Control of H- and J-Type p Stacking
FULL PAPER
3,4,5-(Tris-2-ethylhexyloxy)benzoic acid (2e): Light yellow waxy material
(87%); 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=7.25 (s, 2H), 3.81
(m, 6H), 1.67–0.86 ppm (m, 43H); UV/Vis (CH2Cl2): lmax (e)=303
(5100), 276 nm (9700mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for C31H53O5
[MꢀH]ꢀ: 505.3898; found: 505.3899.
imidazole (10.5 g) were taken together in a flask and were stirred at
1308C for 24 h under an argon atmosphere. The reaction mixture was
cooled to room temperature and poured into methanol (100 mL). The
red precipitate was filtered and the solid was washed several times with
methanol. The crude product was purified by using column chromatogra-
phy with silica gel as the stationary phase and 5% MeOH in CHCl3 as
the eluent. The pure product was obtained as a bright red powder
(35%). M.p. 258–2608C; 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=
8.50 (d, J=7.6 Hz, 4H), 8.36 (d, J=8.0 Hz, 4H), 7.08 (s, 2H), 7.00 (s,
4H), 4.53 (m, 4H), 3.98 (m, 12H), 3.88 (m, 4H), 1.80–1.15 (m, 72H),
0.88 ppm (m, 18H); UV/Vis (CHCl3): lmax (e)=528 (79100), 491 (48300),
460 nm (17900mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for C90H125N4O12
[M+H]+: 1453.9288; found: 1453.9285.
4-[(S)-3,7-Dimethyloctyloxy]-3,5-diACTHNUGTRNEUNG(octyloxy)benzoic acid (2 f): White
1
waxy material (90%); H NMR (400 MHz, CDCl3, TMS, 300 K): d=7.19
(s, 2H), 4.00–3.97–3.88 (m, 6H), 1.82–0.85 ppm (m, 49H); UV/Vis
(CH2Cl2): lmax (e)=303 (4900), 276 nm (8700mꢀ1 cmꢀ1); HRMS (ESI):
m/z calcd for C33H57O5 [MꢀH]ꢀ: 533.4211; found: 533.4215.
3,4-[Bis-(S)-3,7-dimethyloctyloxy]-5-octyloxybenzoic acid (2g): White
1
powder (91%); m.p. 60–628C; H NMR (400 MHz, CDCl3, TMS, 300 K):
d=7.31 (s, 2H), 4.09–4.00 (m, 6H), 1.85–1.14 (m, 32H), 0.95–0.85 ppm
(m, 21H); UV/Vis (CH2Cl2): lmax (e)=303 (4900), 276 nm
(8700mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for C35H61O5 [MꢀH]ꢀ: 561.4525;
found: 561.4527.
All other PBI gelators were made by following the above procedure.
N,N’-DiACTHUNRTGNEUNG[3,4,5-(tris-4-methylbutyloxy)benzoylaminoethyl]perylene-
3,4:9,10-tetracarboxylic acid bisimide (PBI-4): Yield: 49%; m.p. 285–
2878C; 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=8.66 (d, J=8.0 Hz,
4H), 8.58 (d, J=8.04 Hz, 4H), 7.25 (along with residual solvent peak),
6.98 (s, 4H), 4.56 (m, 4H), 4.06–3.96 (m, 16H), 1.72–1.60 (m, 16H), 0.97–
0.92 ppm (m, 36H); UV/Vis (CHCl3): lmax (e)=528 (80200), 491 (51100),
460 nm (18100mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for C72H88N4NaO12
[M+Na]+: 1223.6291; found: 1223.6290.
