J O U R N A L O F C H E M I S T R Y Materials Easy synthesis of liquid crystalline perylene derivatives Peter Schlichting, Ulrike Rohr and Klaus Mu�llen* Max-Planck-Institut fu�r Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany Received 8th June 1998, Accepted 7th September 1998 Mesophase forming chromophores are an important challenge of material science. This article describes the synthesis of new perylene mesogenes 10.The materials were obtained by twofold Diels–Alder reactions of our recently published 151 isomeric mixture of 3,9- and 3,10-dialkylperylenes with N-heptadecyltriazoline-3,5-diones. In contrast to the analogous derivatives 1 published earlier by our group (see reference 3), the new compounds 10 are prepared by a more eYcient synthetic route and on a larger scale.Furthermore the characteristics of the liquid crystalline behavior of both materials are compared. Liquid crystalline chromophores combine the properties of dyes and the characteristics of liquid crystals. This combination is of particular interest for the design of photoconductive and NLO-active materials1 and the construction of light emitting diodes.2 Additional requirements are thermal and photochemical stability, the existence of a stable mesophase over a broad temperature range and of course, ready synthetic accessibility. N N N N N N O O O O CxH2 x+1 CyH2 y+1 CyH2 y+1 CxH2 x+1 P x- y (1) The perylene mesogens Px-y (1) were originally synthesized in our group by twofold Diels–Alder reaction of 3,10-dialkylperylenes 5 with N-alkyltriazolinediones 6.3 Px-y is an abbreviation used for simplicity, with P meaning perylene, x indicating the length of the alkyl chain attached to the perylene core and y the length of the alkyl chain of the urazole unit.The major disadvantage of the Px-y systems (1) was the lengthy synthesis of the 3,10-dialkylperylenes 5, which were used in the subsequent twofold Diels–Alder reaction.Starting from 1-bromonaphthalene (2), the products 5 were obtained through a three-step synthesis in good yields, however the intermediates required tedious purification methods and the reactions were restricted to small scales. An additional problem of this route was the use of highly toxic thallium salts. Herein we describe a new and easy route for the preparation of the new liquid crystalline perylene derivatives 10.Results and discussion The synthesis started with a twofold bromination of perylene. This reaction yielded a 151 isomeric mixture of 3,9- and 3,10- dibromoperylene which could not be separated by column chromatography or HPLC.4 Due to the fact that this isomeric mixture was used in the subsequent Hagihara-coupling, one also obtained an isomeric mixture of 3,9- and 3,10-dialkyl substituted perylenes 9.In our experiments, however, this mixture of isomers showed no significant diVerences in solubility, absorption and reactivity in comparison with the pure N N N N N N R1 R1 C17H35 H35C17 O O O O Br Br Br R1 R1 R1 R1 N N N O O C17H35 1a R1 = C5H11 b R1 = C6H13 c R1 = C8H17 d R1 = C12H25 4,5 a R1 = C5H11 5 12 11 10 9 8 7 6 5 4 3 2 1 K / DME CH3COOH Tl(CH3COO)3 b R1 = C6H13 c R1 = C8H17 d R1 = C12H25 6 4 2 3 R1MgBr 3,10-isomer 5.4 The advantage of this method is the