J O U R N A L O F C H E M I S T R Y Materials Quaterrylenebis(dicarboximide)s: near infrared absorbing and emitting dyes Yves Geerts,a† Heribert Quante,a Harald Platz,a Rainer Mahrt,b M. Hopmeier,b Arno Bo�hmc and Klaus Mu�llen*a‡ aMax-Planck-Institut fu�r Polymerforschung, Ackermannweg 10, D-55128 Mainz, Germany bFachbereich Physikalische Chemie und Zentrum fu�r MaterialwissenschaVen, Philipps Universita�t, Renthof 5, D35032 Marburg, Germany cBASF AG, ZDP/0-M311, 67056 Ludwigshafen, Germany Received 8th June 1998, Accepted 2nd September 1998 New ladder-type chromophores, the quaterrylenebis(dicarboxdiimide)s 2, 18 and 23, have been synthesised which, despite their extended p-system, exhibit good solubility in organic solvents and film forming properties when adequately substituted.These unprecedented dyes, which absorb and even emit light in the NIR window, are also characterized by oustanding chemical, thermal and photochemical stability with regard to their absorption range. The potential formation of J-aggregates in strongly acidic media has been investigated and has been ruled out by combined 1H NMR and UV–VIS–NIR spectroscopy experiments.In addition, their photophysical and electrochemical characteristics have been explored and are discussed. Introduction The search for novel, near infrared (NIR) absorbing and emitting dyes is a challenge in dyestuV chemistry, mainly because of the potential high-technology applications in optical recording, thermally written displays, laser printers, laser filters, infrared photography and medicine.1 Despite the high demand, only a few NIR dyes, such as cyanine dyes, are eVectively used in practice.A prerequisite in the design of chromophores is the consideration of their chemical, thermal and photochemical stability.2 Perylene derivatives and, in particular, perylenebis(dicarboximide)s 1, are well-known for their outstanding chemical, thermal and photochemical inertness. 3,4 Their uses range from paints and varnishes to hightechnology applications such as tracers in fluorescence analytical assays,5 charge-transport in Langmuir–Blodgett films,6 photovoltaic cells,7 xerography,8 optical switches,9 laser-dyes10 and fluorescent collectors.11 Clearly, new chromophores such as quaterrylenebis(dicarboximide)s 2, which combine the outstanding properties of perylenebis(dicarboximide)s 1 with NIR absorption, are highly desirable.N N O O O O N N O O O O O O O O Ar Ar Ar Ar 1a 1b 12 7 11 8 a b c d 2 5 1 6 The first attempts at extending the p-system of perylene 3 to higher rylenes, namely terrylene 4 and quaterrylene 5, were the perylenebisamidine 9.16 These NIR dyes are characterized carried out by Clar.12 However, due to the lack of adequate by high photochemical and thermal stability.Moreover terry- alkyl substitution, resulting in extreme insolubility, the purifi- leneimides 7 and 8 exhibit oustanding quantum fluorescence cation and characterization of terrylene 4 and quaterrylene 5 yields of 0.9±0.1 and 0.6±0.1, respectively. were not possible.13 In this paper, we report the detailed synthesis and the More recently, we synthesized the first soluble oligorylene characterization of quaterrylenebis(dicarboximide)s 2, 18 and series 6.14 The introduction of tert-butyl groups at the periph- 23, which are higher homologues of perylenebis(dicarboxim- ery of the rigid aromatic structure drastically improved their ide)s 117 and of terrylenebis(dicarboximide)s 7.15 In addition, solubility in common organic solvents. Remarkably enough, the photophysical, thermal and electrochemical properties of terrylene, quaterrylene and even pentarylene were fully characquaterrylenebis( dicarboximide)s 2, 18 and 23 are compared to terized and their photophysical behavior correlated with their those of perylenebis(dicarboximide)s 1 and to terrylenebis- structure.14b (dicarboximide)s 7 and discussed in the light of their structures.We have also reported some new fluorescent dyes emitting at long wavelengths (600<l<750 nm) and even in the NIR range (l>750 nm), which are structurally related to quaterry- Results and discussion lenebis(dicarboximide)s, namely the terryleneimides 7,815 and Synthesis The synthetic pathway to quaterrylenebis(dicarboximide)s 2a,b †Chercheur Qualifie� au Fonds National de le Recherche Scientifique, is illustrated in Scheme 1.The key building block for the synthesis Universite� libre de Bruxelles, Chimie Macromole�culaire, CP 206/1, of quaterrylenebis(dicarboximide)s is the N-substituted pery- Boulevard du Triomphe, 1050 Bruxelles, Belgium. ‡E-mail: muellen@mpip-mainz.mpg.de lene-3,4-dicarboximides 11a,b which are obtained via the partial J.Mater. Chem., 1998, 8(11), 2357–2369 2357N O O R N O O R 16 11 15 12 18 9 17 10 2 5 1 6 2a R = C12H25 20 7 19 8 b R = C6H3-2,6-Pri 2 c R = Bu 3 4 5 N O O N N O N O N N O O R' O O O O Ar Ar Ar Ar N N O N N O O O O O Ar Ar Ar Ar N O O O R R R R Br Br Br Br Br Br Br Br 7a,b a R = H, b R = OAr R' = C8H17, C6H3-2,6-Pri 2 8a,b 9- syn 9- anti However, we recently reported some developments in the field of organometallic aryl–aryl coupling which allows the synthesis of 14a,b in higher yields.15,17 Specifically, two organometallic synthetic pathways from the monobromo Nsubstituted perylene-3,4-dicarboximide 12a,b to the biperylene 14a,b have been attempted.The first synthetic route, a one step Yamamoto homocoupling20 with the zero-valent nickel catalyst bis(cycloocta-1,5-diene)nickel(0) [Ni(cod)2] has successfully been applied and aVorded the biperylenes 14a,b in excellent yields (83–89%).The second synthetic route to the biperylene 14b is based on the Stille heterocoupling of 6 a b c d n n 0 1 2 3 monobromo N-substituted perylene-3,4-dicarboximide 12b with its stannylated analogue 13b in the presence of the zero-valent tetrakis(triphenylphosphine)palladium catalyst decarboxylation of perylenedicarboxylic anhydrides 10a,b.18,19 The bromination of the N-substituted perylene-3,4-dicarboxim- [Pd(PPh3)4].15,21 This route requires an additional step, but presents the advantage of replacing the relatively toxic, air- ides 11a,b at position 9 leads to the monobromo N-substituted perylene-3,4-dicarboximides 12a,b in 94–98% yield.Misono sensitive and expensive Ni(cod)2 by the more conventional Pd(PPh3)4. Moreover, the coupling of two diVerently substi- and Nagao have synthesized the biperylene 14c via an Ullmann coupling of the 9-bromo-N-butylperylene-3,4-dicarboximide tuted perylene derivatives, resulting in non-symmetrically Nsubstituted quaterrylenebis(dicarboximide)s, is therefore pos- 12c in low yield.18,19 The low yield has been attributed to the large amount of side products rendering the purification diY- sible.This significantly widens the scope of applications of the quaterrylenebis(dicarboximide)s which could be introduced as cult and to the inadequate alkyl substitution at the imide position resulting in low solubility of the biperylene 14c.side chain functions in polymers to combine the processability 2358 J. Mater. Chem., 1998, 8(11), 2357–2369N O O R N O O O O O R N O O R N O O R N O O R Br N O O R SnBu3 N O O R N O O R 2a,b 14a–c 10a–c 11a–c 12a –c 13b a R = C12H25 b R = C6H3-2,6-Pri 2 c R = Bu Scheme 1 Synthetic pathway to quaterrylenebis(dicarboximide) 2a.and good film-forming properties of polymers with the intrinsic which consists of introducing phenoxy substituents into the bay-regions of the aromatic core, is well-known in the case of properties of quaterrylenebis(dicarboximide)s. One could also selectively introduce another functional group, e.g. an electron the perylenebis(dicarboximide) 1b.15,16,25 The introduction of substituents in the bay-region of the perylenebis(dicarboxim- donor for photoinduced electron transfer or a biologically active molecule for NIR fluorescence analytical assays.5 ide) 1b presents the additional advantage of further extending the absorption maxima to longer wavelength. In analogy to The last synthetic step of Scheme 1 involves the cyclization of the biperylenes 14a,b into quaterrylenebis perylenebis(dicarboximide) 1b, we have attempted the synthesis of tetraphenoxy substituted quaterrylenebis(dicarboxim- 2a,b in the presence of a base and an oxidizing agent.23,24 Specifically, the cyclization reaction has been carried out