3,4,5-TrisACHTUNGTRENNUNG(octyloxy)benzoylaminoethylamide (3b): Compound 2b (2.88 g,
5.69 mmol) was dissolved in dry dichloromethane (30 mL). Thionyl chlo-
ride (15 mL) was added along with 3 drops of dry DMF. The reaction
mixture was stirred at room temperature for 12 h. The stirring was stop-
ped and the solvents were evaporated under vacuum. The crude product
was obtained as a light yellow solid and it was taken to the next step
without further purification. It was redissolved in dry dichloromethane
(30 mL) and the solution was added dropwise to an ice-cold flask con-
taining ethylene diamine (30 mL). The reaction mixture was stirred in
the same ice bath for another 3–4 h and then at room temperature for
12 h. Then the reaction mixture was diluted with dichloromethane
(60 mL) and washed with water, aqueous NaHCO3, and brine. The organ-
ic layer was dried over Na2SO4 and the solvent was evaporated to get the
crude product, which was then added to ethanol (60 mL) and kept in the
refrigerator for 2 h. The precipitate was filtered under vacuum and dried
to get the crude product as a light yellow waxy material (65%). It was
taken to the next step without further purification. 1H NMR (400 MHz,
CDCl3, TMS, 300 K): d=8.00 (broad peak, 1H), 6.91 (s, 2H), 3.94 (m,
6H), 3.46 (m, 2H), 2.95 (m, 2H), 1.71 (m, 6H), 1.33–1.25 (m, 30H),
0.96 ppm (t, 9H); UV/Vis (CH2Cl2): lmax (e)=295 (3120), 264 nm
(9540mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for C33H61N2O4 [M+H]+:
549.4625; found: 549.4626.
N,N’-DiACHTNUTRGNEUNG[3,4,5-(tris-2-ethylhexyloxy)benzoylaminoethyl]perylene-3,4:9,10-
tetracarboxylic acid bisimide (PBI-5): Yield: 54%; m.p. 215–2178C;
1H NMR (400 MHz, CDCl3, TMS, 300 K): d=8.56 (d, J=7.6 Hz, 4H),
8.43 (d, J=8.1 Hz, 4H), 7.05 (t, 2H), 7.00 (s, 4H), 4.55 (m, 4H), 3.89–
3.82 (m, 16H), 1.76–1.28 (m, 54H), 0.90 ppm (m, 36H); UV/Vis (CHCl3):
lmax (e)=528 (81300), 491 (51400), 460 nm (19100mꢀ1 cmꢀ1); HRMS
(ESI): m/z calcd for C90H124N4NaO12 [M+Na]+: 1475.9108; found:
1475.9108.
N,N’-Di{4-[(S)-3,7-dimethyloctyloxy-3,5-dioctyloxy]benzoylaminoethyl}-
perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI-6): Yield: 48%; m.p.
251–2548C; 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=8.57 (d, 4H,
J=7.7 Hz), 8.47 (d, 4H, J=8.0 Hz), 7.02 (t, 2H), 6.98 (s, 4H), 4.55 (m,
4H), 3.01–3.87 (m, 16H), 1.82–0.84 ppm (m, 60H); UV/Vis (CHCl3): lmax
(e)=528 (80400), 491 (50000), 460 nm (18000mꢀ1 cmꢀ1); HRMS (ESI):
m/z calcd for C94H133N4O12 [M+H]+: 1509.9914; found: 1509.9909.
N,N’-DiACHTNUTRGNEUNG{3,4-bis-[(S)-3,7-dimethyloctyloxy-5-octyloxy]benzoylaminoethyl}-
perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI-7): Yield: 50%; m.p.
218–2208C; 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=8.56 (d, J=
7.7 Hz, 4H), 8.44 (d, J=8.0 Hz, 4H), 7.00 (t, 2H), 6.94 (s, 4H), 4.49 (m,
4H), 3.01–3.82 (m, 16H), 1.81–0.83 ppm (m, 68H); UV/Vis (CHCl3): lmax
(e)=528 (81700), 491 (51200), 460 nm (18500mꢀ1 cmꢀ1); HRMS (ESI):
m/z calcd for C98H140N4NaO12 [M+H]+: 1566.0148; found: 1566.0344.
Compounds 3d–3g were synthesized according to the above-described
procedure for compound 3b.