simplicity Scheme 1 of the procedure and its suitability for large-scale synthesis.J. Mater. Chem., 1998, 8, 2651–2655 2651positions, the Pix-y 10 consist of a 151 isomeric mixture of the 3,9- and 3,10-substituted species.Analogous to the 3,9(10)- dibromoperylene (7), all attempts to separate the two isomers of the Pix-y 10 were unsuccessful. Characterization of the Pix-y materials 10 was achieved by field-desorption mass spectrometry (FD-MS), UV-VIS, 1H NMR and 13C NMR spectroscopy and was found to be in good agreement with the structures 10. No trace of side products was observed by the aforementioned characterization techniques or by thin layer chromatography, which is a particularly sensitive method for chromophores.The published liquid crystalline perylenes Px-y (1) are blue solids showing a maximum of absorption of lmax=585 nm. With X-ray diVraction we showed in earlier publications that the majority of Px-y derivatives 1 form discotic phases.3 Through the variation of the alkyl chains at the perylene core and/or the urazole units the characteristics of the mesophase can be controlled.With no or short alkyl chains (x<3) attached to the peri-positions of the perylene core (e.g. P0–17) smectic phases are obtained.3 The transition temperatures are also aVected if one varies the length of the alkyl chains of the 3,5-dioxotriazole units attached to the perylene.All Px-y derivatives 1 form remarkably stable (broad) mesophases (e.g. P12–11 is liquid crystalline in the temperature region between -23 and 373 °C) due to their pronounced form anisotropy shown by deuteron 2H NMR spectroscopy. The results of 2H NMR spectroscopy indicated that the five-membered, heterocyclic ring clearly deviates from a coplanar conformation. This nonplanarity could cause an entanglement between neighboring perylene units, resulting in an increased phase width of the Px-y compounds 1.3 Similar entanglements were found to be the reason for the increased stability of the mesophase formed by ester substituted triphenylenes.5 The new compounds Pix-y 10 show an absorption spectrum with lmax=585 nm (e#20 000 l mol-1 cm-1), which is the same as for Px-y 1.Similar to Px-y 1 the Pix-y derivatives 10 form mesophases, which qualitatively were detected by polarizing microscopy. The materials show birefringence and shearability, N N N N N N C17H35 H35C17 O O O O R2 (R2) R2 Br (Br) Br H R1 R1 R1 R1 R2 (R2) R2 N N N O O C17H35 b R2 = C6H13 c R2 = C8H17 d R2 = C12H25 9,10 a R2 = C5H11 10 6 a R1 = C3H7 b R1 = C4H9 c R1 = C6H13 d R1 = C10H21 9 7 8 H2 / Pd-C Pd(0) Scheme 2 both typical of liquid crystals. The transition temperatures of 10 were determined by calorimetric (DSC) measurements.From comparision of the transition temperatures of the For this reason we used the isomeric mixture 9 for the diVerent Pix-y derivatives 10 (Table 1, right column) it is clear preparation of the new liquid crystalline perylenes 10.that derivatives with the same alkyl chain length at the urazole Analogous to the already mentioned Px-y 1 the new liquid unit ( y=17) show decreasing transition temperatures into the crystalline perylenes are abbreviated as Pix-y 10. The ‘i’ stands mesophase with increasing length of the alkyl