in a ide) 18. The synthetic pathway to the tetraphenoxy substituted quaterrylenebis(dicarboximide) 18 is given in Scheme 2 and KOH/ethanol melt containing glucose as oxidizing agent at 120 °C.24 The resulting quaterrylenebis(dicarboximide) 2b was shares many similarities with that of the unsubstituted quaterrylenebis( dicarboximide)s 2a,b.readily purified by recrystallization, aVording the desired product 2b in 83% yield, whereas the less soluble quaterrylenebis- The three-fold bromination of 11 under drastic conditions gives the perylene tribromide 15 in excellent yield (91%).The (dicarboximide) 2a was obtained in lower yield (37%) and was purified by extraction of the by-products with chloroform. In selective nucleophilic substitution under basic conditions of the two bromine atoms in the bay-regions with phenol deriva- the case of quaterrylenebis(dicarboximide) 2b, further purifi- cation by column chromatography was only performed for tives aVords 16 in a yield of 33%.The moderate yield is due to side reactions, namely the substitution of all three bromine the preparation of analytical samples. The quaterrylenebis(dicarboximide) 2a is only slightly atoms by phenoxy groups and dehalogenation. Comparable to the synthesis of the biperylenes 14a,b, the soluble in organic solvents (typically <10-5 M) at room temperature and is better viewed as a pigment than a dye.Yamamoto coupling aVords the biperylene 17 in a yield of 88%. The cyclization of 17 to the tetraphenoxy substituted However for numerous applications, good processability, i.e. high solubility in organic media and good film-forming proper- quaterrylenebis(dicarboximide) 18, in a yield of 85%, has been carried out as described for the unsubstituted perylene 14.As ties, is required. As previously mentioned, one way to achieve processability is to introduce quaterrylenebis(dicarboximide) expected, the solubility of quaterrylenebis(dicarboximide) 18 is much higher than that of 2 and reaches ~10-2 M in 2a as a pendant group on a polymer chain. Another method, J.Mater. Chem., 1998, 8(11), 2357–2369 2359N O O R N O O R N O O R N O O R N O O R Br N O O R N O O R Br R' R' R' R' R' R' R' R' R' R' Br Br 18 17 R = C6H3-2,6-Pri 2 R' = OC6H4-4-Bu t 15 11 16 Scheme 2 Synthetic pathway to quaterrylenebis(dicarboximide) 18. chlorinated solvents. These encouraging results suggest that and Oda28 where the catalyst, tetrakis(triphenylphosphine)- nickel(0), is generated in situ.29 The biperylene 22 was then an additional increase of solubility should result from an eightfold substitution by phenoxy groups of the quaterrylenebis- obtained in 79% yield.The reaction conditions used for the cyclization of biperyl- (dicarboximide) core. Therefore, we have embarked on the synthesis of octaphenoxy substituted quaterrylenebis(dicar- enes 14 and 17 resulted, in the case of 22, also in the partial cleavage of the phenoxy groups of the resulting octasubstituted boximide) 23 (Scheme 3).The entry point to the synthetic scheme is the perylenedicar- quaterrylenebis(dicarboximide) 23. Consequently, milder reaction conditions have been applied to aVord the octaphenoxy boximide 20 carrying four phenoxy substituents, which has been synthesized by hydrolysis of one imide function of substituted quaterrylenebis(dicarboximide) 24 in very low yield (0.3%).The separation of octaphenoxy substituted quaterry- perylenebis(dicarboximide) 19 under basic conditions, followed by decarboxylation with copper(I) oxide under vacuum. lenebis(dicarboximide) 24 from numerous side products was conducted by gel permeation chromatography (GPC) on Purification by chromatography and recrystallisation aVords tetraphenoxyperylenedicarboximide 20 in 53% yield.The polystyrene as stationary phase with chloroform as eluent. monobromination of 20 under the mild conditions described by Mitchell26 with N-bromosuccinimide in dimethylformamide Structure elucidation leads selectively to bromoperylenedicarboximide 21 in high yield (98%).Surprisingly enough, the Yamamoto coupling of The structures of quaterrylenebis(dicarboximide)s were proven by 1H and 13C NMR spectroscopy, field desorption mass spec- the bromoperylenedicarboximide 21 under the conditions previously described for the bromoperylenedicarboximides 13 and troscopy (FD-MS), FT-IR spectroscopy and UV–VIS spectroscopy.Due to a plane of symmetry, the 1H NMR spectra of 16 resulted mainly in the cleavage of the phenoxy substituents. The reason for this unexpected side reaction remains enigmatic quaterrylenebis(dicarboximide)s 2b, 18 and 23 have a simpler appearance than those of their synthetic precursors, the bipery- and could not be explained by simple mechanistic considerations.However, this forced us to use another coupling lene diimides 14, 17 and 22. The aromatic region of the 1H NMR spectrum of quaterrylenebis(dicarboximide) 2b exhibits reaction reported by Sontheimer27 and modified by Iyoda 2360 J. Mater. Chem., 1998, 8(11), 2357–2369N O O R N O O R N O O R N O O R N O O R Br N O O R N O O R R' R' R' R' R' R' R' R' R' R' R' R' R' R' R' R' N O O R' R' R' R' R R' R' R' R' R' R' R' R' 23 22 R = Pr R' = OC6H4-4-OC6H13 20 19 21 Scheme 3 Synthetic pathway to quaterrylenebis(dicarboximide) 23.six resonances, as expected from the structure. The assignment, appropriate reference compounds. The parent ions of the quaterbased on 1H,1H correlated NMR analysis, of the resonnances rylenebis(dicarboximide)s 2a,b, 18 and 23 are in good agreement of 2b is given in Table 1.The chemical shifts for H-7,10,17,20 with the calculated masses and isotopic distributions corroboratare almost identical to those of H-8,9,18,19 and no unambigu- ing, therefore, the proposed chemical structures. The FT-IR ous assignment of these protons has been achieved. spectra of the quaterrylenebis(dicarboximide)s 2a,b, 18 and 23 The 13C NMR spectrum of the tetraphenoxy substituted quat- confirm the presence of the characteristic carbonyl bands, which errylenebis(dicarboximide) 18 exhibits thirteen quaternary and appear between 1700 and 1670 cm-1, depending on the substiseven tertiary aromatic C-atoms, in accordancewith the proposed tution at the nitrogen atoms.structure. However, a comprehensive assignment of the reson- The comparison of the UV–VIS–NIR spectra of perylenebisances to the carbon atoms has been hindered by the lack of (dicarboximide) 1a and terrylenebis(dicarboximide) 7a with the spectrum of quaterrylenebis(dicarboximide) 2b, given in Fig. 1, is very instructive. Specifically, a bathochromic shift of Table 1 1H NMR Chemical shifts of quaterrylene 2b (C2D2Cl4, the absorption maxima from 526 nm for 1a, to 650 nm for 7a 500 MHz, 135 °C) and extending to 764 nm for 2b is clearly observed.The d (ppm) Type H Integration extinction coeYcient increases from e=80 000 M-1 cm-1 for the perylenebis(dicarboximide) 1a to e=120 000 M-1 cm-1 for 8.68 d 2, 5, 12, 15 4 H terrylenebis(dicarboximide) 7a and up to e=162 000 M-1 cm-1 8.68, 8.63 d, d 7, 10, 17, 20, for the quaterrylenebis(dicarboximide) 2b. 8, 9, 18, 19 8 H A comparison with the absorption maximum of the previously 8.56 d 1, 6, 11, 16 4 H 7.42 dd a 2 H reported tetra-tert-butylquaterrylene 6c,14 shows that the two 7.29 d b 4 H dicarboximide functions at the peri-position of the quaterrylene- 2.80 q c 4 H bis(dicarboximide) 2b are responsible for a bathochromic shift of 1.19 d d 24 H more than 100 nm, as expected from the comparison of the J.Mater. Chem., 1998, 8(11), 2357–2369 2361tion maxima of the quaterrylenebis(dicarboximide) 2b with that of the tetraphenoxy substituted quaterrylenebis(dicarboximide) 18 and tetraphenoxy substituted perylenebis(dicarboximide) s 23 indicates a bathochromic shift of 19 (lmax=762 nm) and 28 nm (lmax=790 nm), respectively.The observed bathochromic shifts are due to the electron donating eVect of the phenoxy groups, and the eVect has already been observed in the case of tetraphenoxy substituted perylenebis(dicarboximide) s.16,17 Also of practical relevance, films of good optical quality are easily cast from a solution of the tetraphenoxy substituted quaterrylenebis(dicarboximide) 18.The VIS–NIR spectra of 18, both in solution and as a film, show diVerent aspects. Instead of the sharp absorption maximum at 781 nm accompanied by a