtration (D4 glass filter), washed with 2 M
aqueous HCl and distilled water, and dried at 110 °C for 16 h: Yield
1.66 g (95%) red solid, mp >300 °C; Rf (silica gel, chloroform/ethanol
20:1) 0.36; UV/vis (CHCl3) λmax (Erel) = 461.4 (0.23), 489.8 (0.61),
526.6 nm (1.00); fluorescence (CHCl3, λexc = 490 nm) λmax (Irel) =
531.8 (1.00), 574.6.0 nm (0.55); fluorescence quantum yield (CHCl3,
λexc = 490 nm, E490nm/1cm = 0.0992, reference S-13 with Φ = 1.00) 0.10;
MS (DEP/EI) m/z (%) 686.3 (11) [M+ + 2H] 685.3 (21) [M+ + H],
684.3 (62) [M+], 149.1 (40), 148.1 (40), 147.1 (100), 134.1 (42),
132.1 (15), 105.1 (12), 91.1 (21), 77.0 (12), 55.1 (10), 44.0 (56), 41.1
(13); HRMS (FAB+, quadrupole, C44H36N4O4) calcd m/z 684.2737,
found m/z 684.2737, Δ = 0.0000.
EXPERIMENTAL SECTION
General. All FAB spectra were recorded in 3-nitrobenzylalcohol as
the matrix.
■
2,7-Diaminobenzo[lmn][3,8]phenanthrolin-1,3,6,8-tetraone (4,
Spacer 1). Isochromeno[6,5,4-def ]isochromen-1,3,6,8-tetraone (3,
500 mg, 1.87 mmol) was dissolved in melt imidazole (5 g), treated
with hydrazine hydrate (234 mg, 4.68 mmol), stirred at 100 °C for 17
h, allowed to cool, precipitated with 2 M aqueous HCl (300 mL),
collected by vacuum filtration (D4 glass filter), washed with 2 M
aqueous HCl and distilled water, and dried at 110 °C for 16 h: Yield
2,9-Bis-(4-aminobutyl)anthra[2,1,9-def;6,5,10-d′e′f ′]diiso-
quinolin-1,3,8,10-tetraone (13, Spacer 5). Perylene-3,4:9,10-tetra-
carboxylic bisanhydride (8, 1.00 g, 2.55 mmol) was heated with
E
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imidazole (10 g) at 140 °C, treated with butan-1,4-diamine (1.13 g,
12.8 mmol), stirred at 140 °C for 4 h, allowed to cool, precipitated
with 2 M aqueous HCl (300 mL), collected by vacuum filtration (D4
glass filter), washed with 2 M aqueous HCl and distilled water, and
dried at 110 °C for 16 h: Yield 1.20 g (95%) red solid, mp >250 °C;
MS (MALDI, anthracene) m/z 533.6 [M+ + H].
N,N′′-Bis(1-hexylheptyl)-N′-(4-amino-2,3,5,6-tetramethylphenyl)-
benzo[ghi]perylene-2,3,8,9,11,12-hexacarboxylic-2,3,8,9-bis-
(dicarboximide)-11,12-dicarboximide (16). 2,10-Bis(1-hexylheptyl)-
furo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f ′]diisoquinoline-
1,3,5,7,9,11(2H,10H)-hexone (2, 300 mg, 0.353 mmol) and 2,3,5,6-
tetramethylbenzene-1,4-diamine (290 mg, 1.77 mmol) in quinoline
were heated at 160 °C for 12 h, allowed to cool, treated with 2 M
aqueous HCl (40 mL), and extracted three times with chloroform.
The combined organic phases were dried with magnesium sulfate,
evaporated, and purified by column separation (silica gel 40−63 μm,
toluene): Yield 446 mg (76%) brownish yellow solid, mp >250 °C; Rf
N,N′’-Bis(1-hexylheptyl)-N′-(amino)benzo[ghi]perylene-
2,3,8,9,11,12-hexacarboxylic-2,3,8,9-bis(dicarboximide)-11,12-
imide (15). Method 1: 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno-
[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone
(2, 300 mg, 0.360 mmol) and hydrazine hydrate (88.6 mg, 1.77 mmol)
in imidazole (2.5 g) were stirred at 120 °C for 4 h, allowed to cool,
precipitated with 2 M aqueous HCl (40 mL), collected by vacuum
filtration (D4 glass filter), washed with 2 M aqueous HCl and distilled
water, dried at 110 °C for 16 h, and purified by column separation
(silica gel 40−63 μm, toluene): Yield 87.0 mg (28%) yellow solid.
Method 2: 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone (2, 100
mg, 0.118 mmol), hydrazinium sulfate (67.8 mg, 0.590 mmol), and
imidazole (1.0 g) were stirred at 140 °C for 4 h, allowed to cool,
precipitated with 2 M aqueous HCl (20 mL), collected by vacuum
filtration (D4 glass filter), washed with 2 M aqueous HCl and distilled
water, dried at 110 °C for 16 h, and purified by column separation
(silica gel 40−63 μm, toluene): Yield 79.4 mg (78%) yellow solid.