chain attached for isomeric mixture of 3,9- and 3,10-substituted dialkylperylto the perylene core.In addition to this trend, the isotropization enes 9. To prepare the Pix-y 10, the 3,9(10)-dibromoperylene temperature increases, i.e. the mesophase range broadens. This 7 was coupled with n-alkynes using a palladium catalyzed trend is exactly the same as in the case of the Px-y reaction in 98–100% yield.4 Subsequent hydrogenation of the compounds 1.triple bonds aVorded the 3,9(10)-dialkylperylenes 9 in quanti- Comparison of the transition temperatures of Pix-y 10 with tative yield.4 As in the case of 3,10-dialkylperylenes 5 these Px-y 1 (Table 1) reveals that the Pix-y 10 have slightly lower were then reacted with N-heptadecyltriazoline-3,5-dione 6 in melting points than the Px-y 1. Isotropization temperatures boiling xylene in a twofold Diels–Alder reaction in both bayare similar, if both classes of compounds have the same alkyl regions of the dialkylperylenes 9 to yield the blue Pix-y 10 chains attached to the perylene core (i.e.same x). The diVer- diaddition products in 95–98% yield.3 The materials show ences in the transition temperatures into the mesophase (Tm) good solubility in organic solvents.The purification steps were are especially pronounced when x is small. For example Pi5–17 much easier than in the case of the Px-y compounds 1, the 10a melts at 47 °C while P5–17 1a shows the transition into dibromoperylene 7 and the dialkyne substituted derivatives 8 the mesophase at 89 °C, a diVerence of 42 °C. In summary, the could be recrystallized and the dialkylperylenes 9 were used fact that the melting temperature Tcreases while the for the next reaction without further purification. Unlike the Px-y derivatives 1, with the alkyl substituents at the 3,10- isotropization temperature Ti is almost the same for the Table 1 Comparison of the phase transition temperatures of Px-y and Pix-y derivatives (Cryst=crystalline, Iso Liq=isotropic liquid ) measured with diVerential scanning calometry (DSC); all data taken from the 2nd heating cycle, scan rate 10 °Cmin-1 x Px-17 Pix-17 5 1a Cryst 89 Colho 226 Iso Liq (°C) 10a Cryst 47 Colho 238 Iso Liq (°C) 6 1b Cryst 76 Colho 245 Iso Liq (°C) 10b Cryst 32 Colho 243 Iso Liq (°C) 8 1c Cryst 57 Colho 288 Iso Liq (°C) 10c Cryst 29 Colho 287 Iso Liq (°C) 12 1d Cryst 16 Colho 316 Iso Liq (°C) 10d Cryst 14 Colho 320 Iso Liq (°C) 2652 J.Mater. Chem., 1998, 8, 2651–2655makes them readily available for diVerent investigations and applications. This was one of the requirements for microwave conductivity detections, which will be presented in a following paper.6 As terminal difunctionalized dialkylperylenes 11 can be synthesized in a similar way to the dialkylperylenes,3 the improved route presented here oVers a possibility for the preparation of functionalized Pix-y derivatives 10 as well, if functionalized alkynes are employed in the coupling reactions.In contrast, the synthesis of 3,10-substituted and terminal functionalized dialkylperylenes starting from 1-bromonaphthalene (2) (Scheme 1) is not possible, since the functional groups are incompatible with the cyclization conditions.The functional Pix-y 10 compounds can then be used to build up liquid crystalline perylene polymers, which is a major goal of our present work. Experimental Measurements 1H NMR: Varian Gemini 200 (200 MHz), Bruker AC 300 (300 MHz), Bruker AMX 500 (500 MHz). 