shoulder at 709 nm observed in solution, as a film 18 displays two absorption maxima of nearly equal intensity at 724 and 795 nm. The high extinction coeYcients of quaterrylenebis(dicarboximide)s 2a,b, 18 and 23, which are Fig. 1 UV–VIS–NIR spectra of perylenebis(dicarboximide) 1a (solid only equalled in the NIR range by a few squarylium dyes,1 line) terrylenebis(dicarboximide) 7a (dotted line) and quaterrylenebis- suggest their use in optical data storage, where an excellent (dicarboximide) 2b (solid bold line) in CH2Cl2. signal to noise ratio could be reached.31 UV–VIS spectrum of perylene 3with the one of perylenebis(dicar- J-Aggregates and absorption behavior in strongly acidic boximide) 1a.The UV–VIS–NIR spectrum of quaterrylenebis- media. A totally new situation arises when the quaterrylenebis- (dicarboximide) 2b appears less structured than those of the (dicarboximide) 2b is dissolved in strongly acidic media. reference chromophores: the quaterrylene 6c, the perylenebis- Characteristically enough, a bathochromic shift of 112 nm is (dicarboximide) 1b, and the terylenebis(dicarboximide) 7a.We obtained when 2b is dissolved in a mixture of sulfuric acid attribute this feature to the enlarged p-system of quaterrylenebisand oleum (57%) (451) instead of chlorinated solvents. (dicarboximide) 2b in regards to 1b and 7a. Specifically, two peaks are observed, one at l=813 nm with an e of 111 000 M-1 cm-1, while the l of the second reaches a Properties value as high as 912 nm with an e of 581 000 M-1 cm-1.The value of lmax is slightly higher than those reported earlier.17 Solubility. The solubility of the quaterrylenebis(dicarboximide) s 2a,b, 18 and 23, which is the key to their processability, This is due, we believe, to traces of water in the sulfuric acid/oleum mixture, inducing diVerences in the oleum/ has been investigated in chlorinated solvents at room and elevated temperatures. The results are collected in Table 2.sulfuric ratio (see below). After dilution with water, the quaterrylenebis(dicarboximide) 2b can be recovered, which The low solubility of quaterrylenebis(dicarboximide) 2a compared to the much higher solubility of 2b is striking.indicates that the chromophore is chemically stable even in the presence of strong acids and oxidizing agents. The fact Despite the presence of two long dodecyl chains, quaterrylenebis( dicarboximide) 2a remains poorly soluble. The improved that 2b remains chemically unaltered also indicates that the large bathochromic shift and the sharp increase of e are solubility of quaterrylenebis(dicarboximide) 2b is due to facially encumbering substituents,31 i.e.the two 2,6-diisopro- presumably due to the protonation of the carboximide functions. The role of the protonation of this group on the NIR pylphenyl groups at the imide position, which decrease the tendency of the quaterrylenebis(dicarboximide) core to form spectrum of quaterrylenebis(dicarboximide) 2b was further confirmed by slightly changing the nature of the acidic medium.p-stacks. The solubility of the quaterrylenebis(dicarboximide) core is further increased by the introduction of four substitu- A dramatic change of the spectrum of 2b in concentrated sulfuric acid, in comparison to chlorinated solvents, is also ents in the bay-region, as shown by the good solubility of 18 at room temperature.Note as well that either the introduction observed. However, the NIR spectrum of quaterrylenebis- (dicarboximide) 2b in concentrated sulfuric acid and in a of eight substituents in the bay-regions or four substituents in the bay-region and the additional eVect of 2,6-diisopropylphe- sulfuric acid/oleum mixture are not superimposable (Fig. 2). Specifically, in concentrated sulfuric acid, three absorption nyl groups give rise to similar solubilities. maxima are present at 868, 907 and 992 nm, with e of 137 000, 493 000 and 143 000 M-1 cm-1, respectively, whereas only two Absorption behavior. From a practical aspect, it is worth mentioning the almost colorless solutions, which are only absorption maxima are observed in the sulfuric acid/oleum mixture.slightly blue, of quaterrylenebis(dicarboximide) 2b. This weak absorption in the visible window strictly contrasts with the Similarly, a large bathochromic shift and a dramatic increase of e, by a factor 5.4, have also been observed for terrylenebis- deeply orange–red and blue colored solutions of perylene 1a and terrylene 7a, respectively, observed for comparable concen- (dicarboximide) 7a in sulfuric acid as compared to a chloroform solution.15 Together, the large bathochromic shift and trations.As hitherto mentioned, the substitution of the quaterrylenebis( dicarboximide) in the bay-regions oVers not only a the dramatic increase of e could suggest for both the quaterrylenebis( dicarboximide) 2b and terrylenebis(dicarboximide) 7a way to increase the solubility, but also to finely tune the absorption maximum.For instance, comparison of the absorp- the formation of a J-aggregate.32 J-Aggregates are supramol- Table 2 Solubility and colors in solution of quaterrylenebis(dicarboximide)s Solubility in Solubility in Color in Compound CH2Cl2 at r.t./mg ml-1 C2H2Cl4 at 135 °C/mg ml-1 chlorinated solvents 2a — — purple–green 2b <0.2 ~2 green 15 ~30 >80 green 20 ~40 >80 green 2362 J.Mater. Chem., 1998, 8(11), 2357–2369strongly acidic solutions, i.e. tightly packed aggregates or individual molecules, 1H NMR experiments in D2SO4 were conducted on the oligomeric series: perylenebis(dicarboximide) 1a, terrylenebis(dicarboximide) 7a and quaterrylenebis(dicarboximide) 2b.Since the three members of this oligomeric series behave similarly, and for the sake of clarity, only the 1H NMR spectra of the perylenebis(dicarboximide) 1a and the quaterrylenebis( dicarboximide) 2b are presented in Fig. 4. Fig. 2 UV–VIS–NIR spectra of quaterrylenebis(dicarboximide) 2b in a mixture of sulfuric acid and oleum (57%) (451) (solid line) and in concentrated sulfuric acid (96%) (dotted line).N N N N SO3Na SO3 – Cl Cl Cl Cl 24 Three observations are made: Firstly, the 1H NMR spectra of 1a, 7a and 2b are suYciently resolved in a viscous solvent such as D2SO4. Secondly, the 1H NMR spectra of 1a, 7a, and 2b are independent of concentration in the range 10-2–10-3 M. Thirdly, the chemical shifts of the protons of 1a, 7a, and 2b, located on the N-substituent and on the aromatic core, are comparable within the oligomeric series.It also follows from the 1H NMR spectra of 1a, 7a and 2b that the protons adjacent to the isopropyl groups on the phenyl substituents at the imide positions undergo rapid exchange with deuterium in D2SO4. This has also been confirmed by FD-MS analysis. Clearly, the well-resolved and concentration independent spectra of 1a, 7a and 2b are inconsistent with the Fig. 3 UV–VIS spectra of perylenebis(dicarboximide) 1a in CH2Cl2 formation of any aggregates in solution.Moreover, 1H NMR (dotted line) and in concentrated sulfuric acid (96%) (solid line). spectra of a commercially available dye forming J-aggregates in D2O, namely the benzimidocyanine 24, have been recorded ecular assemblies of chromophores in which head-to-tail at 30 and 80 °C.Beside the characteristic peak of the solvent, arrangement of transition dipole moments results in a sharp, the expected peaks of the dye were so broad that they could intense and bathochromically shifted absorption band com- not be detected, indicating the formation of tightly packed pared to the isolated chromophore.32 aggregates.This last finding corroborates the view that no JAfter discussing the absorption spectra of terrylenebis(dicar- aggregates are formed in the case of the oligomeric series 1a, boximide) 7a and quaterrylenebis(dicarboximide) 2b in 7a and 2b in concentrated sulfuric acid. strongly acidic media, it is important to consider also that of Therefore, the exact nature of the species present in perylenebis(dicarboximide) 1a.Three observations are easily strongly acidic solutions of perylenebis(dicarboximide) 1a, made from the comparison between Fig. 2 and 3. Firstly, a terrylenebis(dicarboximide) 7a and quaterrylenebis(dicarboxilarge bathochromic shift of all the visible spectrum occurs also mide) 2b remains unknown. One can only conclude that the for perylenebis(dicarboximide) 