Method 3: 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone (2, 100
mg, 0.118 mmol), hydrazinium chloride (37.1 mg, 0.353 mmol),
and imidazole (1.6 g) were stirred at 140 °C for 12 h, allowed to cool,
precipitated with 2 M aqueous HCl (20 mL), collected by vacuum
filtration (D4 glass filter), washed with 2 M aqueous HCl and distilled
water, dried at 110 °C for 16 h, and purified by column separation
(silica gel 40−63 μm, toluene): Yield 76.4 mg (75%) yellow solid, mp
̃
(silica gel, CHCl3/ethanol 5:1) 0.93; IR (ATR) ν = 3407.8 (w),
2956.3 (w), 2924.8 (w), 2856.9 (w), 1983.4 (w), 1772.7 (w), 1712.9
(s), 1662.3 (s), 1625.5 (m), 1595.2 (w), 1521.8 (w), 1563.8 (w),
1521.8 (w), 1457.7 (w), 1414.6 (m), 1394.6 (w), 1363.8 (m), 1317.2
(vs), 1275.1 (w), 1250.0 (w), 1233.4 (w), 1201,1 (w), 1174.9 (w),
1113.4 (w), 946.2 (w), 873.2 (w), 843.9 (w), 811.3 (m), 766.0 (w),
1
746.0 (w), 724.9 (w), 660.2 cm−1 (w); H NMR (600 MHz, CDCl3,
3
27 °C, TMS) δ = 0.81 (t, J(H,H) = 6.9 Hz, 12 H, 4 × CH3), 1.06−
1.65 (m, 32 H, 16 × CH2), 1.85−2.04 (m, 4 H, 2 × β-CH2), 2.14−
2.44 (m, 16 H, 2 × β-CH2, 12 × CH3), 5.20−5.36 (m, 2 H, 2 × NCH),
9.06−9.53 (m, 4 H, 4 × CHperylene), 10.51 ppm (s, 2 H, 2 × CHperylene);
13C NMR (150 MHz, CDCl3, 27 °C, TMS) δ = 14.0, 15.7, 15.9, 22.6,
27.0, 29.2, 31.8, 32.4, 55.3, 123.5, 123.8, 124.1, 125.0, 125.2, 126.9,
127.3, 127.4, 127.7, 128.3, 130.4, 133.0, 133.4, 133.8 ppm; MS (DEP/
EI) m/z (%) 996 (77) [M+ + H], 995 (100) [M+], 814 (18), 813 (34),
812 (21), 657 (10), 632 (12), 631 (23), 630 (26), 149 (20), 148 (59),
147 (25), 134 (14), 97 (11), 83 (19), 70 (15), 69 (38), 57 (14), 56
(18), 55 (51), 43 (21), 41 (24); HRMS (FAB+, quadrupole,
C64H74N4O6) calcd m/z 994.5608, found m/z 994.5595, Δ =
−0.0013. Anal. Calcd for C64H74N4O6 (994.6): C, 77.23; H, 7.49;
N, 5.63. Found: C, 77.44; H, 7.47; N, 5.47.
̃
>250 °C; Rf (silica gel, CHCl3/ethanol 5:1) 0.74; IR (ATR) ν =
3509.7 (w), 3396.2 (w), 3138.8 (w), 3114.8 (w), 2953.1 (w), 2921.9
(m), 2853.3 (m), 2630.9 (w), 1748.8 (w), 1699.5 (m), 1651.1 (vs),
1595.8 (m), 1576.0 (m), 1499.7 (w), 1456.5 (w), 1440.8 (w), 1404.0
(w), 1363.0 (m), 1349.7 (s), 1321.7 (m), 1270.3 (w), 1252.0 (m),
1177.7 (w), 1145.4 (w), 1119.4 (w), 1050.8 (w), 938.3 (w), 901.7 (w),
842.2 (w), 812.9 (s), 802.9 (w), 761.8 (w), 749.6 (m), 723.1 cm−1
(w); UV/vis (CHCl3) λmax (Erel) = 344 (0.66), 359 (0.73), 433 (0.42),
457 (0.86), 489 nm (1.00); fluorescence (CHCl3, λexc = 460 nm) λmax
(Irel) = 478 (0.61), 499 (1.00), 533 nm (0.71); fluorescence quantum
yield (CHCl3, λexc = 460 nm, E460nm/1cm = 0.0267, reference S-13 with
Φ = 1.00) 0.04; MS (DEP/EI) m/z (%) 863 (21) [M+ + H], 862 (34)
[M+], 722 (14), 682 (29), 681 (71), 680 (41), 666 (18), 500 (43), 499
(97), 498 (100), 484 (17), 483 (14), 85 (27), 83 (61), 70 (15), 69
(35), 67 (18), 57 (29), 56 (14), 55 (36), 44 (98), 43 (21), 41 (65);
HRMS (FAB+, quadrupole, C54H62N4O6) calcd m/z 862.4669, found
m/z 862.4663, Δ = −0.0006. Anal. Calcd for C54H62N4O6 (862.5): C,
75.15; H, 7.24; N, 6.49. Found: C, 74.83; H, 7.37; N, 6.58.