13C NMR: Varian Gemini 200 (50.32 MHz), Bruker AC 300 (75.48 MHz), Bruker AMX 500 (125.80 MHz).UV–VIS: Perkin-Elmer Lambda 9, Perkin-Elmer Lambda 15. FD-MS: ZAB2-SE-FPD (VG Instruments). Melting points (uncorrected): Bu� chi melting point apparatus. Thermal analysis: Mettler DSC 30 diVerential scanning calorimeter. Thin layer chromatography (TLC): Ready-to-use silica gel 60 F254 plates (Merck). Column chromatography: Silica gel, particle size 70–230 mesh (Merck, Fig. 1 Small-angle X-ray diVractograms of P6–17 (1b) at 127 °C and Pi6–17 (10b) at 140 °C. Geduran Si 60) and aluminium oxide (Merck, Geduran AL 90) using the eluents indicated. The argon used was passed through an oxygen scavenger (BTS catalyst, BASF AG), silica corresponding Px-y materials 1, leads to even broader mesogel and KOH pellets. THF, piperidine, DME and DMF were phases for the Pix-y 10.This eVect might be caused by the purified and dried according to standard procedures.7 slightly higher irregularity in the case of the new Pix-y Hydrogen gas was purchased from Linde and used without compounds 10 due to the presence of an isomeric mixture. further purification. The small-angle X-ray diVractograms The mesophases of 10 were characterized by small-angle were measured on a Siemens Kristallflex D-500 diVractometer X-ray scattering.Similar to the corresponding Px-17 com- (beam divergence 0.3), equipped with a hot stage. Cu-Ka pounds 1a–d, all the Pix-17 derivatives 10a–d form discotic radiation was selected by a graphite crystal monochromator. phases with hexagonal superstructure (Colho). Fig. 1 shows the All samples were heated to measurement temperature and kept characteristic scattering peaks of a Colho phase for P6–17 1b at this temperature for 30 min prior to measurement as well as for Pi6–17 10b.(measurement time ~2 h). The intense (100)-reflections at 2h=4.05° (P6–17 1b) and 2h=3.95° (Pi6–17 10b) correspond to an intercolumnar dis- Synthesis tance of approximately 22 A° in both cases.Each derivative shows the (001)-reflection at 2h=25.5° which indicates an 3,9- and 3,10-Dialkylperylenes (151 isomeric mixture). The intracolumnar distance of 3.5 A ° . The hexagonal superstructure diVerent 3,9(10)-dialkylperylenes were prepared according to of both substances was proven from the (110)-reflection our recently published procedure: ‘New synthetic routes to occurring at 2h=7.00° (P6–17 1b) and 2h=6.85° (Pi6–17 10b).alkyl-substituted and functionalized perylenes’.4 N-Heptadecyltriazoline-3,5-dione (6). Heptadecyltriazoline- Conclusions dione 6 was obtained in a five-step reaction starting from The isomeric mixture Pix-y 10 forms very stable liquid stearic acid employing the procedure described by Saville.8 crystalline phases similar to the known Px-y derivatives 1, and therefore, exhibit the same attractive physical properties.Synthesis of Px-y (1) Besides the fact that the mesophases are slightly broader, the 4,4¾-Dibromo-1,1¾-binaphthyl (3). 