Crown ether derivatised pyromellitic diimides

Article abstract of DOI:10.1071/CH14128

Pyromellitic diimide functionalised on the aromatic core with azacrown ethers have been synthesised and characterised by analytical methods including X-ray crystallography. Changes in their UV-vis spectra by the addition of metal salts have been investigated.

Full text of DOI:10.1071/CH14128

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2014, 67, 1264–1269
Full Paper
http://dx.doi.org/10.1071/CH14128
Crown Ether Derivatised Pyromellitic Diimides
A
,
A B
Saman Sandanayake and Steven J. Langford
A
School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.
Corresponding author. Email: steven.langford@monash.edu
B
Pyromellitic diimide functionalised on the aromatic core with azacrown ethers have been synthesised and characterised by
analytical methods including X-ray crystallography. Changes in their UV-vis spectra by the addition of metal salts have
been investigated.
Manuscript received: 10 March 2014.
Manuscript accepted: 16 April 2014.
Published online: 16 May 2014.
Introduction
containing alkyl side chains gave higher yields than the corre-
sponding phenyl derivatives. The stepwise addition of the
secondary amine to 1a, b is advantageous for the formation of
more complex systems. In the course of this research, it appears
the reaction temperature plays a critical role in this process. Too
high an elevation does not lead to the intended disubstituted
system, but instead begins to lead to degradation with a wide
product distribution as evinced by TLC analysis. UV-vis
absorption spectra of 2a–d are very similar with maxima at
499 nm. The highly coloured nature of compounds 2a–d com-
pared with that of 1a, b can be attributed in part to the
introduction of nitrogen, leading to more extensive overlap of
orbitals, as has been well reported in the related core-substituted
Tetracarboxylic diimide derivatives of rylenes, particularly of
naphthalene (NDI) and perylene (PDI) (Chart 1), have been
extensively studied for their well behaved redox and fluores-
cence properties, primarily towards components of photo-
synthetic mimics and as organic field-effect transistor materials
[
1,2]
for organic electronics.
While substitution of NDIs at the
diimide nitrogens have very little influence on the photophysical
and electrochemical properties, core substitution has been
shown to drastically change the optical, electronic, and chemical
[
3]
properties. What this means is that careful selection of sub-
stitution can fine-tune the properties of NDIs for specific
applications. This is in contrast to the early development of
NDIs, which, as a result of their unremarkable optical properties,
[
7,8]
NDIs.
[
3]
were forgotten until the turn of the century.
Reaction of 2a or 2b with excess dibutylamine, or 2c or 2d
with morpholine, gives the target compounds 3a–d in good
yields following chromatography (Scheme 2).
Outside of polymer science, the smallest member of the
aromatic diimides, pyromellitic diimide (PMD), have received
little attention, due in part to synthetic challenges in achieving
stable derivatives, but more likely a result of the uninteresting
optical and redox properties of the parent pyromellitic
Dark blue single crystals of 3c, d suitable for X-ray crystal-
lography were grown from MeCN solution. The molecular
structure of each is shown in Fig. 1. As indicated, the groups
extending from the pyromellitic core are all off-set to the PMD
core as a result of the steric restrictions imposed by the imide
oxygens. This effect makes it hard to deliver long-range
ordering through p–p interactions within the crystal lattice.
As a result, the macromolecular structure is unremarkable.
There is ordering in both 3c and 3d that results from regions
containing the crown ether groups and phenyl groups but these
might be better termed polar and less-polar regions.
[
4]
anhydride. From our perspective, core substitution of the
pyromellitic diimides is interesting due to the proximity of
donating and withdrawing groups, leading to potential push–
pull characteristics. Surprisingly, few attempts have been made
to functionalise pyromellitic diimides in order to enhance the
[5]
chromophoric properties. In this paper, we investigate core
functionalisation of pyromellitic diimides with amines and
azacrown ethers and study their properties in the absence and
presence of metal salts.
