By using the Suzuki–Miyaura reaction, a variety of 1,7- and1,12-disubstituted and 1,6,7,12-tetraaryl-substituted per-ylenetetracarbox-3,4:9,10-diimides have been synthesisedstarting from the corresponding halogen derivatives. Untilnow, the 1,12- and 1,6,7,12-sustitutions were difficult to ac-cess and only single examples have been reported. Dehy-drohalogenation was observed to be competitive with the Su-zuki–Miyaura reaction. The extent of this side reaction de-pends on the substitution pattern of the perylene diimidecore and on the nature of the boronic acid derivative. Photo-chemical pericyclisation also reduces the yield of the desiredproducts. A mechanistic analysis has been performed on the
Introduction
Perylenetetracarbox-3,4:9,10-diimides have been knownsince 1913,[1–4] and they were initially used as vat dyes. Sincethe 1950’s these compounds have been used as pigments.The key step of numerous syntheses is the Scholl reaction.[5]
Nowadays, a large number of derivatives adapted to variousapplications are synthesised.[2,6] Such compounds are usedin the fields of organic electronics,[7,8] as sensitizers inorganic solar cells,[9–11] organic light-emitting diodes(OLED),[12] dyes,[2,13,14] fluorescent labels[15] (for instancefor bioimaging probes[16] or application in the field of envi-ronmental analysis[17]), single-molecule spectroscopy andmicroscopy,[18] liquid crystals,[19] and supramolecular struc-tures,[20,21] for instance for transmembrane structures[22] oras stabilisers of DNA G-quadruplexes.[23] Compounds pos-sessing two perylene moieties have been used to study intra-molecular excitation energy transfer.[24] These investigationshave contributed, for example, to an increased understand-ing of light-harvesting systems in green plants.
[a] Equipe de Photochimie, Institut de Chimie Moléculaire deReims, UMR 7312, CNRS, Université de Reims ChampagneArdenne, UFR Sciences,B.P. 1039, 51687 Reims, FranceE-mail: [email protected]://www.univ-reims.fr/http://www.cnrs.fr/
[b] Laboratoire de Recherche en Nanosciences, Université deReims Champagne Ardenne, UFR Sciences,B.P. 1039, 51687 Reims, FranceSupporting information for this article is available on theWWW under http://dx.doi.org/10.1002/ejoc.201402625.
special case of 1,12-diphenylperylenediimides, in whichbenzene is eliminated as a consecutive process of such a re-action. The energies of the frontier orbitals were determined.By using cyclic voltammetry, the energy of the LUMO wasmeasured, and the energy gap between the frontier orbitalswas determined based on optical spectroscopy (UV andfluorescence). With these two parameters, the energies of theHOMO were determined. The 1,6,7,12-tetraaryl- and 1,12-diarylperylenediimides have been optically resolved byusing HPLC with a chiral stationary phase. Determination ofabsolute configuration was carried out by recording circulardichroism (CD) spectra of the enantiomers.
The substitution pattern has a significant influence onchemical and physical properties, and this can determinewhich field of application is most suitable. Due to the sym-metry elements of perylene, three different positions areidentified (Figure 1). In the very frequently encounteredperylenetetracarbox-3,4:9,10-diimides, the peri-positions(3,4 and 9,10) are substituted. Some compounds carrying
Figure 1. Perylenetetracarbox-3,4:9,10-diimides with position num-bers.
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
imides in other positions have also been reported.[25] Per-ylene derivatives carrying only one imide function in a peri-position have been used as building blocks for a large vari-ety of perylene derivatives as core enlarged perylene dyes.[26]
More recently, various ortho-substituted derivatives havebeen synthesised.[8,10,11] Thus, 2,5,8,11-tetraaryl- or tetra-alkylperylenetetracarbox-3,4:9,10-diimide derivatives havebeen synthesised by using C–H activation at the perylenecore.[27] Perylenetetracarbox-3,4:9,10-diimide derivativeswith bay substitution have often been synthesised andwidely applied; in these cases the corresponding halogenderivatives are commonly used as precursors. Most fre-quently, the synthesis starts with halogenation of perylene-tetracarbox-3,4:9,10-dianhydride in the bay-position.[10,21]
The corresponding transformation of perylenetetracarbox-3,4:9,10-diimides is also used. The electron density in thesepositions is particularly high, which favours electrophilicsubstitution type reactions.[28] In the case of partial halo-genation, this reaction is more or less selective and oftenneeds particular optimisation efforts.[29] For instance, whendisubstitution is desired, the main halogenation product re-sults from reaction in the 1- and 7-positions.[30] However,1,6-di- or 1,6,7-trihalogenated products are also ob-tained.[31,32] 1,6,7,12-Tetrahalogenated perylenetetracarbox-3,4:9,10-diimides have also been synthesised.[33–35] In thiscase, all bay positions are substituted. More recently,octachloroperylenetetracarbox-3,4:9,10-dianhydride or -di-amides have been synthesised in which all bay- and ortho-positions are halogenated.[36,37] Perylene-3,4:9,10-diimidesthat are chlorinated or brominated in bay positions are usedfor further transformations through substitution of thesehalogens.[8,10,21,34–36,38,39] Based on the large number of re-ports in the literature, one may conclude that the substitu-tion of two halogen atoms in two bay positions either in1,6- or in 1,7-positions is straightforward and that a largevariety of substituents can be placed in these positions.Thus, C–N or C–O bonds have been introduced by nucleo-philic substitution with amines or alcohols.[8,11,21] Organo-metallic reactions such as the Suzuki–Miyaura[40] or theSonogashira reaction were used to form C–C bonds in thesepositions. However, completing the corresponding reactionsin all four bay positions has proved to be much more de-manding. Only the reaction with alcohols, mainly phenolderivatives, was easily performed.[41] Consequently, a vari-ety of 1,7,6,12-tertaaryloxy derivatives have been synthe-sised. Reports on establishing four substituents linked withC–C bonds in these positions are extremely rare. So far, toour knowledge, only one substitution pattern of this typehas been reported. Thus 1,6,7,12-tertaphenyl perylenetetra-carbox-3,4:9,10-diimides have been synthesised from eitherthe corresponding tetrachloro[34] or tetrabromo[35] precur-sors. Such a substitution pattern has an impact on the twist-ing between the two naphthalene moieties of the perylenesystem.[21,37,39,42–44] Modification of the twisting angle af-fects the solubility and electronic character of the molecule,and may change many other properties. In this context, itis certainly interesting to mention that this structure param-eter was also discussed for natural products possessing a
perylene core.[45] Due to their biological activities and, moreprecisely, pharmacological activities, these compounds havebeen studied intensively.