10 g Thallium trifluoro- new perylene mesogens Pix-y 10 have almost the same liquid acetate and 7.6 g 1-bromonaphthalene were dissolved in 150 ml crystalline properties as the Px-y derivatives 1.Due to the ease trifluoroacetic acid and stirred at room temperature for 3 h. of preparation of the Pix-y derivatives 10, larger amounts of The color of the reaction mixture gradually turned from deep the liquid crystalline chromophores can be synthesized, which purple to gray and the product precipitated. After addition of 150 ml of water the crude product was filtered through a Table 2 Small-angle X-ray scattering-reflections of P6–17 1b at 127 °C Bu�chner funnel, dried under vacuum, recrystallized from diox- and Pi6–17 10b at 140 °C ane and chromatographed over a short column (silica gel– P6–17 1b Pi6–17 10b petroleum ether) The product crystallized as white needles and could be isolated in 38% yield (2.9 g), melting point: 216 °C; (100) 2h=4.05° 2h=3.95° 1H-NMR (200 MHz, CDCl3): d=8.36–8.32 (d; 2 H, 3J=8 Hz, (110) 2h=7.00° 2h=6.85° 2 Ar-H), 7.99–7.95 (d; 2 H, 3J=8 Hz, 2 Ar-H), 7.57–7.53 (m; (001) 2h=25.5° 2h=25.5° 2 H, 2 Ar-H), 7.35–7.24 (m; 6 H, 6 Ar-H); 13C-NMR J.Mater. Chem., 1998, 8, 2651–2655 2653(50 MHz, CDCl3): d=137.72, 133.90, 132.02, 129.49, 128.20, 3J=8.8 Hz, 2 Ar-H), 7.97 (s, 2 H, 2 Ar-H), 7.40–7.10 (m; 2 H, 2 Ar-H), 3.72–3.65 (t; 4 H, 3J=6.7 Hz, CH2-N), 2.72–2.55 127.90, 127.51, 123.00.FD-MS (8 kV): m/z=410.00 (100%) [M+]. (m; 4 H, 2 Ar-CH2), 1.82–1.78 (m; 4 H, 2 CH2), 1.70–1.63 (m; 4 H, 2 CH2), 1.55–1.18 (m; 68 H, 34 CH2), 0.92–0.81 (m; 12 H, 4 CH3). 13C-NMR (125 MHz, C2D2Cl4, 110 °C): d= 4,4¾-Di(n-hexyl )-1,1¾-binaphthyl (4). 8.0 g (12.1 mmol) 4,4¾- Dibromo-1,1¾-binaphthyl (3) and 200 mg Ni(dppe)Cl2 (dppe= 145.02, 144.98, 144.48, 141.18, 129.98, 129.83, 126.39, 125.02, 124.96, 113.82, 113.70, 113.15, 110.98, 41.33, 40.50, 32.86, diphenylphosphinoethane) were suspended in 50 ml of dry ether under an argon atmosphere. 9.16 g (48.40 mmol) 32.20, 32.09, 29.93, 29.53, 29.16, 28.10, 28.03, 27.59, 27.17, 27.13, 26.70, 22.83, 22.69, 13.93. UV (CH2Cl2): lmax (e)= Butylmagnesium bromide in 20 ml ether were added at room temperature with a syringe through a septum.The reaction 585 nm (11252), 539 nm (8542), 503 nm (4465). FD-MS (8 kV): m/z=1091.00 (100%) [M+]. mixture was stirred at room temperature until it began to reflux spontaneously. When the solution started to cool it was heated to reflux for 18 h. The cooled reaction mixture was Synthesis of the Pix–y compounds hydrolyzed by addition of 5 ml of methanol. The solvent was Pi5–17 (10a).Synthesis was performed using Method A: evaporated and the crude product dried under vacuum and 250 mg (0.63 mmol) 3,9(10)-di(n-pentyl )perylene (9a) and purified by chromatography with silica gel and pentane as 1.3 g (3.85 mmol) N-heptadecyltriazolinedione (6) yielded eluent.The yield was 7.95 g (93%) of white crystals, mp: 56 °C. 630 mg (94%) of the deep blue product. DSC: Tm=47 °C, Ti= 1H-NMR (200 MHz, CDCl3): d=8.17–8.14 (d; 2 H, 3J=8 Hz, 238 °C. 1H-NMR (500 MHz, C2D2Cl4, 110 &de: d=8.21–8.16 2 Ar-H), 7.60–7.41 (m; 8 H, 8 Ar-H), 7.36–7.21 (m; 2 H, 2 (m; 2 H, 2 Ar-H), 8.10 (s, 2 H, 2 Ar-H), 7.47–7.40 (m; 2 H, Ar-H), 3.21–3.08 (t; 4 H, 3J=7 Hz, 2 Ar-CH2), 1.98–1.80 (m; 2 Ar-H), 3.71–3.66 (t; 4 H, 3J=6.7 Hz, CH2-N), 2.70–2.55 4 H, 2 Ar-CH2-CH2), 1.56–1.30 (m; 12 H, 6 CH2), 0.99–0.85 (m; 4 H, 2 Ar-CH2), 1.78–1.76 (m; 4 H, 2 CH2), 1.63–1.60 (t; 6 H, 3J=7 Hz, 2 CH3). 