Dye 5 (Spacer 1). 2,7-Diaminobenzo[lmn][3,8]phenanthrolin-
1,3,6,8-tetraone (4, 83.0 mg, 0.280 mmol) and 2,10-bis(1-hexyl-
heptyl)furo[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-
1,3,5,7,9,11(2H,10H)-hexone (2, 500 mg, 0.588 mmol) in quinoline
(8 mL) were heated at 160 °C for 12 h, allowed to cool, treated with 2
M aqueous HCl (40 mL), and extracted three times with chloroform
(3 × 80 mL). The combined organic phases were dried with
magnesium sulfate, evaporated, and purified by column separation
(silica gel 40−63 μm, toluene): Yield 340 mg (62%) yellow solid, mp
̃
>300 °C; Rf (silica gel, chloroform/ethanol 40:1) 0.60; IR (ATR) ν =
2948.4 (w), 2923.4 (m), 2854.9 (w), 1794.2 (w), 1739.1 (m), 1704.0
(s), 1661.7 (vs), 1624.9 (w), 1595.4 (w), 1583.7 (w), 1558.1 (w),
1538.5 (w), 1520.5 (w), 1456.0 (w), 1412.7 (w), 1393.3 (w), 1363.3
(m), 1337.8 (w), 1306.5 (vs), 1274.4 (w), 1240.1 (m), 1212.0 (w),
1199.1 (w), 1183.2 (w), 1172.1 (m), 1123.7 (w), 1099.1 (w), 1020.7
F
dx.doi.org/10.1021/jo4005662 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(w), 981.3 (w), 937.3 (w), 879.4 (w), 866.0 (w), 849.0 (w), 829.0 (w),
812.5 (s), 778.4 (w), 764.2 (m), 748.0 (m), 726.4 (w), 657.7 cm−1
Dye 10 (Spacer 3). Method 1: 2,10-Bis(1-hexylheptyl)furo-
[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11-
(2H,10H)-hexone (2, 200 mg, 0.236 mmol) and 2,9-diaminoanthra-
[2,1,9-def;6,5,10-d′e′f′]diisoquinolin-1,3,8,10-tetraone (9, 40.0 mg,
0.094 mmol) in quinoline (5 mL) were heated at 160 °C for 12 h,
allowed to cool, treated with 2 M aqueous HCl (20 mL), and extracted
three times with chloroform (3 × 50 mL). The combined organic
phases were dried with magnesium sulfate, evaporated, and purified by
column separation (silica gel 40−63 μm, toluene): Yield 110 mg
(56%) orange solid.
Method 2: Perylene-3,4:9,10-tetracarboxylicbisanhydride (8, 100
mg, 0.255 mmol) and 15 (551 mg, 0.638 mmol) in quinoline (3 mL)
were heated at 160 °C for 12 h, allowed to cool, treated with 2 M
aqueous HCl (15 mL), and extracted three times with chloroform (3
× 50 mL). The combined organic phases were dried with magnesium
sulfate, evaporated, and purified by column separation (silica gel 40−
63 μm, toluene): Yield 345 mg (65%) orange solid, mp >300 °C; Rf
1
(w); H NMR (600 MHz, CDCl3, 27 °C, TMS) δ = 0.82 (t, 24 H,
3J(H,H) = 7.1 Hz, 8 × CH3), 1.20−1.48 (m, 64 H, 16 × CH2), 1.91−
2.00 (m, 8 H, 4 × β-CH2), 2.30−2.40 (m, 8 H, 4 × β-CH2), 5.26−5.35
(m, 4 H, 4 × NCH), 9.06−9.10 (m, 4 H, 4 × CHperylene), 9.20−9.30
3
(m, 4 H, 4 × CHnaphthalene), 9.50 (d, 4 H, J(H,H) = 8.5 Hz 4 ×
CHperylene), 10.43−10.46 ppm (m, 4 H, 4 × CHperylene); 13C NMR (150
MHz, CDCl3, 27 °C, TMS) δ = 14.0, 22.6, 27.0, 29.2, 31.7, 55.4, 123.4,
124.4, 125.3, 125.9, 127.0, 127.7, 127.9, 128.6, 132.6, 133.5 159.8,
163.5 ppm; UV/vis (CHCl3) λmax (ε) = 362.8 (66600), 382.3
(124400), 410.2 (30100), 436.5 (73000), 466.5 nm (105000);
fluorescence (CHCl3, λexc = 436 nm) λmax (Irel) = 489.4 (0.99),
505.1 nm (1.00); fluorescence quantum yield (CHCl3, λexc = 436 nm,
E436nm/1cm = 0.0075, reference S-13 with Φ = 1.00) 0.19; MS (FAB+)
m/z (%) 1958.8 (10) [M+ + 2H], 1957.7 (1) [M+ + H], 1956.8 [M+],
1230.1 (25), 1230.1 (25). Anal. Calcd for C122H124N8O16 (1956.9): C,
74.82; H, 6.38; N, 5.72. Found: C, 74.51; H, 6.47; N, 5.72.