In this paper, we report on the synthesis and the charac-terisation of a variety of perylenetetracarbox-3,4:9,10-di-imides carrying two or four aryl substituents in the bay po-sitions. Selective halogenation and hydrodehalogenation fol-lowed by the Suzuki–Miyaura reaction[46] are the key oper-ations of the synthesis. Pure enantiomers of the inherentlychiral perylenediimides were obtained through optical reso-lution using HPLC.
Results and Discussion
Synthesis of Perylene Derivatives
In our study, we focused on three substitution patterns:1,7- and 1,12-diaryl- and 1,6,7,12-tetraarylperylenetetracar-box-3,4:9,10-diimides. These substitutions should induce atwisting between the two naphthalene moieties of the per-ylene core. The precursors for the 1,7-diaryl and the1,6,7,12-tetraaryl derivatives have been obtained as pre-viously discussed (Scheme 1). Bromination of perylenetetra-carboxylic 3,4:9,10-dianhyride 1 yields the 1,7-dibromo per-ylenetetracarboxylic dianhyride 2 along with the 1,6-di-bromo and the 1,6,7-tribromo derivatives.[21,30–32,34] Thetwo regioisomers may be separated either by crystallisationor by chromatography. Transformation with 2,6-diisopropylaniline or 1-octylamine yielded diimine derivatives 3a and3b.[32,47,48] Under similar reaction conditions, 1,6,7,12-tetra-chloroperylenetetracarboxlic 3,4:9,10-dianhyride (4) wastransformed into the corresponding diimides 5a and5b.[41,49,50] Recently, compound 6a, possessing two chlorineatoms in the bay positions 1 and 12, has been de-scribed.[51,52] When compounds such as 5a are transformedunder Ullmann-type reaction conditions in a basic reactionmedium, condensation of two or three perylenediimides oc-curs.[52–55] Highly selective transformations have been car-ried out with CuI and proline in dimethyl sulfoxide(DMSO). In the absence of base (K2CO3), no couplingproducts were observed; instead, partial dehalogenation intwo neighbour bay positions occurred. Under these condi-tions and after partial conversion, compound 6a was iso-lated in 48% yield.[51] We performed further experiments tooptimise this transformation and, particularly, to increasethe conversion (Table 1). We started with a reaction mixturein DMSO with CuI (6 equiv.) and l-proline (7 equiv.). After15 h, the conversion reached 70% and no further transfor-mation was observed upon additional heating (entry 1).Under these conditions, 6a was isolated with a yield of50%. Complete conversion after 16 h was observed when20 equiv. of both CuI and proline were used, and the yieldwas significantly increased. Further attempts to improve theyield or reduce the reaction time by further increasing theamounts of CuI and proline to 25 equiv. were unsuccessful(entry 3). Under these conditions, traces of the fully dehalo-genated product were detected. This result indicates the dif-ferent reactivity of the tetrachloro-derivative 5a and the
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPER
Scheme 1. Synthesis of halogenated perylenetetracarbox-3,4:9,10-diimides.
dichloro-derivative 6a. No conversion was observed withCuCl, CuBr or CuII salts, or in more acidic media (presenceof acetic acid) or in ethanol as solvent. Replacement ofproline by another amino acid such as alanine was also un-successful. The regiospecificity of this reaction was ex-plained by the key intermediate 7. In the absence ofbases such as K2CO3 this intermediate is transformed intocompound 6a.[51] Otherwise, Ullmann-type condensationoccurs.[10,53,54]
Table 1. Optimisation of the synthesis of 6a.
Entry CuI Proline t T Yield Conv.[equiv.] [equiv.] [h] [°C] [%] [%]
[a] Traces of starting material and fully hydrodehalogenated com-pound.