The target compounds 3a–d were synthesised as outlined in
Scheme 1. The dibromides 1a and 1b were prepared according
to literature reported methods in four steps starting with com-
mercially available 1,2,4,5-tetramethylbenzene. The imide
substitution using octyl and phenyl groups were chosen to aid
solubility and crystallisation, respectively. Reaction of the
dibromide 1a or 1b with 1-aza-15-crown-5 or 1-aza-18-
crown-6 at elevated temperature in dimethylacetamide (DMA)
gave the corresponding highly-coloured monobromides 2a–d
in good to excellent yields depending on the nature of the
crown ether and the imide substitution. Generally, compounds
Compound series 3a–d are very weakly fluorescent however,
they are intensely blue in colour with extinction coefficient (e)
ꢀ1
ꢀ1
of 10500 M cm at 604 nm (lCT) in methanol for both 3a
and 3b, in stark contrast to 1a, b which are both are pale yellow
in colour (lmax 365 nm in CH Cl ), the former attributable to the
[
6]
2
2
overlap of two amine lone pairs from crown nitrogen and
morpholine nitrogen with the aromatic ring.
þ
þ
Addition of alkali metal ions such as Na or K , as their
acetate salts, leads to significant changes in the UV-vis absorp-
tion spectra of 3a–d in methanol solution converting the deep
blue solutions to bright red in colour (DlCT 100 nm). The
reference molecule 4, which is dark blue in colour
Journal compilation Ó CSIRO 2014
www.publish.csiro.au/journals/ajc

Crown Ether Derivatised Pyromellitic Diimides
1265
Pyromellitic
diimide
Naphthalene
diimide
Perylene
diimide
Terrylene
diimide
Chart 1. Four common members of the rylene diimide family.
Br
Br
Br
Br
Br
Br
Br
O
O
O
O
HO C
CO H
2
2
i
ii
iii
iv
O
O
R
1
N
N R
1
HO C
CO H
2
2
O
O
O
O
Br
1
1
a (R1 ꢀ n-octyl)
b (R1 ꢀ phenyl)
Scheme 1. Synthesis of pyromellitic diimide dibromide (1). Reagents and conditions: (i) Br
2
, I
2
, CH
2
2 4 4
Cl ; (ii) (a) KMnO , pyridine; (b) KMnO , pyridine,
H
2
O, NaOH; (iii) Ac
2 8 2
O, AcOH; (iv) C H17NH or aniline, AcOH.
O
N
O
n
n
O
O
O
O
O
O
O
O
Br
O
N
O
O
O
N
O
O
O
i
ii
R1
N
N
R1
R1
N
R1
R1
N
N
R1
O
O
O
O
O
Br
Br
R2
1
1
a (R1 ꢀ n-octyl)
b (R1 ꢀ phenyl)
2a (n ꢀ 0, R1 ꢀ n-octyl)
2b (n ꢀ 1, R1 ꢀ n-octyl)
3a (n ꢀ 0, R1 ꢀ n-octyl, R2 ꢀ dibutylamine)
3b (n ꢀ 1, R1 ꢀ n-octyl, R2 ꢀ dibutylamine)
3c (n ꢀ 0, R1 ꢀ phenyl, R2 ꢀ morpholine)
3d (n ꢀ 1, R1 ꢀ phenyl, R2 ꢀ morpholine)
2c (n ꢀ 0, R1 ꢀ phenyl)
2
d (n ꢀ 1, R1 ꢀ phenyl)
Scheme 2. Synthesis of crown ether derivatives 2-3. Reagents and conditions: (i) crown ether, dimethylacetamide, 1208C; (ii) excess dibutylamine
or morpholine, 1408C.
(
lCT 630 nm) does not change its spectral properties with
rotation around nitrogen–carbon bond as a result of rigidifying
the crown ether limits the characteristics of the charge-transfer
band. This spectral change observed upon addition of metal ions
to 3a and 3b is very similar to the changes observed upon
addition of trifluoroacetic acid (TFA) to compounds 3a, 3b, and
4 (Chart 2). The absorption maxima for lCT are around 534 nm
for all three molecules in the presence of acid.
alkaline metal ions even at high concentrations indicating the
importance of the crown ether group in characterising the
change. The spectral changes that occur during sodium ion
binding to compound 3a in methanol are given in Fig. 2 as a
representative example. Very similar spectral changes were
observed for crown-6 derivative 3b.