̃
(silica gel, chloroform/ethanol 40:1) 0.65; IR (ATR) ν = 2923.1 (m),
2854.1 (m), 2360.0 (m), 2338.0 (m), 1974.5 (w), 1950.0 (w), 1936.8
(w), 1913.6 (w), 1903.3 (w), 1875.1 (w), 1862.6 (w), 1839.4 (w),
1819.9 (w), 1796.4 (w), 1778.0 (w), 1765.4 (w), 1744.6 (m), 1726.7
(m), 1704.2 (s), 1698.0 (m), 1692.5 (m), 1659.4 (vs), 1649.9 (w),
1642.0 (w), 1629.2 (w), 1612.0 (w), 1592.0 (s), 1573.3 (w), 1565.3
(w), 1548.5 (w), 1535.8 (w), 1529.8 (w), 1513.1 (w), 1493.7 (w),
1483.5 (w), 1467.8 (w), 1462.0 (w), 1451.9 (w), 1443.3 (w), 1432.7
(w), 1422.2 (w), 1413.2 (m), 1402.3 (m), 1391.8 (w), 1365.6 (m),
1345.4 (w), 1309.9 (vs), 1241.5 (m), 1211.0 (m), 1170.3 (m), 1126.3
(m), 968.1 (w), 954.0 (w), 939.5 (w), 903.0 (w), 877.9 (w), 849.1
(w), 808.1 (m), 776.4 (w), 762.1 (w), 748.0 (w), 734.0 (m), 698.4
(w), 672.1 (w), 658.0 cm−1 (w); 1H NMR (400 MHz, CDCl3, 27 °C,
TMS) δ = 0.82 (t, 24 H, 3J(H,H) = 6.7 Hz, 8 × CH3), 1.19−1.68 (m,
64 H, 16 × CH2), 1.92−2.05 (m, 8 H, β-CH2), 2.28−2.44 (m, 8 H, β-
CH2), 5.25−5.37 (m, 4 H, NCH), 8.25−8.72 (m, 8 H, 8 × CHperylene),
9.18−9.58 (m, 8 H, 8 × CHperylene), 10.32−10.46 ppm (m, 4 H, 4 ×
CHperylene); 13C NMR (100 MHz, CDCl3, 27 °C, TMS) δ = 14.0, 22.6,
27.0, 29.3, 29.7, 31.8, 32.4, 55.4, 122.7, 123.2, 123.5, 124.6, 125.1,
125.9, 127.7, 128.3, 129.4, 132.6, 133.4, 134.9 160.1, 163.7 ppm; UV/
vis (CHCl3) λmax (ε) = 378.6 (83700), 410.9 (30900), 436.5 (80300),
466.5 (130300), 492.1 (70400), 528.9 nm (112400); fluorescence
(CHCl3, λexc = 436 nm) λmax (Irel) = 536.3 (1.00), 579.1 (0.48), 627.0
nm (0.11); fluorescence quantum yield (CHCl3, λexc = 436 nm,
E436nm/1cm = 0.0088, reference C25 with Φ = 1.00) 1.00. Anal. Calcd
for C132H128N8O16 (2080.9): C, 76.13; H, 6.20; N, 5.38. Found: C,
75.96; H, 6.31; N, 5.24.
Dye 7 (Spacer 2). 2,7-Bis-(4-amino-2,3,5,6-tetramethylphenyl)-
benzo[lmn][3,8]phenanthrolin-1,3,6,8-tetraone (6, 105 mg, 0.187
mmol) and 2,10-bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone (2, 350
mg, 0.411 mmol) in quinoline (8 mL) were heated at 160 °C for
12 h, allowed to cool, treated with 2 M aqueous HCl (40 mL), and
extracted three times with chloroform (3 × 80 mL). The combined
organic phases were dried with magnesium sulfate, evaporated, and
purified by column separation (silica gel 40−63 μm, toluene): Yield
276 mg (69%) yellow solid, mp >300 °C; Rf (silica gel, chloroform/
̃
ethanol 40:1) 0.65; IR (ATR) ν = 2948.0 (w), 2923.2 (m), 2855.0
(w), 1794.7 (w), 1739.0 (m), 1704.0 (s), 1661.9 (vs), 1624.5 (w),
1595.2 (w), 1583.7 (w), 1557.9 (w), 1538.1 (w), 1520.0 (w), 1456.5
(w), 1412.7 (w), 1393.0 (w), 1363.2 (m), 1337.7 (w), 1306.0 (vs),
1274.2 (w), 1240.5 (m), 1211.8 (w), 1199.0 (w), 1183.2 (w), 1172.1
(m), 1123.7 (w), 1099.1 (w), 1020.7 (w), 981.3 (w), 937.0 (w), 879.4
(w), 866.5 (w), 849.5 (w), 829.0 (w), 812.5 (s), 778.4 (w), 764.2 (m),
1
748.3 (m), 657.5 cm−1 (w); H NMR (600 MHz, CDCl3, 27 °C,
TMS) δ = 0.82 (t, 24 H, 3J(H,H) = 7.1 Hz, 8 × CH3), 1.20−1.48 (m,
64 H, 16 × CH2), 1.91−2.00 (m, 8 H, 4 × β-CH2), 2.22 (s, 12 H, 4 ×
CH3), 2.32 (s, 12 H, 4 × CH3), 2.29−2.40 (m, 8 H, 4 × β-CH2),
5.26−5.35 (m, 4 H, 4 × NCH), 9.06−9.10 (m, 4 H, 4 × CHnaphthalene),
9.20−9.30 (m, 4 H, 4 × CHperylene), 9.50 (d, 4 H, 3J(H,H) = 8.5 Hz, 4
× CHperylene), 10.43−10.46 ppm (m, 4 H, 4 × CHperylene); 13C NMR
(150 MHz, CDCl3, 27 °C, TMS) δ = 14.0, 15.4, 16.0, 22.6, 27.0, 29.2,
31.8, 32.4 55.3, 123.6, 124.2, 125.3, 127.0, 127.5, 127.8, 128.4, 131.8,
132.8, 134.4, 162.2, 167.0 ppm; UV/vis (CHCl3) λmax (Erel) = 362.2
(0.69), 379.4 (1.00), 410.4 (0.24), 436.5 (0.61), 466.4 nm (0.94);
fluorescence (CHCl3, λexc = 436 nm) λmax (Irel) = 475.8 (1.00), 508.1
nm (0.70); fluorescence quantum yield (CHCl3, λexc = 436 nm,
E436nm/1cm = 0.0135, reference S-13 with Φ = 1.00) 0.27; MS (FAB+)
m/z (%) 2220.2 (10) [M+ − H].
Dye 12 (Spacer 4). Method 1: 2,10-Bis(1-hexylheptyl)furo-
[3′,4′:4,5]pyreno[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11-
(2H,10H)-hexone (2, 1.00 g, 1.18 mmol) and 2,9-bis-(4-amino-
2,3,5,6-tetramethylphenyl)anthra[2,1,9-def;6,5,10-d′e′f ′]diiso-
quinoline-1,3,8,10-tetraone (11, 384 mg, 0.561 mmol) in quinoline (5
mL) were heated at 160 °C for 12 h, allowed to cool, treated with 2 M
aqueous HCl (20 mL), and extracted three times with chloroform (3
× 50 mL). The combined organic phases were dried with magnesium
sulfate, evaporated, and purified by column separation (silica gel 40−
63 μm, toluene): Yield 830 mg (63%) orange solid.