1a in concentrated sulfuric acid diVerent behavior of 1a, 7a and 2b in chlorinated solvents in comparison to chloroform solution.Secondly, the absorp- and strongly acidic media must be related to the protonation tion peaks of 1a in concentrated sulfuric acid are not sharper and are only slightly more intense than their corresponding peaks in chloroform solution.The increase in intensity for the absorption maxima of 1a in concentrated sulfuric acid in comparison to chloroform solution, i.e. by a factor 1.4, is significantly less pronounced than for terrylenebis(dicarboximide) 7a and quaterrylenebis(dicarboximide) 2b, i.e. by a factor 5.4 and 3.0, respectively. Thirdly, the shape of the absorption curve of 1a in concentrated sulfuric acid remains somewhat similar to the one in chloroform solution (Fig. 3). This observation contrasts with the very diVerent shapes of the absorption curves of the quaterrylenebis(dicarboximide) 2b in concentrated sulfuric acid and in chloroform solution. It should be concluded for the perylenebis(dicarboximide) 1a that, despite the large bathochromic shift observed, the absence of a sharp and intense absorption in concentrated sulfuric acid seems not to indicate the formation of J-aggregates.32 It is well documented that temperature and concentration dependent 1H NMR experiments are particularly suited to the investigation of the presence of aggregates in solution.33 Fig. 4 1H NMR Spectra of (a) perylenebis(dicarboximide) 1a and (b) quaterrylenebis(dicarboximide) 2b [D2SO4 (96%), 500 MHz, 30 °C].Therefore, to elucidate the nature of the species present in J. Mater. Chem., 1998, 8(11), 2357–2369 2363of the carboximide functions, and do not result from chemical In a semiquantitative analysis, the radiative lifetime tFM, defined as the reciprocal of the radiative transition probability, modification or from aggregation of the chromophores.can be estimated from the Strickler–Berg35 equation, which for dilute solutions becomes eqn. (1), Photophysical behavior. Based on the remakably large quantum yield of fluorescence (wf) of perylene 1a and terrylene 7a approaching unity in solution,15,34 one would have expected 1 tFM =2.88×10-9 n2 v� -3-1 Pe(v� ) v� dv� (1) that quaterrylenebis(dicarboximide) 2b will, to some degree, emit light in the NIR window. However, no luminescence where n is the refractive index and v� -3-1 is the reciprocal could be detected for quaterrylenebis(dicarboximide) 2b in of an appropriate average over the fluorescence spectrum dilute solutions.Similarly, a dramatic decrease of wf has been defined in eqn. (2). observed for quaterrylenebis(dicarboximide) 6c (wf=0.05) in comparison with perylene 6a and terrylene 6b.14 Remarkably enough, it was recently discovered that the lack of emission v� -3-1 = PF(v)dv PF(v)dv v3 (2) of 2b is related to traces of unknown impurities. Normally, samples of quaterrylenebis(dicarboximide) 2b purified by column chromatography on silica gel with methylene chloride as eluent and precipitation in methanol, do not emit in The essential values needed eqn.(1) and (2) can be inferred chloroform solution, even though no impurities were observed from the absorption spectrum as well as from the steady state by 1H NMR and UV–VIS–NIR spectroscopy, FD-MS, and PL spectrum. Insertion of these parameters then leads to a thin layer chromatography. Nevertheless if quaterrylenebis- radiative lifetime of about tFM=65 ns.(dicarboximide) 2b is further purified by several extractions in Further information about the photophysical properties of ethyl acetate, an emission centered at 797 nm in chloroform quaterrylenebis(dicarboximide) 2b are given by time resolved solution is observed (Fig. 5). Characteristically, the emission photoluminescence measurements. In Fig. 6(a) a transient of maxima [lmax (em)] of quaterrylenebis(dicarboximide) 2b the PL detected at the PL maximum at 800 nm is displayed.extends to even longer wavelength in the NIR window than The measurement shows a monoexponential decay with a those of terrylenebis(dicarboximide) 7a [lmax (em)=673 nm], surprisingly short fluorescence decay time of about 320 ps. All benzoylterryleneimide 8a [lmax (em)=701 nm] and perylenebis- transients taken at diVerent wavelength of the PL spectrum amidine 9 [lmax (em)=768 nm].15,16 exhibit exactly the same time dependence, as can be seen from In Fig. 5 the absorption as well as the steady state photoluminescence (PL) are shown for the sake of comparison. The ground state absorption spectrum shows a strong inhomogeneously broadened S0–S1 (0–0) transition centered at 763 nm followed by inhomogeneously broadened vibronic satellites centered at 695 and 626 nm, respectively.Deconvolution of the ground state absorption spectrum with Gaussian profiles allows the estimation of the absorption coeYcient e as well as the oscillator strength f of the observed transitions. The molar extinction coeYcients for the optical transitions are e= 90000 cm2 mol-1, corresponding to an oscillator strength of about f=0.9, and e=51700 cm2 mol-1, relating to f=0.67, for the pure electronic (0–0) and the dominant vibronic (0–1) transitions, respectively.The dominant vibrational mode is energetically oVset by about 1300 cm-1, indicating a ring breathing mode. Comparing the transition intensities of the pure electronic transition with the ones of the vibronic transitions, it becomes evident that the quaterrylenebis(dicarboximide) 2b is a very rigid material showing a slight distortion in the excited state only.Furthermore, the slight deviations from mirror symmetry indicate only minor diVerences in the nuclear configurations of the ground and the excited state. Therefore, we conclude that the large Stokes shift (about 35 nm) observed in emission is mainly due to solvation eVects.Fig. 6 (a) Time dependence behaviour of the emission detected at Fig. 5 Absorption and emission spectra of quaterrylenebis(dicarboxi- 800 nm after excitation with 100 fs pulses. (b) Semilogarithmic plot of PL decays monitored at diVerent detection energies. mide) 2b in CHCl3. The photoluminescence excitation is at 740 nm. 2364 J. Mater. Chem., 1998, 8(11), 2357–2369Fig. 6(b), in which the transients are displayed on a semi- the perylenebis(dicarboximide) 1b, the terrylenebis(dicarboximide) 7b, and the quaterrylenebis(dicarboximide) 18 do not logarithmic scale. diVer significantly. This proves that no time and energy dependent rate, e.g. filling process, is involved in the radiative transition.However, Photochemical stability. The photostability of quaterrylene- the decay time seems to be surprisingly short compared to bis(dicarboximide) 2b has been estimated by exposing under other members of this molecular family. Following the work air a polystyrene film of roughly 10 mm containing 0.5 wt% of on radiationless transitions in molecules one can roughly dyes to UV light (l=366 nm) for a prolonged period of time.15 estimate that the probability of nonradiative transitions After 10 days of irradiation, no significant alteration of the increases exponentially with decreasing energy gap DE between absorption spectrum could be observed, demonstrating the the potential minima for the state involved [eqn.