13C-NMR (50 MHz, CDCl3): d= (m; 4 H, 2 CH2), 1.50–1.15 (m; 64 H, 32 CH2), 0.89–0.86 (m; 139.22, 137.64, 133.99, 132.52, 128.20, 128.11, 126.00, 125.92, 12 H, 4 CH3). 13C-NMR (125 MHz, C2D2Cl4, 110 °C): d= 125.86, 124.55, 33.81, 32.74, 31.24, 30.09, 23.66, 14.70. IR: n�= 144.69, 144.63, 144.51, 141.10, 130.01, 129.80, 126.43, 125.01, 2961, 1379, 849, 763 cm-1. FD-MS (8 kV): m/z=422.68 [M+]. 124.93, 113.83, 113.67, 113.13, 110.89, 41.23, 40.12, 32.87, 32.21, 32.11, 29.90, 29.51, 29.15, 28.10, 27.98, 27.58, 27.17, 3,10-Di(n-hexyl )perylene (5). 2 g (4.7 mmol) 4,4¾-Bis-n- 27.12, 26.70, 22.83, 22.71, 14.23. UV (CH2Cl2): lmax (e)= hexyl-1,1¾-binaphthyl (4) were dissolved in 50 ml dimethoxy- 585 nm (10593), 539 nm (8912), 503 nm (3876). FD-MS ethane (DME) (dried over potassium) under an argon atmos- (8 kV): m/z=1063.0 (100%) [M+]. phere. 2 g potassium was added in small pieces in an argon stream. The reaction mixture was stirred in the dark at room Pi6–17 (10b).Synthesis was performed using Method A: temperature for 2 days and monitored by thin layer chromatog- 250 mg (0.60 mmol) 3,9(10)-di(n-hexyl )perylene (9b) and raphy. After completion of the reaction the excess potassium 1.2 g (3.57 mmol) N-heptadecyltriazolinedione (6) yielded was removed carefully and the solution was stirred under an 620 mg (95%) of the deep blue product.DSC: Tm=32 °C, Ti= oxygen atmosphere for 1 day. The color changed from deep 243 °C. 1H-NMR (500 MHz, C2D2Cl4, 110 °C): d=8.03–8.01 blue to orange indicating the oxidation of the perylene anions. (d; 2 H, 3J=8.8 Hz, 2 Ar-H), 7.96 (s, 2 H, 2 Ar-H), 7.50–7.20 The DME was removed by distillation and the crude product (m; 2 H, 2 Ar-H), 3.71–3.66 (t; 4 H, 3J=6.7 Hz, CH2-N), purified by column chromatography (silica gel–CH2Cl2), mp: 2.69–2.55 (m; 4 H, 2 Ar-CH2), 1.83–1.78 (m; 4 H, 2 CH2), 131 °C. 1H-NMR (200 MHz, CDCl3): d=8.19–8.17 (d; 2 H, 1.70–1.65 (m; 4 H, 2 CH2), 1.56–1.18 (m; 68 H, 34 CH2), 3J=8 Hz, 2 Ar-H), 8.08–8.05 (d; 2 H, 3J=8 Hz, 2 Ar-H), 0.91–0.83 (m; 12 H, 4 CH3). 13C-NMR (125 MHz, C2D2Cl4, 7.87–7.84 (d; 2 H, 3J=8 Hz, 2 Ar-H), 7.51–7.45 (dd; 2 H, 110 °C): d=145.01, 144.93, 144.21, 141.20, 129.98, 129.80, 3J=8 Hz, 2 Ar-H), 7.31–7.29 (d; 2 H, 3J=8 Hz, 2 Ar-H), 126.35, 125.01, 124.93, 113.80, 113.72, 113.13, 110.89, 41.30, 3.01–2.96 (t; 4 H, 3J=7 Hz, 2 Ar-CH2), 1.80–1.70 (m; 4 H, 2 40.10, 32.81, 32.19, 32.01, 29.91, 29.52, 29.16, 28.10, 28.02, Ar-CH2-CH2), 1.50–1.32 (m; 12 H, 6 CH2), 0.92–0.87 (t; 6 27.58, 27.15, 26.99, 26.68, 22.81, 22.70, 13.90.UV (CH2Cl2): H, 3J=7 Hz, 2 CH3). 13C-NMR (75 MHz, d8-THF): d= lmax (e)=585 nm (10903), 539 nm (8937), 503 nm (4003). 138.32, 132.91, 131.94, 129.57, 128.77, 126.62, 126.05, 123.57, FD-MS (8 kV): m/z=1091.20 (100%) [M+]. 119.83, 33.24, 31.66, 30.45, 29.40, 22.54, 13.95. UV (Dioxan): lmax (e)=451nm (16595), 423nm (12882), 401 nm (5754).Pi8–17 (10c). Synthesis was performed using Method A: FD-MS (8 kV): m/z=420.52 (100%) [M+]. 