Method 2: Perylene-3,4:9,10-tetracarboxylicbisanhydride (7, 100
mg, 0.255 mmol) and 16 (635 mg, 0.638 mmol) in quinoline (3 mL)
were heated at 160 °C for 12 h, allowed to cool, treated with 2 M
aqueous HCl (15 mL), and extracted three times with chloroform (3
× 50 mL). The combined organic phases were dried with magnesium
sulfate, evaporated, and purified by column separation (silica gel 40−
63 μm, toluene): Yield 419 mg (63%) orange solid, mp >300 °C; Rf
G
dx.doi.org/10.1021/jo4005662 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(silica gel, chloroform/ethanol 20:1) 0.80; IR (ATR) ν
̃
= 2924.8 (m),
Dye 17. 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone (2, 401
mg, 0.472 mmol) and (P)(+) 6,6′-dimethylbiphenyl-2,2′-diamine
(100 mg, 0.472 mmol) in quinoline (1.5 mL) were heated at 160 °C
for 12 h, allowed to cool, treated with 2 M aqueous HCl (20 mL), and
extracted three times with chloroform (3 × 80 mL). The combined
organic phases were dried with magnesium sulfate, evaporated, and
purified by column separation (silica gel 40−63 μm, toluene, second
band): Yield 930 mg (20%) yellow solid, mp >300 °C; Rf (silica gel,
2855.3 (m), 2362.0 (m), 2337.0 (m), 1983.3 (w), 1949.8 (w), 1929.0
(w), 1900.3 (w), 1875.1 (w), 1853.3 (w), 1834.6 (w), 1819.9 (w),
1806.2 (w), 1797.0 (w), 1787.7 (w), 1777.6 (w), 1765.7 (w), 1754.5
(w), 1744.4 (w), 1738.2 (w), 1722.1 (m), 1709.8 (s), 1691.8 (w),
1678.7 (w), 1665.5 (vs), 1659.5 (vs), 1649.8 (w), 1641.6 (w), 1630.8
(w), 1620.4 (w), 1611.8 (w), 1594.0 (s), 1572.9 (w), 1565.1 (w),
1548.4 (w), 1529.9 (w), 1513.1 (w), 1501.8 (w), 1493.7 (w), 1480.4
(w), 1432.3 (w), 1426.4 (w), 1413.5 (w), 1365.9 (m), 1344.3 (s),
1334.6 (s), 1317.7 (vs), 1274.0 (w), 1233.0 (w), 1250.1 (w), 1233.0
(w), 1200.4 (w), 1174.2 (w), 1118.6 (w), 1017.4 (w), 957.9 (w), 851.9
(w), 811.8 (m), 767.6 (w), 748.2 (w), 724.2 (w), 662.7 cm−1 (w); 1H
̃
chloroform/ethanol 40:1) 0.81; IR (ATR) ν = 3377.4 (w), 2953.9
(m), 2923.6 (vs), 2855.1 (s), 2362.1 (w), 2337.3 (w), 1774.8 (w),
1716.4 (s), 1702.2 (s), 1660.6 (vs), 1625.9 (m), 1594.4 (m), 1524.3
(w), 1463.5 (m), 1413.8 (m), 1364.4 (s), 1317.3 (s), 1276.4 (m),
1242.6 (m), 1209.8 (w), 1174.1 (w), 1163.7 (w), 1121.2 (w), 971.5
(w), 941.8 (w), 850.5 (w), 812.1 (m), 766.2 (m), 747.6 (w), 659.4
3
NMR (600 MHz, CDCl3, 27 °C, TMS) δ = 0.82 (t, 24 H, J(H,H) =
6.8 Hz, 8 × CH3), 1.18−1.65 (m, 64 H, 16 × CH2), 1.89−2.01 (m, 8
H, β-CH2), 2.22 (s, 12 H, 4 × CH3), 2.30 (s, 12 H, 4 × CH3), 2.28−
2.43 (m, 8 H, β-CH2), 5.24−5.39 (m, 4 H, NCH), 8.76−8.95 (m, 8 H,
8 × CHperylene), 9.10−9.30 (m, 4 H, 4 × CHperylene), 9.41−9.54 (m, 4
H, 4 × CHperylene), 10.30−10.45 ppm (m, 4 H, 4 × CHperylene); 13C
NMR (100 MHz, CDCl3, 27 °C, TMS) δ = 14.0, 15.5, 15.9, 22.6, 27.0,
29.2, 29.7, 31.8, 32.4, 55.3, 123.5, 123.6, 124.2, 125.3, 126.9, 127.5,
127.8, 128.4, 130.3, 132.2, 132.9, 133.5, 134.2, 135.2, 162.8, 167.1
ppm; UV/vis (CHCl3) λmax (ε) = 376.3 (80600), 410.9 (33500), 436.5
(81400), 466.5 (133400), 491.4 (66400), 528.2 nm (107600);
fluorescence (CHCl3, λexc = 436 nm) λmax (Irel) = 535.8 (1.00),
579.4 (0.49), 626.5 nm (0.11); fluorescence quantum yield (CHCl3,
λexc = 436 nm, E436nm/1cm = 0.0045, reference C25 with Φ = 1.00) 1.00.
Anal. Calcd for C152H152N8O16 (2345.1): C, 77.79; H, 6.39; N, 4.77.