(3)],36 photochemical inertness of quaterrylenebis(dicarboximide) 2b in a polymer matrix.knr3exp A- cDE 2phvB (3) where v is the vibrational frequency and c is a quantity expressible in terms of molecular parameters. By comparing The synthesis of three quaterrylenebis(dicarboximide)s 2a,b, quaterrylenebis(dicarboximide) with perylene on the basis of 18 and 23 diVering by their substitution pattern has been this expression and taking into account that the main excess achieved.The extension of the p-system of the quaterrylenebisenergy is dissipated through C–H vibrational modes (ca. (dicarboximide)s 2a,b, 18 and 23, in comparison to the 300 cm-1) an increase of the nonradiative transition prob- perylenebis(dicarboximide)s 1, has several intriguing conseability of roughly a factor 25 can be estimated, which concurs quences for their photophysical and electrochemical properties.fairly well with the PL decay time of tFM=320 ps measured. Firstly, the quaterrylenebis(dicarboximide)s 2a,b, 18 and 23 Moreover, by insertion of the values obtained throughout the are characterized by an intense absorption in the NIR, between analysis above the quantum eYciency expressed as Q=t/tFM 750 and 800 nm in chlorinated solvents, whereas the absorption can be estimated to approximatively 5%.of perylenebis(dicarboximide)s 1 ranges between 520 and 590 nm. Secondly, the quaterrylenebis(dicarboximide) 2b pre- Electrochemical behavior. The reduction potentials of substi- sents an emission centered at 797 nm with a quantum eYciency tuted perylenebis(dicarboximide) 1b and quaterrylenebis- estimated at 5%, which is significantly lower than those of (dicarboximide) 18 are collected in Table 3.The cyclic voltam- perylenebis(dicarboximide)s 1 which approach one. Thirdly, mogram (CV) shows a four-fold reduction of the quaterrylene- a definite stabilization of the tri- and tetra-anion of the bis(dicarboximide)s 18. The first two electrons are localized quaterrylenebis(dicarboximide) 18 occurs, whereas little on the carbonyl groups because only a small diVerence is diVerence is observed between the two first reduction potentials observed for the first (-0.74 V) and second reduction poten- of 18 and 1b.Fourthly, the quaterrylenebis(dicarboximide) tials (-1.10 V) of quaterrylenebis(dicarboximide) 18 as com- 2b exhibits, in strongly acidic solvents, an extremly intense pared to the smaller homologue, perylenebis(dicarboximide) absorption around 900 nm.However, this intense absorption 1b, at -0.85 and -1.11 V, respectively. This suggests that the cannot be explained by the formation of J-aggregates in two first reduction potentials are independent of the size of solution, and is more likely caused by the protonation of the the conjugated p-system, indicating that the electrons go in to carboximide functions.the quaterrylenebis(dicarboximide) 18 and the perylenebis- In addition to these new photophysical and electrochemical (dicarboximide) 1b in two diVerent locations, presumably at properties the quaterrylenebis(dicarboximide)s 2a,b, 18 and the two imide functions, without appreciable interaction.37 23 also display good chemical, photochemical and thermal In contrast, a definite charge stabilization, due to the stability. Clearly, this unusual ensemble of properties qualifies extension of the p-system of the quaterrylenebis(dicarboxim- the quaterrylenebis(dicarboximide)s 2a,b and 18 as functional ide) 18 in comparison to the perylene 1b, is observed for the NIR materials and suggests the synthesis of even larger reduction to the tri- and tetra-anion.The third reduction rylenebis(dicarboximides) dyes. potential of the quaterrylenebis(dicarboximide) 18 (-1.97 V) We gratefully acknowledge the financial support of BASF AG has a much lower absolute value than the one of the and the Bundesministerium fu� r Forschung und Technologie.corresponding perylenebis(dicarboximide) 1b (-2.64 V). Remarkably enough, a fourth reduction is observed for the quaterrylenebis(dicarboximide) 18. Moreover, this fourth Experimental reduction potential lies at -2.26 V, i.e. 0.38 V lower than the Spectral data were obtained on Nicolet FT-IR 320 (IR), third reduction potential of perylenebis(dicarboximide) 1b.Perkin-Elmer Lambda 9 and 15 (UV–VIS), Varian Gemini 200, Bruker AC 300 or AMX 500 (NMR), Potentiostat/ Thermal stability. Thermogravimetric analyses (TGA) con- Galvanostat PAR Model 173 (CV), Finnigan MAT 312 (FD- ducted under nitrogen atmosphere show that quaterrylenebis- MS) and Mettler TG 50 (TGA) instruments. For the cyclovol- (dicarboximide) 18 possesses a high thermal stability.The first tammetric experiments with 18 (in THF, with Bu4NPF6 added) weight loss is observed between 485 and 500 °C and correa Potentiostat/Galvanostat PAR Model 173 was used. The sponds to the cleavage of the isopropyl groups. In this respect, setup for photoluminescence consisted of an XeCl excimer pumped dye laser system (15 Hz rep. rate and 10 ns pulse Table 3 Reduction potentials versus saturated calomel electrode of width) running at 740 nm.The emission from the sample was perylenebis(dicarboximide) 1b and quaterrylenebis(dicarboximide) 18 collected and focussed into the entrance slit of a 270 cm grating in tetrahydrofuran at 0 °C monochromator fitted with a charge coupled device (CCD) array for detection. Fluorescence lifetime measurements were E/V vs.SCE performed with an Kerr-lens mode-locked Ti5sapphire laser operating at 740 nm and producing 100 fs pulses at a repetition Charge Perylene 1b Quaterrylene 18 rate of 80 MHz. Here, as in the time integrated experiments, -1 -0.85 -0.74 the emission was dispersed in a monochromator and monitored -2 -1.11 -1.10 by a streak camera to follow the potoluminescence decay with -3 -2.64 -1.97 a time resolution of about 6 ps.All measurements were -4 — -2.26 performed at room temperature. The photostability tests were J. Mater. Chem., 1998, 8(11), 2357–2369 2365conducted with a UV lamp (Camag, 0.25 A, 220 V), placing N-Dodecyl-9-bromoperylene-3,4-dicarboximide 12a the polystyrene films 12 cm away from the lamp. The 2.5 g (5.1 mmol) N-Dodecylperylene-3,4-dicarboximide 11a melting points (mp) are reported uncorrected. All solvents were dissolved in 750 ml methylene chloride and a catalytic for reactions were distilled before use.Ni(cod)2 was puramount of iron powder was added. After 15 min, 8 g chased from Strem Chemicals, all other chemicals were (50 mmol) of bromine in 50 ml methylene chloride were added purchased from Aldrich and used as received. 3,4,9,10- to the reaction mixture. The temperature was slowly increased Perylenetetracarboxylic dianhydride and N-(2,6-diisopro- and the reaction mixture was refluxed for 3 h. After cooling pylphenyl )perylene-3,4-dicarboximide (11b) were obtained to room temperature, the excess bromine and most of the from BASF AG. The N-propyl-1,657,12-tetra(4-hexyloxy- methylene chloride were evaporated under vacuum.The phenoxy)perylene-3,459,10-bis(dicarboximide) (19) has been resulting concentrated solution was poured into a large volume previously described in the literature.17,25 of methanol and this solution was stored at -20 °C for 1 h. The resulting precipitate was filtered and washed with plenty N-Dodecylperylene-3,4,9,10-tetracarboxylic acid 3,4-anhydride of methanol.Drying under vacuum aVorded 2.73 g of the title 9,10-dicarboximide§ compound 12a as a red powder (94% yield). dH (500 MHz, C2D2Cl4, 135 °C) 8.6–8.5 (m, 2H, H-2,5), 15.0 g (38 mmol) 3,4,9,10-Perylenetetracarboxylic dianhydride 8.5–8.3 (m, 4H, H-12,7,1,6), 8.15 (d, 1H, H-10), 7.90 (d, 1H, and 84.0 g (0.45 mmol) dodecylamine were added to a mixture H-8), 7.71 (dd, 1H, H-11), 4.23 (t, 2H, a-CH2), 1.84 (m, 2H, of 1 L propan-1-ol and 0.5 L water. The reaction mixture was b-CH2), 1.48 (m, 2H, c-CH2), 1.35 [br, 16H, (CH2)8], 0.94 (t, stirred at 65 °C for 7 h.After cooling to room temperature, 3H, CH3); nmax/cm-1 2954, 2921, 2870, 2851, 1694 (CNO), 150 mL of concentrated HCl were added to the reaction 1651 (CNO), 1616, 1594, 1562, 1497, 1467, 1455, 1383, 1359, mixture and 1 L of water was added.The precipitate was 1333, 1296, 1244, 812, 805, 751; lmax(CH2Cl2)/nm (e) (absorp- separated from the liquid phase by centrifugation and dri tion) 255 (18930), 263 (34690), 480 (31240), 504 (32090); m/z under vacuum, aVording 20 g of the title compound as an (FD) 569.4 (M+, 100%) [C34H34NO2Br (568.55 g mol-1) orange powder (94% yield).N-Dodecylperylene-3,4,9,10- calc.: C, 71.83; H, 6.03; N, 2.46; Br, 14.05. Found: C, 70.59; tetracarboxylic acid 3,4-anhydride 9,10-dicarboximide 10a was H, 5.71; N, 2.40; Br, 14.21%]; mp 231 °C. used directly for the next reaction without further purification. For characterization purposes, a small amount was purified N-(2,6-Diisopropylphenyl )-9-bromoperylene-3,4-dicarboximide by chromatography on silica gel with chloroform as eluent. 12b dH (300 MHz, C2D2Cl4, 135 °C) 8.68 (d, 2H, H-8,11), 8.66 (d, 2H, H-2,5), 8.60 (d, 2H, H-7,12), 8.59 (d, 2H, H-1,6), 4.20 10 g (21 mmol) N-(2,6-diisopropylphenyl )perylene-3,4-dicar- (t, 2H, a-CH2), 1.79 (m, 2H, b-CH2), 1.41 (m, 2H, c-CH2), boximide 11b were dissolved under slight heating in 1 L 1.28 [br, 16H, (CH2)8], 0.87 (t, 3H, CH3); nmax/cm-1 2954, chlorobenzene.Bromine (15 g, 95 mmol) was added and the 2924, 2850, 1765 (CNO), 1743, 1724 (CNO), 1697 (CNO), reaction mixture was stirred for 4.5 h at 50 °C. Chlorobenzene 1656 (CNO), 1616, 1595, 1580, 1508, 1434, 1407, 1350, 1340, and unreacted bromine were removed under vacuum. The 1324, 1297, 1274, 1253, 1241, 1153, 1127, 1033, 1018, 866, resulting solid was recrystallised from methylene chloride– 810, 739; lmax(H2SO4)/nm (e) (absorption) 390 (8170), 544 methanol, yielding 11.4 g (98%) of the title compound 12b.