Having a range of halogenated perylene derivatives withdifferent substitution patterns in hand, we performed Su-zuki–Miyaura reactions with arylboronic acids. As pointedout, the synthesis of the corresponding 1,12-diaryl and
1,6,7,12-tetraaryl derivatives is particularly challenging,whereas the corresponding 1,7-diaryl derivatives are moreeasily accessible. Derivatives carrying two substituents inthe 1- and 12-positions or four substituents in 1-, 6-, 7- and12-positions are particularly interesting because the twonaphthalene moieties of the perylene core are twisted. Thus,atropisomerism or helicity with high inversion barriers isinduced.[42] We started with the transformation of 1,7-di-bromoperylenetetracarbox-3,4:9,10-diimides 3a and 3b. Byusing standard reaction conditions of the Suzuki–Miyaurareaction for the transformation with different arylboronicacids, 1,7-aryl derivatives of general structure 8a and 8bwere obtained in high yields (Scheme 2 and Table 2, entries1–6). The reaction was also performed with arylboronicacids carrying either an electron-donating (entry 2) or anelectron-withdrawing substituent (entries 3, 4 and 6) withalmost the same efficiency. Transformations with potassiumtetrafluoroborates or phenylboronic acid pinacol ester didnot improve the yield of the synthesis. Corresponding reac-tions of the 1,6,7,12-tetrachloroperylenetetracarbox-3,4:9,10-diimides 5a and 5b, leading to compounds of gene-ral structure 9a and 9b were less efficient (Scheme 2 and
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
Table 3, entries 1–4). However, the yield of 14a was con-siderably improved when potassium phenyltetrafluoro-borate[56] was used instead of phenylboronic acid (entry 2).Thus, this family of compounds becomes more readily ac-
Scheme 2. Synthesis of 1,7-diaryl- and 1,6,7,12-tetraarylperylenete-tracarbox-3,4:9,10-diimides by using the Suzuki–Miyaura reaction.
Table 2. Suzuki–Miyaura reactions of derivatives 3a and 3b leadingto 1,7-diaryl-substituted perylenetetracarbox-3,4:9,10-diimides(Scheme 2).
cessible.[34,35] Transformations with arylboronic acids carry-ing an electron-withdrawing substituent such as m- or p-cyanophenylboronic acid were unsuccessful under the reac-tion conditions discussed herein.
Table 3. Suzuki–Miyaura reactions of derivatives 5a and 5b leadingto 1,6,7,12-diaryl-substituted perylenetetracarbox-3,4:9,10-diimides(Scheme 2).
The Suzuki–Miyaura reaction with 1,12-dichloroper-ylenetetracarbox-3,4:9,10-diimides 6a leading to com-pounds of general structure 16 turned out to be more chal-lenging (Scheme 3 and Table 4). Transformation withphenyl boronic ester yielded the corresponding arylationproduct 17 in good yield (entry 1). The reaction with (p-methoxyphenyl)boronic acid was less efficient. The aryl-ation product 18 was isolated along with considerableamounts of monoarylation product 21 (entry 2). A hydro-dehalogenation is involved in the formation of this product.The Suzuki–Miyaura reaction with para- and meta-cyano-phenyl boronic acid was also less efficient (entries 3 and 4),which may be explained by the reduced nucleophilicity ofsuch boron derivatives. In the case of product 19, traces ofa side product resulting from monoarylation and hydrode-halogenation (cf. 21) were also detected. We attempted to
Table 4. Suzuki–Miyaura reactions with perylene derivative 6a(Scheme 3).
[a] Compound 21 was isolated with a yield of 46%.
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPER
Scheme 3. Suzuki–Miaura reaction and hydrodehalogenation of perylene derivative 6a.
improve the yield by using potassium phenyltrifluoroborateor phenylboronic acid pinacol ester. In both cases, com-pound 22 was isolated in good yields.
The palladium-catalysed hydrodehalogenation of aro-matic compounds has been frequently performed and inves-tigated in detail.[57] The reaction has been carried out witha variety of metal catalysts and reaction conditions.[58]
Hydrodehalogenation sometimes occurs as a side processof the Suzuki–Miyaura reaction, as illustrated inScheme 4.[59–61] According to the general Suzuki–Miyaurareaction mechanism, the perylene derivative PerX is addedto the catalytically active species L2Pd0 (oxidative addition).The aryl moiety of the boronic acid is then added in thetransmetalation step. This step may be accelerated by thepresence of alcohol in the reaction medium, leading to atetracoordinate boron species.[61] In the basic reaction me-dium, boronic acid and halide are eliminated. Reductive eli-mination then yields the cross-coupling product Per-Ar andthe catalytically active species. Alternatively, after the oxi-dative addition of PerX, the halogen in the resulting inter-mediate may be substituted by an ethoxy ligand.[62] Elimi-nation of acetaldehyde leads to the hydride [L2PdPerH]. Asimilar mechanism has also been discussed in the hydro-halogenation reaction with Ni catalysts[63] or for palladium-catalysed reductive homocoupling of aromatic halides.[64]
Hydrodehalogenation as a side process of the Suzuki–Mi-yaura reaction may also be induced by hydrogen transfer
from N,N-dimethylformamide (DMF) to a correspondingintermediate [L2PdArX].[65] In the competition between theSuzuki–Miyaura reaction and the hydrodehalogenation, thelatter is favoured by steric hindrance in either arylhalideor boronic acid substrates.[61] We have also performed thereaction with Pd complexes carrying more bulky ligandssuch as S-phos (2-dicyclohexylphosphino-2�,6�-dimeth-oxybiphenyl). Generally, such catalysts are more efficientbut, in the present study, in only one case was a Suzuki–Miyaura coupling in competition with a hydrodehalogena-tion detected. In the case of the transformation of 6a(Scheme 3 and Table 4), the first halogen atom is easily sub-stituted by an aryl group. In the second substitution, hydro-dehalogenation becomes competitive and the yield of thedesired product decreases (entry 2). Considerable amountsof compound 21 were isolated. Using potassium phenyltri-fluoroborate or phenylboronic acid pinacol ester, com-pound 22 was obtained in high yield from the reaction ofthe 1,12-dichloroperylene derivative 6a (Scheme 3). Onehalogen atom was engaged in a Suzuki–Miyaura couplingwhereas the second reacted through hydrodehalogenation.When exposed to daylight, 22 efficiently undergoes photo-cyclisation, as previously reported.[66] A competition be-tween Suzuki–Miyaura reaction and hydrodehalogenationhas previously been observed for the arylation of a dihalo-gen pyridine compound.[67] Recently, a mono-hydrodehalo-genation product has also been obtained in a Stille cross-
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
Scheme 4. Mechanism of competing Suzuki–Miyaura reaction and hydrodehalogenation.