Found: C, 77.61; H, 6.46; N, 4.64.
1
cm−1 (w); H NMR (600 MHz, CDCl3, 27 °C, TMS) δ = 0.72−0.86
(m, 12 H, 4 × CH3), 0.87−1.43 (m, 32 H, 32 × CH3), 1.87−1.98 (m,
4 H, 2 × β-CH2), 2.16 (s, 3 H, CH3), 2.18 (s, 3 H, CH3), 2.31−2.38
(m, 4 H, 2 × β-CH2), 5.28−5.32 (m, 2 H, NCH), 6.85−7.00 (m, 2 H,
2 × CHaromat.), 7.40−7.80 (m, 4 H, 4 × CHaromat.), 9.10−9.26 (m, 2 H,
2 × CHperylene), 9.30−9.45 (m, 2 H, 2 × CHperylene), 10.33−10.48 ppm
(m, 2 H, 2 × CHperylene); 13C NMR (150 MHz, CDCl3, 27 °C, TMS) δ
= 14.0, 19.9, 22.6, 27.0, 29.1, 29.2, 31.7, 32.5, 55.3, 124.1, 125.1, 127.7,
128.5 ppm; UV/vis (CHCl3) λmax (ε) = 377.5 (37400), 410.9 (15600),
436.8 (39400), 467.3 nm (60900); fluorescence (CHCl3, λexc = 437
nm) λmax (Irel) = 478.7 (1.00), 511.9 (0.69), 548.8 nm (0.18);
fluorescence quantum yield (CHCl3, λexc = 437 nm, E437nm/1cm
=
0.0127, reference S-13 with Φ = 1.00) 0.02; MS (FAB+) m/z (%)
1670.8 (100) [M+ + H], 1669.9 (59) [M+]. Anal. Calcd for
C68H74N4O6 (1042.6): C, 78.28; H, 7.15; N, 5.37. Found: C, 78.26;
H, 7.09; N, 5.24.
Dye 14 (Spacer 5). 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno-
[2,1,10-def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone
(2, 350 mg, 0.413 mmol) and 2,9-bis(4-aminobutyl)anthra[2,1,9-
def;6,5,10-d′e′f′]diisoquinoline-1,3,8,10-tetraone (13, 100 mg, 0.188
mmol) in quinoline (8 mL) were heated at 160 °C for 12 h, allowed to
cool, treated with 2 M aqueous HCl (20 mL), and extracted three
times with chloroform (3 × 50 mL). The combined organic phases
were dried with magnesium sulfate, evaporated, and purified by
column separation (silica gel 40−63 μm, toluene): Yield 198 mg
(48%) dark red solid, mp >300 °C; Rf (silica gel, chloroform/ethanol
Dye 18. 2,10-Bis(1-hexylheptyl)furo[3′,4′:4,5]pyreno[2,1,10-
def:7,8,9-d′e′f′]diisoquinoline-1,3,5,7,9,11(2H,10H)-hexone (2, 401
mg, 0.472 mmol) and (P)(+) 6,6′-dimethylbiphenyl-2,2′-diamine
(50.1 mg, 0.236 mmol) in quinoline (1.5 mL) were heated at 160 °C
for 12 h, allowed to cool, treated with 2 M aqueous HCl (20 mL), and
extracted three times with chloroform (3 × 80 mL). The combined
organic phases were dried with magnesium sulfate, evaporated, and
purified by column separation (silica gel 40−63 μm, toluene, first
yellow fluorescent band): Yield 370 mg (83%) yellow solid, mp >300
̃
20:1) 0.25; IR (ATR) ν = 2952.7 (m), 2924.6 (s), 2855.5 (m), 1768.6
(w), 1700.4 (vs), 1659.2 (vs), 1625.4 (m), 1593.9 (s), 1578.0 (w),
1559.6 (w), 1540.2 (w), 1522.2 (w), 1506.8 (w), 1456.7 (w), 1438.0
(w), 1400.2 (m), 1363.3 (m) 1343.4 (m), 1316.2 (s), 1272.2 (m),
1239.2 (m), 1204.0 (w), 1173.1 (w), 1125.5 (w), 1125.5 (w), 1101.2
(w), 973.8 (w), 943.4 (w), 846.5 (w), 810.1 (m), 795.1 (w), 765.7
(w), 744.9 (w), 659.1 (w), 626.0 (w), 616.6 cm−1 (w); UV/vis
(CHCl3) λmax (ε) = 374.1 (61000), 410.9 (26900), 436.5 (64000),
466.5 (98900), 489.8 (36600), 528.2 nm (43000); fluorescence
(CHCl3, λexc = 436 nm) λmax (Irel) = 535.4 (1.00), 576.0 nm (0.68);
̃
°C; Rf (silica gel, chloroform) 0.83; IR (ATR) ν = 2953.4 (m), 2925.5
(m), 2856.1 (m), 2349.7 (w), 1772.6 (w), 1713.2 (s), 1662.1 (vs),
1625.8 (w), 1595.2 (w), 1523.6 (w), 1458.3 (w), 1414.3 (w), 1364.6
(s), 1317.9 (s), 1277.6 (w), 1211.2 (w), 1164.2 (w), 1102.3 (w), 972.1
(w), 942.0 (w), 846.1 (w), 812.3 (w), 766.4 (w), 748.3 (w), 659.4
fluorescence quantum yield (CHCl3, λexc = 436 nm, E436nm/1cm
=
1
cm−1 (w); H NMR (600 MHz, CDCl3, 27 °C, TMS) δ = 0.82−0.88
0.0219, reference C25 with Φ = 1.00) 0. 75. Anal. Calcd for
C140H144N8O16 (2193.1): C, 76.62; H, 6.61; N, 5.11. Found: C, 76.53;
H, 6.72; N, 5.17.