The interaction of nitrogen lone pair of the azacrown with the
alkali metal ion combined with metal ion induced restriction on
The stability constants were calculated using Benesi–
Hilderbrand equation and are given in Table 1. The metal ion

1
266
S. Sandanayake and S. J. Langford
(
a)
C(29)
C(14)
O(6)
C(28)
C(15)
C(16)
C(2)
C(30)
C(13)
C(11)
N(1)
O(7)
C(12)
O(1)
C(31)
C(32)
O(2)
C(27)
N(4)
C(1)
C(25)
C(10)
C(9)
C(3)
C(4)
C(26)
C(36)
C(8)
O(8)
C(33)
O(5)
C(24)
N(3)
O(4)
C(5)
C(6)
C(35)
C(23)
C(7)
N(2)
C(17)
C(18)
C(22)
C(21)
C(20)
O(9)
C(34)
O(3)
C(19)
(
b)
C(34)
C(35)
C(33)
O(9)
C(19)
C(36)
O(8)
O(7)
O(10)
C(32)
C(31)
C(20)
C(18)
C(37)
C(21)
C(17)
N(2)
O(3)
C(38)
C(22)
O(4)
C(24)
C(8)
C(6)
N(4)
C(10)
C(9)
C(1)
O(6)
C(30)
C(27)
C(7)
C(4)
C(23)
C(29)
O(5)
C(5)
C(28)
N(3)
C(3)
C(2)
N(1)
O(1)
C(25)
C(26)
O(2)
C(11)
C(12)
C(16)
C(15)
C(14)
C(13)
Fig. 1. Single-crystal X-ray structures of (a) 3c and (b) 3d drawn as ORTEP diagrams. The lattice solvent MeCN
has been omitted for clarity. Part of the crown ether in 3d was modelled as disordered over two positions, only the
major component is shown.
0
0
0
0
.8
.6
.4
.2
0
0
0
0
0
2
4
8
1
2
4
mM
.1 mM
.4 mM
.8 mM
.0 mM
.0 mM
.0 mM
2.0 mM
0.0 mM
0.0 mM
4
Chart 2.
binding abilities of 3a and 3b are somewhat lower than its
parent crown ether as given in Table 1. The metal binding nature
of the parent crown ether has been altered by the presence of
carbonyl groups close to the crown ether ring and the presence of
the push–pull pyromellitic group. It is probable that the electron
density shift/delocalisation of the nitrogen lone pair into the
aromatic ring, supported by the strong electron pulling of two
imide derivatives, could reduce the nitrogen–metal interaction
3
00
400
500
600
700
800
Wavelength [nm]
3
Fig. 2. Sodium ion induced UV-vis spectral changes of 3a in CH OH
solution. The sodium ions were added as the acetate salts.

Crown Ether Derivatised Pyromellitic Diimides
1267
Table 1. Metal ion-crown ether complex stability constant, log b for
3a, 3b, their parent crown ethers N-methyl-monoaza-15-crown-5 and
and dimethylacetamide (4 mL) was heated at 1208C, under
nitrogen for 18 h. Solvent was removed under reduced pressure
and the crude material was chromatographed on flash silica
[9]
the corresponding 18-crown-6 analogue
(dichloromethane with 2–4 % v/v methanol). This material was
redissolved in ethyl acetate and washed with deionised water
3
a
3b
N-methyl-monoaza-
N-methyl-monoaza-
1
5-crown-5
18-crown-6
(2 ꢁ 50 mL). The organic layer was separated and dried under
reduced pressure to obtain 2b as a dark red film (79 mg, 100 %).
dH 3.77–3.57 (m, 24H), 1.64–1.58 (m, 4H), 1.29–1.21 (m, 20H),
Sodium
2.65
2.66
3.93
3.91
3.39
3.07
3.93
5.33
Potassium
0
1
2
.85–0.81 (m, 6H). d 165.14, 164.21, 145.83, 137.43, 130.29,
C
05.39, 71.61, 70.93, 70.77, 70.70, 54.61, 38.83, 31.98, 29.35,
9.31, 28.59, 27.11, 22.84, 14.12. m/z (ESI) 758.5, 760.5
þ
reducing the total metal ion binding ability of the crown ether
moiety, compared with the parent crown ether. The results clearly
show the new compounds do not discriminate sodium from
potassium ions. Interestingly, the addition of alkali metal ions
does not significantly enhance the fluorescence of the system.