(42800), 581 (60440); m/z (EI ) 559.3 (M+, 86%), 405.2 dH (300 MHz, CDCl3, 30°C) 8.64 (d, 1H, H-2), 8.62 (d, (M+-C11H22, 24%), 392.2 (M+-C12H24, 100%), 248.2 1H, H-5), 8.45 (d, 1H, H-1), 8.42 (d, 1H, H-6), 8.37 (d, 1H, (perylene+, 60%) (calc.M+, 558.7); mp >300 °C. H-12), 8.27 (d, 1H, H-7), 8.20 (d, 1H, H-10), 7.87 (d, 1H, H- 8), 7.69 (t, 1H, H-11), 7.47 (dd, 1H, H-16), 7.33 (d, 2H, HN- Dodecylperylene-3,4-dicarboximide 11a 15), 2.77 [m, 2H, CH(CH3)2], 1.18 [d, 12H, CH(CH3)2]; dC (125.5 MHz, CDCl3, 30°C) 163.85, 145.69, 136.90, 136.77, 5.0 g (8.9 mmol) 10a and 200 mL of a 12 wt% KOH solution 133.02, 132.09, 132.02, 131.31, 130.94, 130.43, 130.08, 129.66, were introduced into a 250 mL autoclave.The temperature 129.44, 129.21, 129.11, 128.21, 126.69, 126.20, 124.47, 123.98, was raised to 230 °C for 18 h. After cooling to room tempera- 123. 81, 121.43, 120.75, 120.48, 29.13, 23.96; nmax/cm-1 1701 ture, the resulting precipitate was filtered oV, washed with (CNO), 1660 (CNO); lmax(CH2Cl2)/nm (e) (absorption) 263 plenty of water and dried under vacuum.The resulting solid (34056), 355 (3065), 484 (34762), 509 (35319); (fluorescence) was extracted with diethyl ether and precipitated in a large 540; m/z (FD) 561.1 (M+, 100%) [C34H26NOBr volume of methanol. Then the red powder was dried under (560.49 g mol-1) calc.: C, 72.86; H, 4.68; N, 2.50; Br, 14.26.vacuum to aVord 3.25 g of the title compound (75% yield). Found: C, 71.93; H, 4.71; N, 2.50; Br, 13.77%]; mp >300 °C. N-Dodecylperylene-3,4-dicarboximide 11a was used directly Rf (silica gel ) 0.45 (CH2Cl2), 0.09 (toluene). for the next reaction without further purification. For characterization purposes a small amount (500 mg) was purified by N-(2,6-Diisopropylphenyl )-9-(tributylstannyl )perylene-3,4- column chromatography on silica gel with toluene as eluent.dicarboximide 13b dH (300 MHz, CDCl3, 30°C) 8.49 (d, 2H, H-2,5), 8.32 (d, 2H, H-7,12), 8.29 (d, 2H, H-1,6), 7.83 (d, 2H, H-9,10), 7.55 13.5 g (24 mmol) of the monobromoperylene 12b, 26.3 g (dd, 2H, H-8,11), 4.16 (t, 2H, a-CH2), 1.77 (m, 2H, b-CH2), (45 mmol) hexabutylditin and 0.1 g (0.1 mmol, 0.3 mol%) 1.42 (m, 2H, c-CH2), 1.28 [br, 16H, (CH2)8], 0.87 (t, 3H, Pd(PPh3)4 were refluxed in 700 ml toluene for 4 days.The CH3); dC (75.5 MHz, CDCl3, 30°C) 163.89 (C=O), 137.25, solvent was removed under vacuum. Purification was carried 134.74, 131.45, 130.85, 129.68, 128.37, 127.21, 123.72, 121.71, out by column chromatography on silica gel with CH2Cl2 as 120.36, 40.74, 32.00, 29.73, 29.70, 29.52, 29.36, 28.45, 27.43, eluent, aVording 16 g of the title compound as a red solid 22.67, 13.96; nmax/cm-1 2956, 2916, 2850, 1691 (CNO), 1652 (88% yield).(CNO), 1595, 1571, 1469, 1381, 1354, 1295, 1262, 1249, 1105, dH (500 MHz, CDCl3, 30°C) 8.66 (d, 1H), 8.65 (d, 1H), 1079, 1032, 1022, 813, 762, 753; lmax(CH2Cl2)/nm (e) (absorp- 8.50 (d, 1H), 8.47 (d, 1H), 8.46 (d, 1H), 8.40 (d, 1H), 7.88 tion) 263 (33100), 480 (28810), 502 (28330); m/z (FD) 489.3 (d, 1H), 7.84 (d, 1H), 7.69 (t, 1H), 7.49 (t, 1H), 7.35 (d, 2H), 2.79 (h, 2H), 1.69–1.56 (m, 6H), 1.44–1.33 (m, 6H), 1.31–1.27 (M+, 100%), 978.3 (M2+, 77%) [C34H35NO2 (489.66 g mol-1) (m, 6H), 1.20 (d, 12H), 0.92 (t, 9H); dC (125.5 MHz, C2D2Cl4, calc.: C, 83.40; H, 7.21; N, 2.86.Found: C, 82.87; H, 7.04; N, 30 °C) 164.0, 149.7, 145.7, 140.1, 138.0, 137.7, 136.3, 133.4, 2.71%]; mp 179 °C. 132.0, 131.1, 130.5, 129.8, 129.4, 129.2, 127.0, 126.8, 124.0, 123.7, 122.7, 120.8, 120.0, 119.9, 29.3, 29.2, 27.3, 24.0, §IUPAC name: N-dodecyl-13,15-dioxo-9,10-(methanoepiminomethano) perylene-3,4-dicarboxylic anhydride 13.6, 10.8; nmax(KBr)/cm-1 1699 (CNO), 1663 (CNO); 2366 J.Mater. Chem., 1998, 8(11), 2357–2369lmax(CHCl3)/nm (e) (absorption) 267 (4.45), 496 (4.56), 521 added in a 250 ml Schlenk flask under argon. The reaction (4.54); m/z (FD) 772.5 (M+, 100%) calc. M+, 772.5); mp mixture was vigorously stirred at 120 °C for 2.5 h. After 158–159 °C. cooling to room temperature, the solidified solution was dissolved in water and poured into 500 mL water–hydrochloric N,N¾-Bis(dodecyl )-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) acid (551). The resulting precipitate was filtered and dried 14a under vacuum.Purification was carried out by extraction using CHCl3 as solvent until no colored side product could be Ni(cod)2 (180 mg, 0.67 mmol), cyclooctadiene (600 mg, extracted. Drying the resulting dark blue powder aVorded 5.6 mmol) and 2,2¾-bipyridyl (105 mg, 0.67 mmol) were added 369 mg of the title compound (83% yield ).to 80 ml DMF in a 100 ml Schlenk flask under argon. The dC(CP MAS TOSS, 4.5 kHz) 161.54 (CNO), 140–115 (C, mixture was stirred at room temperature for 1 h and bromoaromatic), 40.60, 30.75, 23.43, 14.42; lmax/cm-1 2921, 2851, perylenedicarboximide 12a (382 mg, 0.67 mmol) was added to 1690 (CNO), 1650 (CNO), 1594, 1575, 1548, 1502, 1455, the purple solution.After 36 h at 65 °C, the reaction mixture 1430, 1404, 1382, 1354, 1288, 1244, 1126, 1115, 810; was cooled to room temperature and poured into 120 mL lmax(H2SO4)/nm (e) 208 (0.375), 374 (0.055), 622 (0.170), water–hydrochloric acid–methanol (15152). The resulting pre- 858 (0.219), 896 (0.419), 989 (0.469), 1134 (0.021); lmax cipitate was filtered oV, washed with water and dried under [H2SO4–oleum (57%) (451)]/nm (e) 281 (524300), 323 (57700), vacuum, yielding 293 mg (89%) of the title compound 14a as 784 (34400), 876 (337000); m/z (FD) 974.2 (M+, 100%) (calc.a deep red powder. M+, 975.3); mp >300 °C. dH (500 MHz, C2D2Cl4, 135 °C) 8.53 (2d, 4H, H-5,2), 8.38 (d, 2H, H-7), 8.32 (d, 2H, H-6), 8.28 (2d, 4H, H-1,12), 8.12 N,N¾-(2,6-Diisopropylphenyl )quaterrylene-3,4513,14-bis- (d, 2H, H-8), 7.88 (d, 2H, H-10), 7.69 (t, 4H, H-11), 4.22 (t, (dicarboximide) 2b 4H, a-CH2), 1.81 (m, 4H, b-CH2), 1.48 (m, 4H, c-CH2), 1.34 [br, 32H, (CH2)8], 0.94 (t, 6H, CH3); dC(125.5 MHz, C2D2Cl4, N,N¾ -Bis(2,6-diisopropylphenyl )- 9,9¾-biperylene-3,453¾,4¾-bis- 135 °C) 164.85, 164.84, 137.58, 137.45, 134.40, 132.59, 132.56, (dicarboximide) (750 mg, 0.78 mmol), 80 g KOH and 6 g 132.53, 131.10, 131.08, 130.94, 130.52, 130.50, 129.41, 127.71, glucose, were added in a 250 ml Schlenk flask under argon. 127.23, 125.44, 124.75, 123.12, 123.10, 121.94, 121.66, 41.91, The reaction mixture was vigorously stirred at 120 °C for 2.5 h. 33.14, 30.87, 30.84, 30.82, 30.65, 30.50, 29.55, 28.55, 23.83, After cooling to room temperature, the solidified solution was 15.16; nmax/cm-1 2955, 2923, 2852, 1696, 1651, 1594, 1563, dissolved in water and poured into 500 mL water–hydrochloric 1497, 1384, 1359, 1245, 805, 750; lmax(CH2Cl2)/nm (e) (absorp- acid (551).The resulting precipitate was filtered and dried tion) 263 (56150), 481 (51030), 504 (53160); m/z (FD) 977.3 under vacuum.Purification was carried out by column chroma- (M+, 100%) [C68H68N2O4 (977.30 g mol-1) calc.: C, 83.57; tography on silica gel using CH2Cl2 as eluent. Precipitation H, 7.01; N, 2.87. Found: C, 83.09; H, 7.11; N, 2.92%]; from CH2Cl2 in methanol aVorded 620 mg of the title commp 204 °C. pound as a green powder (83% yield). dH(300 MHz, C2D2Cl4, 135 °C) 8.68 (d, 4H, H-2, 5, 12, 15), N,N¾-Bis(2,6-diisopropylphenyl )-9,9¾-biperylene-3,453¾,4¾- 8.68, 8.63 (d, 4H, H-7, 10, 17, 20, 8, 9, 18, 19), 8.56 (d, 4H, bis(dicarboximide) 14b H-1, 6, 11, 16), 7.42 (dd, 2H, Ph-H-24), 7.29 (d, 4H, Ph-H- 23), 2.80 [m, 4H, CH(CH3)2], 1.19 [d, 24H, CH(CH3)2]; Ni(cod)2 (496 mg, 1.78 mmol), cod (161 mg, 1.48 mmol) and nmax/cm-1 1702 (CNO), 1659 (CNO); lmax(CH2Cl2)/nm 2,2¾-bipyridyl (278 mg, 178 mmol) were added to 80 ml DMF (e)264 (97377), 274 (100124), 317 (9195), 375 (14689), 764 in a 100 ml Schlenk flask under argon.The mixture was stirred (162024); lmax [H2SO4–oleum (59%) (451)]/nm (e)281 at room temperature for 1 h and bromoperylenedicarboximide (698994), 326 (58801), 783 (83173), 876 (654705); m/z (FD) (1 g, 1.78 mmol) was