(m, 24 H, 8 × CH3), 1.24−1.40 (m, 64 H, 32 × CH3), 1.93−2.05 (m,
8 H, 4 × β-CH2), 2.31−2.43 (m, 8 H, 4 × β-CH2), 2.61 (s, 6 H, 2 ×
CH3), 5.30−5.38 (m, 4 H, 2 × NCH), 7.04−7.09 (m, 2 H, 2 ×
3
CHaromat.), 7.41 (t, J(H,H) = 7.7 Hz, 2 H, 2 × CHaromat.), 7.65 (d,
3J(H,H) = 7.5 Hz, 2 H, 2 × CHaromat.), 9.00−9.29 (m, 10 H, 10 ×
3
CHperylene), 9.45 (d, J(H,H) = 8.0 Hz, 4 H, 2 × CHperylene), 9.48 (d,
3J(H,H) = 8.4 Hz, 4 H, 2 × CHperylene), 9.48−9.75 (m, 6 H, 6 ×
CHperylene), 10.31−10.35 ppm (m, 4 H, 2 × CHperylene); 13C NMR (150
MHz, CDCl3, 27 °C, TMS) δ = 14.0, 20.6, 22.6, 27.0, 28.9, 29.2, 30.9,
31.8, 32.5, 123.8, 124.0, 125.3, 126.4, 127.2, 127.8, 128.4, 128.5, 129.6,
131.7, 133.6, 136.0, 141.4, 166.0, 169.6, 206.9 ppm; UV/vis (CHCl3)
H
dx.doi.org/10.1021/jo4005662 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
λmax (ε) = 382.3 (73900), 412.4 (28000), 438.7 (70900), 470.3 nm
(110900); fluorescence (CHCl3, λexc = 439 nm) λmax (Irel) = 479.5
(1.00), 512.9 (0.62), 548.8 nm (0.18); fluorescence quantum yield
(CHCl3, λexc = 439 nm, E439nm/1cm = 0.0124, reference S-13 with Φ =
1.00) 0.27; MS (MALDI+, anthracene) m/z (%) 1873.1 [M+ + H],
1872.1 [M+]. Anal. Calcd C122H132N6O12 (1872.9): C, 78.18; H, 7.10;
N, 4.48. Found: C, 78.24; H, 7.12; N, 4.35.
Janssen, R., Salbeck, J., Eds.; Elsevier: Amsterdam, 2007; Vol. 8(2−3).
(c) Scheibe, G. Angew. Chem. 1936, 49, 563;(d) Scheibe, G.
Absorption Spectroscopic Data of the Position, Intensity, and
Structure of Bands. In Optische Anregung organischer Systeme; Foerst,
W., Ed.; Verlag Chemie: Weinheim, Germany, 1966; pp 108−130,
LCCC Nr. 66-25750. Chem. Abstr. 1969, 70, 32979.
(8) Langhals, H.; Kirner, S. Eur. J. Org. Chem. 2000, 365−380.
(9) Kalinin, S.; Speckbacher, M.; Langhals, H.; Johansson, L. B.-Å.
Phys. Chem. Chem. Phys. 2001, 3, 172−174.
(10) (a) Langhals, H.; Demmig, S.; Potrawa, T. J. Prakt. Chem. 1991,
333, 733−748. (b) Demmig, S.; Langhals, H. Chem. Ber. 1988, 121,
225−230.
(11) (a) Schuetz, S.; Kurz, J.; Pluempe, H.; Otten, H.; Bock, M. Ger.
Patent DE 1230031 19661208 (Dec. 8, 1966); Chem. Abstr. 1967, 66,
65334. (b) Dine-Hart, R. A. J. Polym. Sci., Part A: Polym. Chem. 1968,
6, 2755−2764.
(12) (a) Gorteau, V.; Bollot, G.; Mareda, J.; Perez-Velasco, A.; Matile,
S. J. Am. Chem. Soc. 2006, 128, 14788−14789. (b) Gangneux, P.;
Marechal, E. Bull. Soc. Chim. Fr. 1973, 1466−1483.
(13) Cassella Farbwerke Mainkur A.-G. Ger. Patent DE 1147702
(Aug. 5, 1960); Chem. Abstr. 1963, 59, 82653.
(14) (a) Kaul, B. L.; Graciet, J.-C.; Barashkov, N. N.; Molloy, T. C.
Eur. Patent Appl. EP 1172417 A2 20020116 (Jul. 14, 2000);
Chem.Abstr. 2002, 136, 103834. (b) Xue, L.; Ranjan, N.; Arya, D. P.
Biochemistry 2011, 50, 2838−2849.
(15) Langhals, H.; Hofer, A.; Bernhard, S.; Siegel, J. S.; Mayer, P. J.
Org. Chem. 2011, 76, 990−992.
(16) (a) Mislow, K.; Rutkin, P.; Lazarus, A. K. J. Am. Chem. Soc.
1957, 79, 2974−2975. (b) Jones, W. M.; Wilson, J. W., Jr. Tetrahedron
Lett. 1965, 21, 1587−1592. (c) Mislow, K. Angew. Chem. 1958, 70,
638−689.
ASSOCIATED CONTENT
* Supporting Information
Spectroscopic data of 8 and 10. This material is available free of
■
S
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: langhals@lrz.uni-muenchen.de.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support by the Fonds der Chemischen Industrie and
the CIPSM cluster Munich Center for Integrated Protein
Science is gratefully acknowledged.