3,4,5-(Tris-3-methylbutyloxy)benzoylaminoethylamide (3d): Light yellow
solid (64%); m.p. 968C; 1H NMR (400 MHz, CDCl3, TMS, 300 K): d=
6.98 (s, 2H), 6.59 (broad peak, 1H), 4.05–3.98 (m, 6H), 3.48 (m, 2H),
2.93 (m, 2H), 1.71–1.61 (m, 9H), 0.96–0.94 ppm (m, 18H); UV/Vis
(CH2Cl2): lmax (e)=295 (3110), 264 nm (9530mꢀ1 cmꢀ1); HRMS (ESI):
m/z calcd for C24H43N2O4 [M+H]+: 423.3217; found: 423.3217.
3,4,5-(Tris-2-ethylhexyloxy)benzoylaminoethylamide (3e): Light yellow
waxy material (65%); H NMR (400 MHz, CDCl3, TMS, 300 K): d=6.97
Acknowledgements
1
(s, 2H), 6.55 (broad, 1H), 4.02–3.99 (m, 6H), 3.51–3.40 (m, 2H), 2.94 (m,
2H), 1.54–1.30 (m, 27H), 0.91–0.88 ppm (m, 18H); UV/Vis (CH2Cl2):
lmax (e)=295 (3150), 264 nm (9530mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for
C33H61N2O4 [M+H]+: 549.4625; found 549.4625.
Financial support by DFG for the research training school GRK 1221
“Control of electronic properties of aggregated p-conjugated molecules”
is gratefully acknowledged. S.G. thanks the Alexander von Humboldt
Foundation for a postdoctoral fellowship.
4-[(S)-3,7-Dimethyloctyloxy]-3,5-diACTHNUGRTNEUNG(octyloxy)benzoylaminoethylamide
(3 f): Light yellow waxy material (62%); 1H NMR (400 MHz, CDCl3,
TMS, 300 K): d=6.98 (s, 2H), 6.54 (broad, 1H), 4.02–3.99 (m, 6H), 3.50–
3.46 (m, 2H), 2.95 (t, 2H), 1.82–0.85 ppm (m, 49H); UV/Vis (CH2Cl2):
lmax (e)=295 (3330), 264 nm (9670mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for
C35H64N2O4 [M+H]+: 577.4938; found: 577.4938.
[1] a) J.-M. Lehn, Supramolecular Chemistry—Concepts and Perspec-
tives, Wiley-VCH, Weinheim (Germany), 1995; b) G. M. Whitesides,
3,4-[Bis-(S)-3,7-dimethyloctyloxy]-5-octyloxybenzoylaminoethylamide
(3g): Light yellow waxy material (67%); 1H NMR (400 MHz, CDCl3,
TMS, 300 K): d=6.98 (s, 2H), 4.01–3.97 (m, 6H), 3.48–3.46 (m, 2H), 2.95
(m, 2H), 1.71–1.12 (m, 32H), 0.96–0.85 ppm (m, 21H); UV/Vis (CH2Cl2):
lmax (e)=295 (3100), 264 nm (9510mꢀ1 cmꢀ1); HRMS (ESI): m/z calcd for
C37H69N2O4 [M+H]+: 605.5252; found: 605.5252.
[2] a) G. H. Brown, J. J. Wolken, Liquid Crystals and Biological Struc-
tures, Academic Press, New York (USA), 1979; b) G. M. Whitesides,
[3] a) F. M. Hoeben, P. Jonkheijm, E. W. Meijer, A. P. H. J. Schenning,
Topics in Current Chemistry, Vol. 258 (Ed.: F. Wꢀrthner), Springer,
Berlin (Germany), 2005.
N,N’-Di(3,4,5-trioctyloxybenzoylaminoethyl)perylene-3,4:9,10-tetracar-
boxylic acid bisimide (PBI-2): Compound 3b (0.40 g, 0.73 mmol), pery-
lene tetracarboxylic acid bisanhydride (0.136 g), ZnACTHNUGTRENUNG(OAc)2 (0.139 g), and
Chem. Eur. J. 2008, 14, 11343 – 11357
ꢂ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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