added to the purple solution.After two 479.2 (M2+, 37%), 958.5 (M+, 100%), (calc. M+, 959.1); mp days at 70 °C, the reaction mixture was cooled to room >300 °C; Rf (silica gel ) 0.02 (CH2Cl2), 0.81 (THF). temperature and poured into 1 L water–hydrochloric acid (551). The precipitate was filtered oV, washed with water, N-(2,6-Diisopropylphenyl )-1,6,9-tribromoperylene-3,4- dried under vacuum and purified by silica gel column chromadicarboximide 15 tography using CH2Cl2 as eluent.Solvent was evaporated under vacuum, then the resulting solid was redissolved in a To a solution of N-(2,6-diisopropylphenyl )perylene-3,4-dicarminimum of CH2Cl2 and a large excess of methanol was boximide 11 (12 g, 25 mmol) in 1.5 L chloroform, 70 mL of added. The green precipitate was filtered, washed with meth- bromine were added and the reaction mixture was refluxed for anol and dried under vacuum, yielding 710 mg (83%) of the 6 h.After cooling to room temperature, the reaction mixture title compound 14b. was washed with a solution of 15 g KOH and 10 g sodium dH (300 MHz, CDCl3, 30°C) 8.72 (d, 2H, H-5), 8.70 (d, sulfite in 2 L water. The organic layer was separated and dried 2H, H-2), 8.65 (d 2H, H-7), 8.58 (d, 2H, H-6), 8.50–8.55 (m, on magnesium sulfate. Removing the solvent under vacuum 4H, H-12,1), 7.74 (d, 2H, H-8), 7.62 (d, 2H, H-10), 7.55 (d, aVorded 19.5 g of the title compound as an orange solid.The 2H, H-11), 7.48 (dd, 2H, Ph-H-16), 7.34 (d, 4H, Ph-H-15), purity was found to be suYcient for the next reaction.For 2.78 [m, 4H, CH(CH3)2], 1.18 [d, 24H, CH(CH3)2]; dC analytical purposes, 2 g of the orange solid were purified by (125.5 MHz, CDCl3, 30°C) 163.95, 145.74, 145.71, 140.53, column chromatography on silica gel using CH2Cl2 as eluent. 137.44, 137.23, 135.30, 133.71, 132.13, 130.99, 130.57, 129.65, Precipitation from CH2Cl2 in methanol aVorded 1.67 g of the 129.59, 129.48, 129.37, 129.27, 128.32, 127.47, 127.01, 124.08, title compound (91% yield). 124.04, 123.40, 121.34, 121.29, 120.61, 120.47, 29.17, 24.03; dH(500 MHz, CDCl3, 30°C) 9.33 (d, 1H, H-12), 9.11 (d, nmax/cm-1 1702 (CNO), 1662 (CNO); lmax(CH2Cl2)/nm (e) 1H, H-7), 8.94 (s, 1H, H-2), 8.93 (s, 1H, H-5), 8.45 (d, 1H, (absorption) 264 (57790), 355 (6503), 499 (66477), 528 H-10), 7.99 (d, 1H, H-8), 7.80 (t, 1H, H-11), 7.51 (t, 1H, Ph- (83055); (fluorescence) 597; m/z (FD) 480.8 (M2+, 29%), H-16), 7.36 (d, 2H, Ph-H-15), 2.73 [heptet, 2H, CH(CH3)2], 960.8 (M+, 100%) [C68H52N2O4 (961.17 g mol-1) calc.: C, 1.20 [d, 12H, CH(CH3)2]; dc(125.5 MHz, CDCl3, 30° C) 84.97; H, 5.45; N, 2.91.Found: C, 84.02; H, 5.39; N, 2.70%]; 162.54, 145.63, 135.37, 135.15, 134.56, 131.62, 130.92, 130.69, mp >300 °C; Rf (silica gel ) 0.12 (CH2Cl2), 0.84 (THF). 130.33, 130.28, 129.82, 129.78, 129.58, 128.86, 128.75, 127.53, 126.94, 126.91, 126.74, 126.50, 124.14, 120.94, 120.89, 119.24, N,N¾-Bis(dodecyl )quaterrylene-3,4513,14-bis(dicarboximide) 119.02, 29.25, 23.98; nmax(KBr)/cm-1 1711 (CNO), 1672 2a (CNO); lmax(CH2Cl2)/nm (e) 228 (78697), 281 (28194), 379 (3116), 401 (3398), 513 (33013); m/z (FD) 719.0 (M+, 100%) N,N¾-Bis(dodecyl )-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) (977 mg, 1 mmol), 100 g KOH, 4 g glucose and 100 mL were [C34H24NO2Br3 (718.27 g mol-1) calc.: C, 56.86; H, 3.37; N, J.Mater. Chem., 1998, 8(11), 2357–2369 23671.95; Br, 33.37. Found: C, 56.49; H, 3.42; N, 1.72; Br, 32.01%]; methanol aVorded 421 mg of quaterrylenebis(dicarboximides) 18 as a green powder (85% yield).mp >300 °C; Rf (silica gel ) 0.77 (CH2Cl2), 0.48 (toluene). dH(500 MHz, CDCl3, 30°C) 9.09 (d, 4H, H-7, 10, 17, 20), 8.32 (s, 4H, H-2, 5, 12, 15), 7.76 (d, 4H, H-8, 9, 18, 19), 7.41 N-(2,6-Diisopropylphenyl )-1,6-bis(4-tert-butylphenoxy)-9- (t, 2H, Ph-H-24), 7.34 (d, 8H, Ph-H-24), 7.28 (d, 4H, Ph-H- bromoperylene-3,4-dicarboximide 16 23), 7.00 (d, 8H, Ph-H-2), 2.76 [m, 4H, CH(CH3)2], 1.26 (s, 36H, tert-butyl ), 1.13 [d, 24H, CH(CH3)2]; dC(125.5 MHz, N-(2,6-Diisopropylphenyl )-1,6,9-tribromoperylene-3,4-dicarboximide 15 (16 g, 22 mmol), 4-tert-butylphenol (6.6 g, CDCl3, 30°C) 162.99, 153.55, 152.93, 147.00, 145.75, 131.24, 130.85, 130.80, 129.40, 129.19, 128.87, 127.73, 127.47, 127.17, 0.044 mol) and potassium carbonate (6.9 g, 0.05 mol ) were stirred in 500 ml NMP at 120 °C for 6 h.After cooling to 126.42, 125.24, 124.32, 123.94, 122.53, 121.63, 117.39, 34.37, 31.44, 29.23, 24.10; nmax(KBr)/cm-1 1707 (CNO), 1669 room temperature, the reaction mixture was poured into 2 l water–HCl (551). The resulting precipitate was filtered, (CNO); lmax(CH2Cl2)/nm (e) (absorption) 262 (95819), 271 (97645), 382 (12895), 709 (71931), 781 (166571); (fluores- washed with water and dried under vacuum. The desired product was purified by column chromatography on silica gel cence) 806; m/z (FD) 775.2 (M2+, 38%), 1551.3 (M+, 100%) (calc.M+, 1552.0); mp >300 °C; Rf 0.43 (CH2Cl2), 0.03 using CH2Cl2 as eluent. Precipitation from CH2Cl2 into methanol aVorded 6.28 g of the title compound as a red powder (toluene). (33% yield).dH(300 MHz, CDCl3, 30°C) 9.40 (d, 1H, H-12), 9.16 (d, N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)perylene-3,4- 1H, H-7), 8.35 (d, 1H, H-10), 8.34 (s, 1H, H-2), 8.32 (s, 1H, dicarboximide 20 H-5), 7.88 (d, 1H, H-8), 7.69 (t, 1H, H-11), 7.4–7.5 (m, 5H, N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)perylene-3,459,10- Ph-H-16,3,3¾), 7.30 (d, 2H, Ph-H-15), 7.08 (m, 4H, Ph-Hbis( dicarboximide) 19 (15 g, 12 mmol) and 150 g KOH were 2,2¾), 2.72 [m, 2H, CH(CH3)2], 1.35 (s, 18H, tert-butyl ), 1.15 added to 1 L of propan-2-ol.The reaction mixture was refluxed [d, 12H, CH(CH3)2]; dC(125.5 MHz, CDCl3, 30°C) 163.14, for 105 min. After cooling to room temperature, 2.5 L water 153.80, 153.69, 153.17, 153.10, 147.35, 147.33, 145.64, 132.00, and 250 ml of concentrated hydrochloric acid were added.The 131.54, 131.01, 130.87, 130.67, 129.42, 129.32, 129.29, 128.68, resulting precipitate was filtered, washed with water and dried 128.05, 127.83, 127.55, 127.18, 126.63, 126.54, 125.35, 124.36, under vacuum. The crude product was then dissolved in a 124.30, 123.91, 123.02, 121.89, 121.87, 118.43, 118.36, 34.43, suspension of 25 g Cu2O in 800 ml quinoline.The temperature 31.45, 29.09, 23.99; nmax(KBr)/cm-1 1706 (CNO), 1670 was raised to 240 °C under vacuum and 500 ml quinoline were (CNO); lmax(CH2Cl2)/nm (e) 274 (40081), 420 (9949), 513 distilled over a period of 6 h. The reaction mixture was cooled (41553); m/z (FD) 855.2 (M+, 100%) [C54H50NO4Br to room temperature, and 2.5 L water and 150 mL concen- (856.90 g mol-1): calc.: C, 75.69; H, 5.88; N, 1.63; Br, 9.32.trated hydrochloric acid were added. The resulting precipitate Found: C, 75.27; H, 5.92; N, 1.41; Br, 8.69%]; mp 297 °C; Rf was filtered, washed with water and dried under vacuum. 0.86 (CH2Cl2), 0.56 (toluene). Purification was carried out by chromatography on silica gel with toluene as eluent. The second fraction was identified as N,N¾-Bis(2,6-diisopropylphenyl )-1,1¾,6,6¾-tetra(4-tert- the title compound.Precipitation in methanol aVorded 5.70 g butylphenoxy)-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) 17 of the title compound as a red–orange powder (42% yield). dH(300 MHz, CDCl3, 30°C) 8.10 (s, 2H, H-2, 5), 7.72 (d, 770 mg (2.8 mmol) Ni(cod)2, 252 mg (2.34 mmol) cod, 2H, H-9, 10), 7.09 (d, 2H, H-8, 11), 6.7–7.0 (m, 16H, Ph-H), 440 mg (2.8 mmol) 2,2’-bipyridyl and 2 g (2.33 mmol) N-(2,6- 4.08 (t, 2H, -CH2), 3.93 [t, 8H, -CH2 (hexyl )], 2.75 [m, 8H, diisopropylphenyl )-1,6-bis(4-tert-butylphenoxy)-9-bromopery- -CH2 (hexyl )], 1.1–1.6 [m, 26H, (CH2)3 (hexyl ), -CH2 lene-3,4-dicarboximide 13 were reacted as described for the (propyl )], 0.96 [m, 15H, CH3 (hexyl ), CH3 (propyl )]; preparation of 14.Purification was carried out by column lmax(CH2Cl2)/nm (e) (absorption) 277 (1.23), 414 (0.27), 538 chromatography on silica gel with CH2Cl2–toluene as eluent. (0.55); m/z (FD) 1132.8 (M+, 100%) (calc. M+, 1132.5). Recrystallisation from CH2Cl2–methanol aVorded 1.55 g of the title compound as a red powder (86% yield). N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)-9-bromoperylene- dH(500 MHz, CDCl3, 30°C) 9.46 (d, 2H, H-7,7¾), 9.36 (d, 3,4-dicarboximide 21 2H, H-12,12¾), 8.36 (s, 2H, H-5,5¾), 8.34 (s, 2H, H-2,2¾), 7.64 (d, 2H, H-8,8¾), 7.60 (d, 2H, H-10,10¾), 7.4–7.5 (m, 12H, H- 5 g (4.4 mmol) N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)- 11,11¾, Ph-H-3,3¾,16,16¾), 7.29 (d, 4H, Ph-H-15,15¾), 7.09, 7.13 perylene-3,4-dicarboximide 20 and 2 g (11 mmol) NBS were (d, 4H, Ph-H-2,2¾), 2.73 [m, 4H, CH(CH3)2], 1.34 (s, 36H, dissolved in 600 mL of DMF.The reaction mixture was tert-butyl ) 1.15 [d, 24H, CH(CH3)2]; dC(125.5 MHz, CDCl3, reacted for 12 h at 60 °C. After cooling to room temperature, 30 °C) 163.2, 153.8, 153.7, 153.3, 147.3, 147.2, 145.7, 145.7, the reaction mixture was poured into 3 L water–HCl (551). 