[M þ Na] . m/z 758.2985, 760.2974. HRMS Anal. Calc. for
þ
C H BrN NaO [M þ Na] 758.2992, 760.2972.
3
6
54
3
8
0
00
00
N,N-Di-n-octyl-3-(N -aza-18-crown-6)-6-N ,N -di-n-
butylaminopyromellitic diimide 3a
A mixture of 2a (95 mg, 0.12 mmol) was dissolved in dibuty-
lamine (2 mL) and heated at 1408C, under nitrogen for 18 h.
Excess amine was removed under reduced pressure and the
crude material was chromatographed on flash silica (dichloro-
methane with 0–10 % v/v methanol). This material was redis-
solved in ethyl acetate and washed with deionised water
(2 ꢁ 50 mL). The organic layer was separated and dried under
reduced pressure to obtain 3a as a dark blue film (76 mg, 77 %).
dH 3.80–3.70 (m, 28H), 3.40 (t, J 12.3, 4H), 1.64–1.52 (m, 4H),
1.46–1.20 (m, 4H), 1.34–1.19 (m, 24H), 0.89–0.81 (m, 12H). dC
Conclusion
Strong electron push–pull system has been created by introduc-
tion of tertiary amine into the core of pyromellitic diimide. The
observed strong charge transfer band observed is attributed to
charge transfer from nitrogen to the aromatic part of the mole-
cule. The modulation of charge transfer site by metal ion binding
created a very sensitive recognition system. This new electron
push–pull system could be useful in designing molecular elec-
tronics due to its compact size and strong charge transfer nature.
165.53, 165.36, 141.38, 140.79, 132.92, 131.70, 71.41, 71.27,
71.09, 71.03, 70.64, 54.45, 54.24, 38.50, 32.07, 31.06, 29.52,
Experimental
1
NMR experiments were carried out in CDCl at 400 MHz ( H)
29.47, 28.88, 27.30, 22.94, 20.36, 14.98, 14.30. m/z (ESI)
þ
3
1
3
1
851.4 [M þ H] . m/z 851.5529. HRMS Anal. Calc. for
or 100 MHz ( C) on a Bruker DRX400. H NMR spectra are
internally referenced to the residually protonated solvent peak
þ
C H N NaO [M þ Na] 851.5510.
46 76
4
9
1
3
7.26 ppm) and C NMR spectra are referenced to the central
(
carbon peak (77.16 ppm) of CDCl . In all spectra, chemical
0
00
00
N,N-Di-n-octyl-3-(N -aza-15-crown-5)-6-N ,N -di-n-
butylaminopyromellitic diimide 3b
3
shifts are given in d relative to tetramethylsilane. Coupling
constants are reported in Hz. High-resolution mass spectra were
recorded on an Agilent ESI-TOF MS using electrospray ioni-
sation (ESI). UV-vis analyses were carried out in methanol on an
Agilent Cary 100 series UV-vis spectrometer.
A mixture of 2b (68 mg, 0.09 mmol) was dissolved in dibuty-
lamine (2 mL) and heated at 1408C, under nitrogen for 18 h.
Excess amine was removed under reduced pressure and the
crude material was chromatographed on flash silica (dichloro-
methane with 0–10 % v/v methanol). This material was redis-
solved in ethyl acetate and washed with deionised water
0
N,N-Di-n-octyl-3-(N -aza-18-crown-6)-6-bromo-
pyromellitic diimide 2a
(
2 ꢁ 50 mL). The organic layer was separated and dried under
reduced pressure to obtain 3b as a dark blue film (45 mg, 64 %).
3.74–3.59 (m, 24H), 3.41 (t, J 7.3, 4H), 1.62–1.65 (m, 4H),
1.43–1.50 (m, 4H), 1.34–1.19 (m, 24H), 0.89–0.81 (m, 12H).