DEDICATION
■
Dedicated to Prof. Heinrich Noth on the occasion of his 85th
birthday.
̈
(17) Nakanishi, K.; Berova, N. The Excitation Chirality Method
(Circular Dichroism. Principles and Their Applications, 2nd ed.; Berova,
N., Nakanishi, K., Woody, R. W., Eds.; John Wiley & Sons: Weinheim,
Germany, 2000; ISBN 987 047 1 330 035.
REFERENCES
■
(1) (a) Liu, Na; Giessen, H. Angew. Chem. 2010, 122, 10034−10049;
Angew. Chem., Int. Ed. 2010, 49, 9838−9852. (b) Smith, D. R.; Pendry,
J. B.; Wiltshire, M. C. K. Science 2004, 305, 788−792. (c) Soukoulis, C.
M.; Linden, S.; Wegener, M. Science 2007, 315, 47−49. (d) Soukoulis,
C. M.; Kafesaki, M.; Economou, E. N. Adv. Mater. 2006, 18, 1941−
1952. (e) Shalaev, V. M. Nat. Photonics 2007, 1, 41−48.
(2) (a) Veselago, V. G. Sov. Phys. Usp 1968, 10, 509−514. (b) Smith,
D. R.; Padilla, W. J.; Vier, D. C.; Nemat-Nasser, S. C.; Schultz, S. Phys.
Rev. Lett. 2001, 84, 4184−4187. (c) Shelby, R. A.; Smith, D. R.;
Schultz, S. Science 2001, 292, 77−79. (d) Katsarakis, N.; Koschny, T.;
Kafesaki, M.; Economou, E. N.; Ozbay, E.; Soukoulis, C. M. Phys. Rev.
B 2004, 70, 201101. (e) Zhou, J. F.; Zhang, L.; Tuttle, G.; Koschny,
T.; Soukoulis, C. M. Phys. Rev. B 2006, 73, 041101.
(18) (a) Liu, N.; Weiss, T.; Mesch, M.; Langguth, L.; Eigenthaler, U.;
Hirschner, M.; Sonnichsen, C.; Giessen, H. Nano Lett. 2010, 10, 1103.
̈
(b) Lal, S.; Link, S.; Halas, N. J. Nat. Photonics 2007, 1, 641−648.
(c) Hao, F.; Sonnefraud, Y.; Dorpe, P. V.; Maier, S. A.; Halas, N. J.;
Nordlander, P. Nano Lett. 2008, 8, 3983−3988.
(19) Wasielewski, M. R. Acc. Chem. Res. 2009, 42, 1910−1921.
(20) Langhals, H.; Pust, T. Green Sustainable Chem. 2011, 1, 1−6.
(21) (a) Nalbach, P.; Pugliesi, I.; Langhals, H.; Thorwart, M. Phys.
Rev. Lett. 2012, 108, 218302-1−218302-5. (b) Langhals, H.;
Esterbauer, A. J.; Walter, A.; Riedle, E.; Pugliesi, I. J. Am. Chem. Soc.
2010, 132, 16777−16782. (c) Langhals, H.; Poxleitner, S.; Krotz, O.;
Pust, T.; Walter, A. Eur. J. Org. Chem. 2008, 4559−4562.
(3) (a) Pendry, J. B.; Schurig, D.; Smith, D. R. Science 2006, 312,
1780−1782. (b) Schurig, D.; Mock, J. J.; Justice, B. J.; Cummer, S. A.;
Pendry, J. B.; Starr, A. F.; Smith, D. R. Science 2006, 314, 977−980.
(c) Valentine, J.; Li, J.; Zentgraf, T.; Bartal, G.; Zhang, X. Nat. Mater.
2009, 8, 568−571.
(4) (a) Prodan, E.; Radloff, C.; Halas, N. J.; Nordlander, P. Science
2003, 302, 419−422. (b) Wang, H.; Brandl, D. W.; Le, F.; Nordlander,
P.; Halas, N. J. Nano Lett. 2006, 6, 827−832. (c) Hao, F.; Nehl, C. L.;
Hafner, J. H.; Nordlander, P. Nano Lett. 2007, 7, 729−732.
(d) Nordlander, P.; Oubre, C.; Prodan, E.; Li, K.; Stockman, M. I.
Nano Lett. 2004, 4, 899−903. (e) Lassiter, J. B.; Aizpurua, J.;
Hernandez, L. I.; Brandl, D. W.; Romero, I.; Lal, S.; Hafner, J. H.;
Nordlander, P.; Halas, N. J. Nano Lett. 2008, 8, 1212−1218.
(5) (a) Langhals, H. Molecular Devices. Chiral, Bichromophoric
Silicones: Ordering Principles in Complex Molecules. In Silicon Based
Polymers; Ganachaud, F., Boileau, S., Boury, B., Eds.; Springer: Berlin,
2008; p 51−63, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4.
(b) Langhals, H. Chromophores for Picoscale Optical Computers. In
Fundamentals of Picoscience; Sattler, K., Ed.; Taylor & Francis
Publisher: London, 2013; p 705−727.
(6) Forster, T. Naturwissenschaften 1946, 33, 166.
̈
(7) (a) Holmes, R. J.; Forrest, S. R. Org. Electron. 2007, 8, 77−93.
(b) Special Issue: Coupled States of Excitons, Photons, and Plasmons
in Organic Structures. In Organic Electronics; Adachi, C.; Forrest, S. R.,
I
dx.doi.org/10.1021/jo4005662 | J. Org. Chem. XXXX, XXX, XXX−XXX