coupling reaction of 1,12-dichloroperylene derivatives suchas 6a.[68] In this context, it must be pointed out that we didnot detect hydrodehalogenation in the case of the transfor-mation of 1,6,7,12-tetrachloroperylenetetracarbox-3,4:9,10-diimides 5a or 5b (Scheme 2 and Table 2).
Transformation of 1,12-Diarylperylene-3,4:9,10-diimides
Photocyclisations have frequently been reported in stil-bene derivatives or compounds possessing a stilbene moietysuch as polycyclic aromatic molecules.[69,70] An examplewith very similar perylene-3,4:9,10-diimide derivatives wasdescribed by Li et al.[66] Such reactions have also been re-ported for arylperylene-3,4:9,10-diimides, and we observedthem for compounds 21 and 22 (compare Scheme 3). As aresult of this efficient transformation, compound 21 wasnot obtained in pure form (see experimental section). Muchmore surprisingly, we detected similar transformations for1,12-diarylperylene-3,4:9,10-diimides of general structure16 (compare Scheme 3 and Table 4). When exposed to day-light or to the emission of a halogen lamp, such compoundsundergo a photochemical reaction with elimination of onecorresponding benzene derived molecule. This reaction wasslower than the pericyclisation of compounds 21 and 22. Toour knowledge, such a photochemical reaction has not beenreported.[71] We decided to study this transformation inmore detail for the case of compound 17 (Scheme 5). Uponirradiation with visible light, compound 17 undergoes pho-tocyclisation leading to intermediate 23. According to theWoodward–Hoffmann rules for concerted reactions,[72] thispericylic reaction occurs in a conrotatory sense, placing thehydrogen atom and the phenyl substituent at the sp3 hybrid-ised carbon atoms in opposite positions. Such a configura-tion is unfavourable for elimination of benzene.[73] To re-establish aromaticity in ring A, a hydrogen atom must beremoved, which may lead to the formation of a radical spe-cies. In the case of similar reactions of polycyclic aromatic
compounds, it was reported that a phenyl group bonded toa sp3 hybridised carbon (such as the phenyl group in posi-tion 1 of intermediate 23) migrates along the polycyclic sys-tem, thus enabling the release of a second hydrogenatom.[69,74] We suggest that, in our case, rearomatisation atring A occurs through the formation of the tautomeric form24. In a pericyclisation similarly involving a phenyl group,the formation of a stable enol tautomer in connection witha rearomatisation in a benzene system was previously re-ported.[73,75] During the transformation, we detected theformation of benzene, resulting from release of the phenylsubstituent. To gain information on the origin of thehydrogen contained in the generated benzene, we performedthe reaction in the presence of perdeuterated methanol. Un-der these conditions, we have indeed detected monodeuter-ated benzene with an incorporation of d1 = 76%.[76] Thus,we obtained evidence that this hydrogen mainly originatedfrom the solvent and not from the substrate. To gain furtherinformation on the origin of this hydrogen atom, we per-formed the reaction in the presence of monodeuteratedmethanol CH3OD. In this case, we observed exclusively theformation of undeuterated benzene. Thus, additionalhydrogen in the released benzene does not result from pro-tonation of the phenyl ring in intermediates 23 and 24.These observations may indicate the formation of a phenylradical, which abstracts hydrogen from the reaction me-dium, for instance from the methyl group of methanol.Phenyl radicals possess a high energy; however, they maybe formed under photochemical reaction conditions as inthe present case. Intermediates 23 and 24 absorb visiblelight as almost all perylenediimides. Furthermore, and inthe case of intermediate 24, the planarity of the whole stablenaphthoperylene core of 25 is thus established and the aro-matic character is increased. It must be pointed out thatsuch a pericyclisation reaction was not observed for the cor-responding 1,6,7,12-tetraarylperylene derivatives of generalstructure 9a or 9b (see Scheme 2 and Table 3).
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPER
Scheme 5. Pericyclisation of 1,12-diphenylperylenetetracarbox-3,4:9,10-diimide derivative 17.