165.54, 165.39, 141.61, 140.94, 133.32, 131.63, 71.66,
A mixture of N,N-di-n-octyl-3,6-dibromopyromellitic diimide
1
0
1
a
(100 mg, 0.17 mmol), 1-aza-18-crown-6 (150 mg,
.57 mmol), and dimethylacetamide (4 mL) was heated at
d
H
208C, under nitrogen for 18 h. Solvent was removed under
d
C
reduced pressure and the crude material was chromatographed
on flash silica (dichloromethane with 2–4 % v/v methanol). This
material was redissolved in ethyl acetate and washed with
deionised water (2 ꢁ 50 mL). The organic layer was separated
and dried under reduced pressure to obtain 2a as a dark red film
71.39, 71.21, 70.77, 54.77, 54.32, 38.55, 32.10, 31.10, 30.03,
29.54, 29.49, 28.89, 27.33, 22.96, 20.38, 14.39, 14.29. m/z (ESI)
þ
þ
785.4 [M þ H] , 807.3 [M þ Na] . m/z 785.5421, 807.5242.
HRMS Anal. Calc. for C44
[M þ Na] 807.5247.
H
N
73
O
4
[M þ H]þ 785.5428,
8
þ
(135 mg, 99 %). dH 3.59–3.76 (m, 28H), 1.63–1.67 (m, 4H),
0
1
1
7
.25–1.31 (m, 20H), 0.80–0.90 (m, 6H). dC 165.33, 164.36,
46.15, 137.60, 130.32, 105.29, 71.66, 71.13, 71.06, 70.88,
0.54, 54.71, 38.93, 29.46, 29.43, 28.71, 27.23, 22.94, 14.39.
N,N-Di-phenyl-3-(N -aza-18-crown-6)-6-
bromopyromellitic diimide 2d
A mixture of N,N-di-phenyl-3,6-dibromopyromellitic diimide
1b (102 mg, 0.19 mmol), 1-aza-18-crown-6 (120 mg, 0.46 mmol),
and dimethylacetamide (4 mL) was heated at 1208C, under
nitrogen for 18 h. Solvent was removed under reduced pressure
and the crude material was chromatographed on flash silica
þ
m/z (ESI) 802.3, 804.3 [M þ Na] . m/z 802.3262, 804.3252.
þ
HRMS Anal. Calc. for C H BrN NaO [M þ Na] 802.3254,
3
8
58
3
9
8
04.3234.
0
N,N-Di-n-octyl-3-(N -aza-15-crown-5)-6-bromo-
pyromellitic diimide 2b
(dichloromethane with 2–4 % v/v methanol). This material was
crystallised from methanol to yield 2d as dark purple/red
A mixture of N,N-di-n-octyl-3,6-dibromopyromellitic diimide
1
crystals (96 mg, 70 %). d 7.53–7.40 (m, 10H, ArH), 3.82–3.65
H
(m, 2H), 3.63–3.64 (m, 20H). d 164.12, 163.27, 146.86, 137.48,
C
a (63 mg, 0.11 mmol), 1-aza-18-crown-6 (75 mg, 0.34 mmol),

1
268
S. Sandanayake and S. J. Langford
1
7
31.43, 129.79, 129.42, 128.78, 127.00, 105.99, 71.57, 70.98,
þ
film (63 mg, 54 %). lmax/nm 630 (methanol). d 3.63 (t, J 7.4,
H
0.93, 70.83, 70.42, 54.88. m/z (ESI) 730.3, 732.1 [M þ Na] .
4H), 3.39 (t, J7.4, 8H), 1.57–1.68 (m, 4H), 1.19–1.35 (m, 8H),
1.38–1.44 (m, 28H), 0.81–0.90 (m, 18H). d 165.57, 140.66,
m/z 708.1546, 710.1531. HRMS Anal. Calc. for
C H BrN NO [M þ H] 708.1557, 710.1536.
C
þ
132.31, 54.26, 38.55, 32.08, 31.16, 30.04, 29.56, 29.50, 28.89,
þ
3
4
35
3
9
2
7.33, 22.95, 20.12, 14.37, 14.30. m/z (ESI) 695.6 [M þ H] .