250 mg (0.52 mmol) 3,9(10)-di(n-octyl )perylene (9c) and 1.06 g (3.14 mmol) N-heptadecyltriazolinedione (6) yielded Twofold Diels–Alder reaction of the dialkylperylenes 5 or 9 560 mg (94%) of the deep blue product. DSC: Tm=29 °C, Ti= with N-heptadecyltriazolinedione 6 (Method A). 250 mg of 287 °C. 1H-NMR (500 MHz, C2D2Cl4, 110 °C): d=8.20–8.15 dialkyl substituted perylene derivative 5 or 9 were dissolved in (m; 2 H, 2 Ar-H), 8.09 (s, 2 H, 2 Ar-H), 7.48–7.40 (m; 2 H, 25 ml of m-xylene and heated to reflux. A fourfold excess of 2 Ar-H), 3.71–3.65 (t; 4 H, 3J=6.7 Hz, 2 CH2-N), 2.82–2.70 N-heptadecyltriazolinedione 6 was added to the solution in (m; 4 H, 2 Ar-CH2), 1.81–1.71 (m; 4 H, 2 CH2), 1.70–1.59 small portions and the reaction monitored by thin layer (m; 4 H, 2 CH2), 1.45–1.18 (m; 76 H, 38 CH2), 0.90–0.78 (m; chromatography until the starting material (yellow) and the 12 H, 4 CH3). 13C-NMR (125 MHz, C2D2Cl4, 110 °C): d= monoadduct (red) vanished. When the reaction was completed 144.98, 144.96, 144.47, 141.21, 130.01, 129.97, 129.85, 126.38, the hot solution was poured into 200 ml of methanol.The 126.36, 125.02, 124.98, 113.81, 113.72, 113.13, 110.91, 41.32, precipitate was collected by filtration, redissolved in dichloro- 40.18, 32.85, 32.18, 32.07, 29.96, 29.87, 29.53, 29.38, 29.16, methane and added dropwise to hot ethanol. The hot solution 28.13, 28.08, 27.63, 27.45, 27.16, 26.73, 22.85, 22.78, 22.70, was filtered and the product isolated as a blue solid which was 14.03.UV (CH2Cl2): lmax (e)=585 nm (10102), 539 nm further purified by chromatography over silica gel with (8946), 503 nm (4203). FD-MS (8 kV): m/z=1146.5 (100%) dichloromethane as eluent. [M+]. P6–17 (1b). Synthesis was performed using Method A: 250 mg (0.60 mmol) 3,10-di(n-hexyl )perylene and 1.2 g Pi12–17 (10d). Synthesis was performed using Method A: 250 mg (0.42 mmol) 3,9(10)-di(n-dodecyl )perylene (9d) and (3.57 mmol) N-heptadecyltriazolinedione (6) yielded 615 mg (94%) of the deep blue product. DSC: Tm=76 °C, Ti=245 °C. 0.86 g (2.55 mmol) N-heptadecyltriazolinedione (6) yielded 492 mg (93%) of the deep blue product. DSC: Tm=14 °C, Ti= 1H-NMR (500 MHz, C2D2Cl4, 110 °C): d=8.04–8.02 (d; 2 H, 2654 J. Mater. Chem., 1998, 8, 2651–26552 T.Christ, B. Glu� sen, A. Greiner, A. Kettner, R. Sander, 320 °C. 1H-NMR (500 MHz, C2D2Cl4, 110 °C): d=8.10–8.00 V. Stu�mpflen, V. Tsukruk and J. H. Wendorf, Adv. Mater., 1997, (m; 2 H, 2 Ar-H), 8.00 (s, 2 H, 2 Ar-H), 7.35–7.10 (broad; 2 9, 48. H, 2 Ar-H), 3.71–3.68 (t; 4 H, 3J=8 Hz, 2 CH2-N), 2.65 3 (a) C. Go� ltner, D. Pressner, K. Mu� llen and H. W. Spieß, Angew. (broad; 4 H, 2 Ar-CH2), 1.82–1.78 (t; 4 H, 3J=8 Hz, 2 CH2), Chem., 1993, 105, 1722; Angew.Chem., Int. Ed. Engl., 1993, 32, 1.64–1.60 (t; 4 H, 3J=7 Hz, 2 CH2), 1.48–1.22 (m; 92 H, 46 1660; (b) D. Pressner, C. Go� ltner, H. W. Spieß and K. Mu� llen, Ber. Busenges. Phys. Chem., 1993, 97, 1362. CH2), 0.89–0.86 (t; 12 H, 3J=6 Hz, 4 CH3). UV (Dioxan): 4 P. Schlichting, U. Rohr and K. Mu� llen, Liebigs Ann./Recl., 1997, lmax (e)=585 nm (11165), 539 nm (9034), 503 nm (4235). 395. FD-MS (8 kV): m/z=1259.00 (100%) [M+]. 5 M. Werth, S. U. Vallerien and H. W. Spiess, Liq. Cryst., 1991, 10, 759. 6 A. M. van de Craats, J. M. Warman, P. Schlichting, U. Rohr and References K. 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