Determination of Frontier Orbital Energies
Many properties of perylene-3,4:9,10-diimides, and thustheir domains of application, depend on the energies of thefrontier orbitals HOMO (highest occupied molecular or-bital) and LUMO (lowest unoccupied molecular orbital).These energies can be determined by cyclic voltammetry. Inour case, the reduction potential easily gives the energy levelof the LUMO (for a recent correlation of calculated LUMOenergies of perylene derivatives with the reduction poten-tials see Qian et al.[54]). Under the chosen conditions, themeasurement of an oxidation potential was difficult. Onlyfor some samples was a shoulder detected in the corre-sponding wave. The energy gap between the frontier orbit-als corresponds to the electron excitation energy, which isdetermined by UV/Vis spectroscopy. Especially in the caseof low Stokes shifts, a better value of the HOMO–LUMOenergy difference is obtained when the 0–0 transition be-tween S0 and S1 electronic states can be determined fromthe UV/Vis absorption and fluorescence spectra.[77–79] Thecorresponding energy is determined from the intersection(λinter) of the absorption and the normalised emission spec-tra. Typical examples of aryl-substituted derivatives thathave been synthesised in the context of the present studyare depicted in Figure 2. The corresponding data are as-sembled in Table 5. UV and fluorescence data as well as theenergy difference between the frontier orbitals are almostidentical for perylene derivatives carrying two or four halo-gen atoms in the bay positions (entries 1–5). In the seriesof 1,7-diarylated derivatives, the HOMO–LUMO energydifference range between 2.02 and 2.19 eV (entries 6–11).Electron-donating substituents such as p-methoxyphenyl in
compound 11a (entry 7) tend to diminish this energy differ-ence. Electron-withdrawing substituents such as p- or m-cyanophenyl (entries 8, 9 and 11) decrease the absorptionwavelength (λabs) for S1 excitation and also the fluorescencewavelength, whereas electron-donating substituents with p-methoxyphenyl (entry 7) lead to an increase in both wave-lengths. These observations are in line with the fact that the
Table 5. Determination of the HOMO–LUMO gap based on UV/Vis and fluorescence spectroscopy.
[a] Energy difference between absorption and emission band max-ima.
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
Figure 2. Selected examples of absorption and fluorescence spectra of perylenetetracarbox-3,4:9,10-diimides.
perylenetetracarbox-3,4:9,10-diimide core is a rather elec-tron-poor moiety. The same tendency is observed for the1,6,7,12-tetraaryl-substituted perylene derivatives (entries12–14). The HOMO–LUMO energy difference is lower(1.83–1.97 eV). Consequently, absorption and emissionwavelengths are higher. Compared with 1,7-disubstitutedderivatives, the low energy values for the tetra-substitutedderivatives may be explained with an increased twisting andthus a reduced conjugation in the perylene core of thesecompounds. In the case of the 1,12-diaryl-substituted deriv-atives (entries 15–18), a similar tendency is observed. Thevalues for the HOMO–LUMO energy difference vary be-tween 1.92 eV, in the case of p-methoxyphenyl substitution(18) (entry 16), and 2.14 eV, for the m-cyanophenyl deriva-tive 20 (entry18). These values are slightly lower than forthe corresponding 1,7-diarylated perylene derivatives, whichmay be explained by a higher torsion of the perylene corein the first compound family. The 1-phenyl derivative 22 hasthe highest value (2.24 eV) for the frontier orbital energydifference (entry 19) when compared with the 1,7-diphenyl(10a,b; entries 6 and 10), the 1,6,7,12-tetraphenyl (14a; en-try 12) and the 1,12-diphenyl derivatives (17; entry 15). Inline with the present discussion, the latter observation iscertainly due to low torsion of the perylene core structurein the case of 22. Due to a photocyclisation, the benzenearomatic system of the phenyl ring in 25 is in full conjuga-
tion with the perylene system, which further increases theEg value (entry 20). We have further determined the energydifference between absorption and fluorescence emissionband maxima. These values are sometimes denoted asStokes shifts, in particular, when no vibration structures ofthe bands are visible (for further explanations see Klán andWirz[78]). Such values provide information on the structuralsimilarity between the ground state and the S1 excited, vi-brationally relaxed state.[78,79] Small values indicate a rigidstructure, whereas larger values are observed when vi-brational relaxation at the S1 state plays an important role.Thus, halogenated derivatives 3a, 3b, 5a, 5b and 6a (entries1–5) as well as 25 (entry 20) possess rigid structures. Clearly,the aryl-substituted derivatives undergo more significant vi-brational relaxation in the excited state. It is furthermoreinteresting to compare the effects of 1,7-diaryl and 1,12-diaryl substitution. In the first case (entries 6–11), the“Stokes shift” is somewhat lower than for the 1,12-arylatedperylenes (entries 15–18). Generally, p-methoxyphenyl 11a(entry 7) and 18 (entry 16) substitution significantly in-creases these values. As indicated above, this effect may beattributed to some charge transfer character between theelectron-donor aryl substituent and the electron-acceptorperylenediimide core. In the case of the correspondingtetra(p-methoxyphenyl)-perylene derivative 15a, the ten-dency is less clear (entry 13), which may be attributed to
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPERthe more sterically crowded and thus more rigid structure of15a, which limits vibrational relaxation in the excited state.