0
N,N-Di-phenyl-3-(N -aza-15-crown-5)-6-
bromopyromellitic diimide 2c
m/z 695.5477. HRMS Anal. Calc. for C H N O 695.5475.
42 71 4 4
Determination of Association Constants
A mixture of N,N-di-phenyl-3,6-dibromopyromellitic diimide
1
and dimethylacetamide (4 mL) was heated at 1208C, under
nitrogen for 18 h. Solvent was removed under reduced pressure
and the crude material was chromatographed on flash silica
b (140mg, 0.27 mmol), 1-aza-15-crown-5 (140mg, 0.64 mmol),
A 100 mL solution of each compound, with absorbance adjusted
to between 0.3–0.6, were titrated with appropriate amounts of
2.0 M stock solution of sodium acetate, potassium acetate, and
TFA in methanol. UV-vis spectra were recorded after each
addition.
(dichloromethane with 2–4 % v/v methanol). This material was
crystallised from methanol to yield 2c as dark purple/red crystals
(116 mg, 66 %). dH 7.52–7.25 (m, 10H, ArH), 3.82–3.80
X-Ray Structure Determinations
(
m, 8H), 3.69–3.64 (m, 12H) d 164.08, 163.28, 146.65, 137.52,
.
C
Single crystal X-ray data for compounds 3c and 3d were
collected at 123 K using an Oxford Gemini Ultra CCD with
CuKa and MoKa radiation, respectively. The diffraction images
1
7
6
31.42, 129.93, 129.47, 128.85, 127.02, 106.35, 71.69, 70.99,
þ
0.84, 70.81, 54.92. m/z (ESI) 686.3, 688.3 [M þ Na] . m/z
86.1099, 688.1081. HRMS Anal. Calc. for C H BrN NaO
8
3
2
30
3
were processed, including a multi-scan absorption correction,
[10]
þ
[
M þ Na] 686.1114, 688.1081.
using the CrysAlisPro software package.
were solved by standard methods and refined by full matrix
Both structures
0
00
N,N-Di-phenyl-3-(N -aza-15-crown-5)-6-(N -morpholino)
pyromellitic diimide 3c
[11]
least-squares using the SHELX-97 program.
atoms were refined with anisotropic thermal parameters.
Non-hydrogen
A mixture of 2c (35 mg, 0.05 mmol) and morpholine (250 mg,
.87 mmol) was dissolved in dimethylacetamide (2 mL) and
Hydrogen atoms were placed in calculated positions using a
riding model with C–H distances of 0.95–0.99 A˚ and U (H) ¼
2
iso
heated at 1408C, under nitrogen for 3 h. Excess amine was
removed under reduced pressure and the crude material was
chromatographed on flash silica (dichloromethane with 0–10 %
v/v methanol). This material was crystallised from methanol to
yield 3c as dark blue crystals (16 mg, 43 %), mp 210–2118C.
lmax/nm 608, 362 (CH Cl ). d 7.55–7.40 (m, 10H, ArH), 3.91
1.2 ꢀ 1.5 ꢁ U (C). For the structure of 3d, part of the crown
eq
ether moiety was modelled as disordered over two positions, as
detailed in the Supplementary Material.
Crystal Data for 3c
2
2
H
C H N O , M ¼ 670.70, monoclinic, space group P2 /n,
3
6
38
4
9
1
(
t, J 4.5, 4H, CH O of morpholine), 3.77 (t, J 4.5, 4H, NCH ),
2
2
˚
a ¼ 16.1981(6), b ¼ 12.6027(4), c ¼ 15.6378(6) A; a ¼ 90,
3
1
1
.70–3.64 (m, 16H), 3.51 (t, J 4.5, 4H, CH N of morpholine). dC
2
3
˚
b ¼ 95.855(3), g ¼ 908; V ¼ 3175.6(2) A ; Z ¼ 4; D ¼ 1.403
c
64.68, 164.13, 142.36, 141.76, 132.88, 131.82, 130.86, 129.55,
28.77, 127.32, 71.64, 71.29, 71.15, 70.78, 68.04, 54.95, 53.33.