140.1, 132.8, 131.9, 130.7, 129.7, 129.4, 128.9, 128.3, 127.9, The resulting precipitate was filtered, washed with water and 127.9, 127.2, 127.2, 127.0, 126.9, 124.3, 124.2, 123.9, 123.1, dried under vacuum.Precipitation from CH2Cl2 into methanol 121.6, 118.6, 118.5, 34.4, 31.5, 29.1, 24.0; nmax(KBr)/cm-1 aVorded 4.68 g of the title compound 21 as a red powder 1709 (CNO), 1672 (CNO); lmax(CH2Cl2)/nm (e) 275 (66307), 93% yield). 417 (15681), 534 (91474); m/z (FD) 777.1 (M2+, 6%), 1554.1 dH(500 MHz, CDCl3, 30°C) 8.12 (s, 1H, H-2), 8.10 (s, 1H, (M+, 100%) [C108H100N2O8 (1553.99 g mol-1) calc.: C, 83.47; h-5), 8.09 (d, 1H, H-10), 7.38 (s, 1H, H-8), 7.18 (d, 1H, HH, 6.49; N, 1.80. Found: C, 83.31; H, 6.33; N, 1.62%]; mp 11), 6.7–7.0 (m, 16H, Ph-H), 4.05 (t, 2H, -CH2); 3.92 [t, 8H, 259 °C; Rf 0.84 (CH2Cl2), 0.26 (toluene).-CH2 (hexyl )]; 1.77 [m, 10H, -CH2/-CH2 (hexyl )], 1.2–1.6 [m, 24H, (CH2)3], 0.94 [m, 15H, CH3/CH3 (hexyl )]; m/z (FD) 1211.6 (M+, 100%) (calc. M+, 1211.4). N,N¾-Bis(2,6-diisopropylphenyl )-1,6,11,16-tetra(4-tertbutylphenoxy) quaterrylene-3,4513,14-bis(dicarboximide) 18 N,N¾-Dipropyl-1,1¾,6,6¾,7,7¾,12,12¾-octa(4- The synthesis was performed as described for 2.Modifications: hexyloxyphenoxy)-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) 500 mg (0.32 mmol) N,N¾-bis(2,6-diisopropylphenyl )-1,1¾,6,6¾- 22 tetra(4-tert-butylphenoxy)-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) 17, 80 g KOH and 6 g glucose. The desired product 654 mg (1 mmol) Bis(triphenylphoshine)nickel(II) chloride, 450 mg activated zinc and 131 mg (1 mmol) tetraethylam- was purified by column chromatography on silica gel with CH2Cl2–toluene as eluent.Precipitation from CH2Cl2 into monium iodide were poured into a 100 mL Schlenk flask under 2368 J. Mater. Chem., 1998, 8(11), 2357–23696 M. Burghard, C. Fischer, M. Schmelzer, S. Roth, M. Hanack and argon containing 80 mL of THF. After stirring for 4 h at room W. Go� pel, Chem.Mater., 1995, 7, 2104. temperature, 1.2 g (1.06 mmol) N-propyl-1,6,7,12-tetra(4-hex- 7 D.Schlettwein, D. Wo� hrle, E. Karmann and U. Melville, Chem. yloxyphenoxy)-9-bromoperylene-3,4-dicarboximide 21 were Mater., 1994, 6, 3. added. Then, the reaction mixture was stirred for 12 h at room 8 H. O. Loutfy, A. M. Hor, P. Kazmaier and M. Tam, J. Imaging temperature. The reaction mixture was filtered through Al2O3 Sci., 1989, 33, 151. 9 M.P. O’Neil, M. P. Niemczyk, W. A. Svec, D. Gosztola, G. L. and washed with CH2Cl2. Precipitation from CH2Cl2 into Gaines III and M. R. Wasielewski, Science, 1992, 257, 63. methanol aVorded 3.45 g of the title compound as a red 10 R. Gvishi, R. Reisfeld and Z. Bursheim, Chem. Phys. Lett., 1993, powder (75% yield). The purity was suYcient for the next 213, 338.reactions. For analytical purposes, 100 mg were purified by 11 G. Seybold and G. Wagenblast, Dyes Pigm., 1989, 11, 303. column chromatography on silica gel with toluene as eluent. 12 E. Clar, W. Kelly and R. M. Laird, Monatsh. Chem., 1956, 87, 391. 13 E. Clar and J. C. Speakman, J. Chem. Soc., 1958, 2492. dH(300 MHz, CDCl3, 30°C) 8.11 (s, 2H, H-2,2¾), 8.09 (s, 14 (a) K.-H.Koch and K. Mu� llen, Chem. Ber., 1991, 124, 2091; 2H, H-5,5¾), 7.42 (d, 2H, H-10,10¾), 7.1–7.2 (m, 20H, Ph-HA. Bonhen, K.-H. Koch, W. Lu� ttke and K. Mu� llen, Angew. 3,3¾,3,3, H-8,8¾,11,11¾), 6.7–6.9 (m, 16H, Ph-H-2,2¾,2,2¾), Chem., Int. Ed. Engl., 1990, 29, 525; (b) S. De Backer, M. R. 4.05 (t, 4H, N-CH2-), 1.68 (t, 4H, -CH2-CH2-CH3), 1.26 (3s, Negri, S.De Feyter, G. B. Dutt, M. Ameloot, F. C. De Schryver, 72H, tert-butyl ), 0.93 (t, 24H, CH3); m/z (FD) 1909.2 (M+, K. Mu� llen and F. Holtrup, Chem. Phys. Lett., 1995, 233, 538; A. Schmidt, N. R. Armstrong, C. Goeltner and K. Mu� llen, 100%), 955 (M2+, 92%) (calc. M+, 1910.4). J. Phys. Chem., 1994, 98, 11780; S. De Backer, G. B. Dutt, M. dH(300 MHz, CDCl3, 30°C) 8.12 (s, 2H, H-2,2¾), 8.11 (s, Ameloot, F.C. De Schryver, K. Mu� llen and F. Holtrup, J. Phys. 2H, H-5,5¾), 7.42 (d, 2H, H-10,10¾), 7.08 (s, 2H, H-8,8¾), Chem., 1996, 100, 512; Y. H. Meyer, P. Plaza and K. Mu� llen, 6.7–7.0 (m, 34H, H-11,11¾,Ph-H-2,2¾,2,2¾,Ph-H-3,3¾,3,3¾), Chem. Phys. Lett., 1997, 264, 643. 4.06 (t, 4H, -CH2), 3.93 [t, 16H, -CH2 (hexyl )], 1.76 [m, 15 F. Holtrup, G.R. Mu� ller, H. Quante, S. De Feyter, F. C. De 20H, -CH2/-CH2 (hexyl )], 1.3–1.7 [m, 48H, (CH2)3], 0.93 [m, Schryver and K. Mu� llen, Chem. Eur. J., 1997, 3, 219. 16 H. Quante, Y. Geerts and K. Mu� llen, Chem. Mater., 1997, 9, 495. 30H, CH3/CH3 (hexyl )]; m/z (FD) 1131.6 (M2+, 100%), 17 H. Quante and K. Mu� llen, Angew. Chem., Int. Ed. Engl., 1995, 34, 2263.1 (M+, 62%) (calc. M+, 2262.9). 1323; H. Quante, Ph.D. Dissertation, Mainz, 1995. 18 Y. Nagao and T. Misono, Bull. Chem. Soc. Jpn., 1981, 54, 1191. 19 Y. Nagao, Y. Abe and T. Misono, Dyes Pigm., 1991, 16, 19. N,N¾-Dipropyl-1,6,7,10,11,16,17,20-octa(4- 20 T. Yamamoto, A. Morita, Y. Miyazaki, Y. Maruyama, hexyloxyphenoxy)quaterrylenebis(dicarboximide) 23 H. Wakayama, Z. Zhou, Y. Nakamura and T. Kanbara, Macromolecules, 1992, 25, 1214. 500 mg (0.22 mmol) N,N¾-dipropyl-1,1¾,6,6¾,7,7¾,12,12¾-octa(4- 21 H. Azizian, C. Eaborn and A. Pidcock, J. Organomet. Chem., hexyloxyphenoxy)-9,9¾-biperylene-3,453¾,4¾-bis(dicarboximide) 1981, 215, 49. 22, 30 g KOH and 4 g glucose, dissolved in 30 mL of ethanol, 22 (a) J. K. Stille, Angew. Chem., 1986, 98, 504; Angew. Chem., Int. Ed. Engl., 1986, 25, 508; (b) I.P. Beletskaya, J. Organomet. Chem., were reacted as descrf 2. Purification 1983, 250, 551. was carried out by column chromatography on silica gel with 23 Ullmanns Enzyclopa�die der technischen Chemie, 4th edn., Verlag CH2Cl2 as eluent. Recrystallisation from CH2Cl2–methanol Chemie, Weinheim, 1974, vol. 18, p. 686. aVorded 119 mg of a green powder containing the title com- 24 W. Bradly and F. W. Pexton, J. Chem. Soc., 1954, 4432. pound and some degradation products, i.e. loss of hexyloxy- 25 D. Dotcheva, M. Klapper and K. Mu� llen, Macromol. Chem. Phys., 1994, 195, 1905; H. Quante, P. Schlichting, U. Rohr, Y. phenoxy side groups. The title compound was finally purified Geerts and K. Mu� llen, Macromol. Chem. Phys., 1996, 197, 4029. by gel permeation chromatography in chloroform on poly- 26 R. H. Mitchell, Y.-H. Lai and R. V. Williams, J. Org. Chem., styrene as stationary phase, aVording 15 mg (0.3% yield). 1979, 44, 4733. dH(500 MHz, CDCl3, 30°C) 8.08 (s, 4H, H-2,5,12,15), 8.06 27 I. T. 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Scheibe, Kolloid (M-3Ph]+, 49%), (calc. M+, 2261.1). Zeitsch., 1938, 82, 1; (c) E. E. Jelley, Nature, 1936, 138, 1009; (d) E. E. Jelley, Nature, 1937, 139, 631; (e) S. F. Mason, Proc. Chem. Soc., 1964, 119; ( f) D.Mo� bius, Adv. Mater., 1995, 7, 437. 33 K. A. Connors, Binding Constants, Wiley, New York, 1987. References 34 Y. Geerts and K. Mu� llen, Novel Light Emitting Dyes, Oligomers, Polymers, and Organic-Inorganic Hybrid Materials, in Applied 1 J. Fabian and R. Zahradnik, Angew. Chem., 1989, 101, 693; Fluorescence in Chemistry, Biology, and Medicine, ed. W. Rettig, Angew. Chem., Int. Ed. Engl., 1989, 28, 677; J. Fabian, B. Strehmel and S. Schrader, Springer Verlag, in the press. M. Nakazumi and T. J. Matsuoka, Chem. Rev., 1992, 92, 1197. 35 S. J. Strickler and R. A. Berg, J. Chem. Phys., 1962, 37, 814. 2 Y. Suzuki, in Infrared Absorbing Dyes Plenum Press, New York, 36 Electronic processes in organic crystals, ed. M. Pope and C. E. 1990. Swenberg, Clarendon Press, Oxford, New York, 1982. 3 Y. Nagao and T. Misono, Dyes Pigm., 1984, 5, 171. 37 A. J. Bard, personnal communication. 4 A. Rademacher, S. Ma�rkle and H. Langhals, Chem. Ber., 1982, 115, 2927. 5 H. Langhals, Heterocycles, 1995, 40, 477. Paper 8/04337J J. Mater. Chem., 1998, 8(11), 2357&nda