By using cyclic voltammetry, we have determined the re-duction potential of all the perylene derivatives reported inTable 5. The ferrocene/ferrocinium couple [V(Ag/Ag+) –V(Fc/Fc+) = 0.397 V] was taken as reference. Solutions ofthe perylene derivatives (10–3 mol L–1) in dichloromethanecontaining Bu4NPF6 (0.1 mol L–1) have been measured witha scan rate of 100 mVs–1. Typical examples of aryl-substi-tuted derivatives that have been synthesised in the contextof the present study are depicted in Figure 3. From the firstreduction potentials E1/2
red1 and the ferrocene value of–4.8 eV below the vacuum level, the energy of the lowestunoccupied orbitals (LUMO) were calculated.[80,81] Byusing the values for the HOMO/LUMO energy gap deter-mined by UV and fluorescence spectroscopy (Figure 2 andTable 5), the energies of the highest occupied orbitals(HOMO) are calculated. The corresponding values arelisted in Table 6. As previously observed,[34] the substituentsat the imide functions have a slight influence on the re-duction potentials. Generally, derivatives with the reductionpotentials of the N-octyl derivatives 3b, 5b, 10b, 13b and14b (Table 5, entries 2, 4, 10 11, and 14) are more negativethan those of the corresponding derivatives 3a, 5a, 10a, 13aand 14a carrying two 2,6-diisopropylphenyl substituents inthese positions (entries 1, 3, 6, 9 and 12). Concerning arylsubstitution in the bay positions, the following tendencies
Figure 3. Selected examples of cyclic voltammetry measurements of perylenetetracarbox-3,4:9,10-diimides.
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
13 and 16) are only slightly more negative than those of thecorresponding phenyl derivatives (10a, 14a and 17, entries6, 12 and 15). A more significant difference in reductionpotentials is observed when the phenyl-substituted deriva-tives (10a and 17, entries 6 and 15) are compared with p-cyanophenyl (12a, and 19, entries 8 and 17) or m-cyano-phenyl derivatives (13a, and 20, entries 9 and 18). It mustbe further pointed out that no significant difference wasfound in the reduction potentials of arylperylene derivativespossessing two different substitution patterns. For each arylsubstituent, the values for 1,7- (entries 6–11) or 1,12-substi-tution (entries 15–18) are in the same order of magnitude.For the chosen aryl substituents, even the 1,6,7,12-tetraarylderivatives (entries 12–14) have values in this range. Theenergies of the frontier orbitals ELUMO and EHOMO are ob-tained from subtraction. Therefore, inverse tendencies areobserved for these values.
Optical Resolution
Due to steric interactions between substituents in the baypositions of perylenediimides, the planarity of the perylenemoiety is suppressed and these molecular substructures be-come chiral. Thus, 1,6,7,12-tertraarylperylenediimides suchas 9a possess the chiral symmetry group D2 and 1,12-diaryl-perylenediimides such as 16 possess C2 symmetry (Fig-ure 4). The resulting chirality may be compared to helical oratrope chirality. In the case of 1,6,7,12-tetraaryl-substitutedcompounds such as 9a, the racemisation barrier is estimatedto be around 250 kJ mol–1 (180 K).[42] This estimate is basedon a correlation between apparent overlap parameters ofthe substituents and the free activation enthalpy of racemis-ation.[42,82,83] Such analyses have also been performed forphenanthrene and dihydrophenantrene derivatives carryingsubstituents in the 4- and 5-positions.[84] Compounds ofgeneral structure 9a and 16 should be stable with respect toracemisation, and optical resolution using HPLC withchiral stationary phases should be possible.
Figure 4. Molecular symmetry of chiral compounds 9a and 16.
By using WhelkO1(R,R) 5 μm chiral columns(250�4.6 mm for analytical and 250� 10 mm for semipre-parative separations), racemic mixtures of the tetraarylderivatives 1,6,7,12-tetraphenylperylenetetracarboxdiimide
Figure 5. CD spectra of optically resolved perylenes 14a (seeScheme 2, Table 3) and 18 (see Scheme 3, Table 4). The blue linescorrespond to the enantiomers eluted first. The red lines corre-spond to the enantiomers eluted second.
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPER
Figure 6. Consistent chirality description of perylenediimids 9a and 16 by using the description of helical chirality.
(14a) and 1,6,7,12-tetra(4-methoxyphenyl)perylenetetra-carboxdiimide (15a) (Scheme 2, Table 3) and the diaryl de-rivatives 1,12-diphenylperylenetetracarboxdiimide (17) and1,12-di(4-methoxyphenyl)perylenetetracarboxdiimide (18)(Scheme 3, Table 4) have been resolved. Circular dichroism(CD) spectra of the each enantiomer were recorded. Twoexamples are shown in Figure 5. CD spectra are also usedto determine the molecular chirality.[85] Concerning intrin-sic chirality linked to the D2 or the C2 symmetry, the signof the bands between 530 and 680 nm indicates the absoluteconfiguration. In all cases, the enantiomer eluted firstshowed positive monosignated bands. The longest wave-length absorption (S0–S1 transition) was attributed to atransition dipole moment polarised along the long axis ofthe perylenediimide moiety.[86] The shorter wavelength ab-sorption (S0–S2 transition), which appears as a shoulder,was attributed to a transition dipole moment polarisedalong the short axis of the perylenediimide moiety. Bothaxes are orthogonal with respect to each other. In the caseof the positive bands, the CD was attributed to P helixchirality, whereas the negative bands correspond to M helixchirality of similar perylene diimides.[86] Thus, all firsteluted enantiomers possess P helical chirality (Figure 6)and the second eluted enantiomers possess M chirality.