ꢀ3
ꢀ1
3
Mg m ; m ¼ 0.843 mm ; specimen: 0.20 ꢁ 0.12 ꢁ 0.02 mm ;
˚
CuKa ¼ 1.54184 A; y ¼ 66.82438; 5564 reflections collected;
max
þ
m/z (ESI) 693.2 [M þ Na] . m/z 693.2541. HRMS Anal. Calc.
4
719 unique (R ¼ 0.0309); GOF ¼ 1.038; R ¼ 0.0447,
þ
int
1
for C H N NaO [M þ Na] 693.2536.
3
6
38
4
9
wR ¼ 0.0925 [I . 2s(I)].
2
0
00
N,N-Di-phenyl-3-(N -aza-18-crown-6)-6-(N -morpholino)
pyromellitic diimide 3d
Crystal Data for 3d
C H N O .CH CN, M ¼ 755.81, monoclinic, space group
3
8
42
4
10
3
A mixture of 2d (106 mg, 0.14 mmol) and morpholine (250 mg,
.87 mmol) was dissolved in dimethylacetamide (2 mL) and
˚
P2 /n, a ¼ 18.1027(8), b ¼ 9.5146(4), c ¼ 21.6931(9) A; a ¼ 90,
1
2
3
˚
b ¼ 95.487(4), g ¼ 908; V ¼ 3719.3(3) A ; Z ¼ 4; D ¼ 1.350
c
heated at 1408C, under nitrogen for 3 h. Excess amine was
removed under reduced pressure and the crude material was
chromatographed on flash silica (dichloromethane with 0–10 %
v/v methanol). This material was crystallised from methanol to
yield 3d as dark blue crystals (82 mg, 74 %), mp 200–2018C.
lmax/nm 609, 363 (CH Cl ). d 7.56–7.49 (m, 4H, ArH), 7.45–
ꢀ3
ꢀ1
3
Mg m ; m ¼ 0.098 mm ; specimen: 0.25 ꢁ 0.12 ꢁ 0.12 mm ;
˚
MoKa ¼ 0.71073 A; y ¼ 30.51358; 8548 reflections collected;
max
6
500 unique (R ¼ 0.0391); GOF ¼ 1.014; R ¼ 0.0667,
int
1
wR ¼ 0.1157 [I . 2s(I)].
2
2
2
H
Supplementary Material
7
3
1
.39 (m, 6H, ArH), 3.93–3.88 (m, 4H), 3.74–3.59 (m, 24H),
.52–3.48 (m, 4H). d 164.69, 164.11, 142.43, 141.52, 132.49,
C
31.85, 131.06, 129.53, 128.73, 127.29, 71.48, 71.25, 71.04
þ
1
13
H, C, and mass spectroscopy data for compound families 2-3
are available on the Journal’s website. Detailed crystallographic
data are available from the Cambridge Crystallographic Data
Centre as supplementary publication nos. CCDC 986234
and 986235. Copies of the data can be obtained on application
to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:
þ44-1223-336033 or email: deposit@ccdc.cam.ac.uk).
(
broad), 70.60, 68.02, 54.75, 53.14. m/z (ESI) 737.1 [M þ Na] .
m/z 737.2797. HRMS Anal. Calc. for C H N NaO [M þ
3
8
42
4
10
þ
Na] 737.2799.
N,N-Di-n-octyl-3,6-di-(di-n-butylamino)pyromellitic
diimide 4
A mixture of N,N-di-n-octyl-3,6-dibromopyromellitic diimide
Acknowledgements
(
1
1a) (100 mg, 0.17 mmol) and dibutylamine (250 mg,
.94 mmol) was heated at 1208C, under nitrogen for 18 h. The
resulted crude material was chromatographed on flash silica
dichloromethane with 2–4 % v/v methanol) to obtain 4 as a blue
The authors wish to thank Dr Craig Forsyth for his help in solving and
interpreting the crystal structure data for 3c, d. The Australian Research
Council is gratefully acknowledged for funding to support this research
(DP13).
(

Crown Ether Derivatised Pyromellitic Diimides
1269
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