The optical resolution of 1,12-bis(4-methoxyphenyl)per-ylenediimide (18) and 1,6,7,12-tetraarylperylenediimides14a and 15a was successfully carried out. In the case of1,12-diphenylperylenediimide 17, the resolution was notcomplete and the second eluted enantiomer possessing Mhelical chirality was only obtained with an enantiomeric ex-cess of approximately 57%. Furthermore, in solution, com-pound 17 was unstable; an example of one decompositionreaction is discussed above (Scheme 5).
Conclusions
A variety of 1,7-, 1,12-disubstituted and 1,6,7,12-tetra-arylperylenetetracarbox-3,4:9,10-diimides have been syn-thesised by using the Suzuki–Miyaura reaction as key step.The preparation of 1,12-disubstituted and 1,6,7,12-tetraaryl
derivatives proved to be difficult. In the case of tetrasubsti-tuted compounds, this observation may be attributed to ste-ric hindrance, whereas in the case of 1,12-disubstitutedcompounds, the dehydrohalogenation of one halogen com-pound was the major competitive reaction. This competingreaction was efficient in the case of the transformation ofboronic acids carrying a methoxy substituent as an elec-tron-donating group. It was the only reaction when phenyl-trifluoroborate or phenylboronic acid pinacol esters wereused as arylating reagents. When exposed to visible light,1,12-disubstituted derivatives can undergo photocyclisationfollowed by benzene elimination. Despite these difficulties,a variety of 1,12-disubstituted and 1,6,7,12-tetraaryl-perylene derivatives have been obtained in moderate to highyields. The energies of the frontier orbitals of these com-pounds, as well as those of the corresponding halogen pre-cursors have been determined by using cyclic voltammetryand optical spectroscopy (UV and fluorescence). The pro-files of the optical spectra are mainly influenced by the elec-tronic effects of the substituents in the bay positions of theperylene core. The reduction potentials also depend on thesubstitution at the imide nitrogen atoms, and are morenegative in the case of N-octyl derivatives than for the cor-responding N-(2,6-diisopropylphenyl) compounds.
The substitution pattern in the bay position of these newperylene derivatives also modifies solubility, the ability toform charge transfer complexes, and many other properties.Therefore, such compounds may now be considered moresystematically when perylenediimides are investigated indifferent research fields.
The enantiomers of the inherently chiral perylene deriva-tives 1,12-bis(4-methoxyphenyl)perylenediimide 18 and the1,6,7,12-tetraarylperylenediimides 14a and 15a have beenseparated by using HPLC with columns carrying a chiralstationary phase. 1,12-Di(4-phenyl)perylenediimide 18 waspartially resolved. By using CD spectroscopy, the configu-ration of each enantiomer was determined. The polaritiesof the different perylene derivatives are similar because theenantiomer possessing P helix chirality always eluted firstunder the described conditions.
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
Experimental SectionGeneral: All commercially available products were used withoutfurther purification. Solvents were degassed with a flow of argonfor 20 min. Thin-layer chromatography (TLC) analyses were doneusing aluminium sheets coated with silica gel 60 F254. Flash col-umn chromatography (FC) was carried out using silica gel 60 Å(0.04–0.063 mm). NMR spectra were recorded with 500 MHz(BBFO + Z-GRD Probe) (1H: 500 MHz and 13C: 125 MHz) and600 MHz (CPTCI Z-GRD CryoProbe) (1H: 600 and 13C:151 MHz) spectrometers in CD2Cl2 and [D8]toluene. Chemicalshifts are given in ppm, calibrated to the residual solvent peak,[87]
and coupling constants J are expressed in Hertz (s = singlet, br. s= broad singlet, d = doublet, dd = double doublet, t = triplet,quart = quartet, quint = quintet, sext = sextet, sept = septet, m =multiplet). High-resolution mass spectra (HRMS) were performedwith a Q-TOF Micro positive ESI (CV = 30 V). Cyclic voltammo-grams (CVs) were recorded with a potentiostat/galvanostat usingglassy carbon discs as the working electrode, Pt wire as the counterelectrode, Ag/Ag+ electrode as the reference electrode, and ferro-cene/ferrocenium as an internal reference. The scan speed was100 mVs–1. A solution of tetrabutylammonium hexafluorophos-phate (Bu4NPF6) in CH2Cl2 (0.1 m) was employed as the support-ing electrolyte. The energy level of Fc/Fc+ is assumed to be –4.8 eVbelow the vacuum level.[81] The LUMO levels of the products wereestimated from the half-wave potentials of the reduction peaks. TheCD spectra of CH2Cl2 solutions were recorded at 20 °C with a 1 cmcell.
N,N�-Di(2,6-diisopropylphenyl)-1,7-diphenylperylenetetracarboxdi-imide (10a): In a 100 mL round-bottom flask were introducedN,N�-di(2,6-diisopropylphenyl)-1,7-dibromoperylene tetracarbox-ylic acid diimide (3a; 88 mg, 0.10 mmol, 1 equiv.), phenylboronicacid (124 mg, 1.01 mmol, 10 equiv.), anhydrous potassium carb-onate (146 mg, 1.05 mmol, 10.5 equiv.) and tetrakis(triphenylphos-phine)palladium (13 mg, 0.011 mmol, 10% equiv.). The flask wasevacuated and backfilled with argon three times. Toluene (10 mL),ethanol (2 mL) and distilled water (5 mL) were degassed with aflow of argon for 20 min. Then the solvents were added sub-sequently. The reaction mixture was stirred overnight at 85 °C un-der argon. After cooling to room temperature, the mixture was fil-tered to remove the catalyst, extracted with dichloromethane andwashed three times with water. The organic phases were then com-bined and dried with magnesium sulfate. The solvent was removedunder reduced pressure and the crude product was purified by silicagel column chromatography (dichloromethane–petroleum ether,90:10). The resulting dark-red solid was washed with petroleumether to give the product (86 mg, 98%); m.p. � 350 °C. 1H NMR(600 MHz, CD2Cl2, 25 °C): δ = 8.70 (s, 2 H), 8.20 (d, J = 8.1 Hz,2 H), 7.98 (d, J = 8.1 Hz, 2 H), 7.61–7.45 (m, 8 H), 7.35 (d, J =7.8 Hz, 2 H), 2.75 (sept, J = 6.6 Hz, 4 H), 1.14 (d, J = 6.6 Hz, 12H), 1.13 (d, J = 6.6 Hz, 12 H) ppm. 13C NMR (151 MHz, CD2Cl2,25 °C): δ = 164.1, 164.0, 146.4, 142.6, 141.8, 136.1, 135.9, 133.6,131.5, 131.0, 130.6, 130.2, 130.0, 129.9, 129.5, 129.1, 128.8, 124.5,122.6, 122.3, 29.5, 24.2, 24.1 ppm. HRMS (ESI): m/z calcd. forC60H50N2O4Na+ [M + Na]+ 885.3668; found 885.3641. IR (KBr):ν = 3059, 3028, 2963, 2929, 2869, 1739, 1706, 1668, 1590, 1447,1403, 1333, 1235, 1198, 1147, 1053, 971, 937, 839, 815, 749,701 cm–1.
N,N�-Di(2,6-diisopropylphenyl)-1,7-di(4-methoxyphenyl)perylene-tetracarboxdiimide (11a): By using the same conditions describedfor the synthesis of 12a, N,N�-di(2,6-diisopropylphenyl)-1,7-di(4-methoxyphenyl)perylene tetracarboxylic acid diimide (11a) was ob-tained after silica gel column chromatography (ethyl acetate–petro-
B. Pagoaga, L. Giraudet, N. HoffmannFULL PAPER2929, 2869, 2233, 1707, 1668, 1593, 1501, 1465, 1429, 1397, 1331,1240, 1199, 1145, 1057, 838, 812, 741, 696 cm–1.
N,N�-Dioctyl-1,7-diphenylperylenetetracarboxdiimide (10b): In a100 mL round-bottom flask were introduced N,N�-dioctyl-1,7-di-bromoperylene tetracarboxylic acid diimide (3b ; 203 mg,0.26 mmol, 1 equiv.), phenylboronic acid (319 mg, 2.61 mmol,10 equiv.), anhydrous sodium carbonate (125 mg, 1.18 mmol,4.5 equiv.) and tetrakis(triphenylphosphine)palladium (33 mg,0.028 mmol, 10% equiv.). The flask was evacuated and backfilledwith argon three times. Toluene (10 mL), ethanol (2 mL) and dis-tilled water (5 mL) were degassed with a flow of argon for 20 min.Then the solvents were added subsequently. The reaction mixturewas stirred for 3 h at 80 °C under argon and, after cooling to roomtemperature, the mixture was filtered to remove the catalyst, ex-tracted with dichloromethane and washed three times with water.The organic phases were then combined and dried with magnesiumsulfate. The solvent was removed under reduced pressure and thecrude product was purified by silica gel column chromatography(dichloromethane–petroleum ether, 60:40). The resulting purple so-lid was washed with petroleum ether, to give the product (201 mg,89%); m.p. � 350 °C. 1H NMR (500 MHz, CD2Cl2, 25 °C): δ =8.40 (s, 2 H), 7.99 (d, J = 8 Hz, 2 H), 7.56 (d, J = 8 Hz, 2 H), 7.47(br. s, 10 H), 4.13 (t, J = 7.5 Hz, 4 H), 1.70 (quint, J = 7.5 Hz, 4H), 1.26–1.43 (m, 20 H), 0.88 (t, J = 7 Hz, 6 H) ppm. 13C NMR(125 MHz, CD2Cl2, 25 °C): δ = 163.5, 163.4, 142.5, 141.2, 135.2,134.7, 135.2, 130.5, 129.4, 129.3, 129.2, 129.0, 127.6, 122.5, 122.2,40.9, 32.3, 29.8, 29.7, 28.5, 27.6, 23.1, 14.3 ppm. HRMS (ESI): m/zcalcd. for C52H51N2O4 [M + H]+ 767.3849; found 767.3837. IR(KBr): ν = 3055, 2953, 2923, 2852, 1697, 1656, 1593, 1589, 1491,1446, 1434, 1407, 1331, 1264, 1246, 1170, 1132, 1088, 1029, 932,860, 811, 776, 754, 698 cm–1.
N,N�-Dioctyl-1,7-di(3-cyanophenyl)perylenetetracarboxdiimide(13b): In a 100 mL round-bottom flask were introduced N,N�-dioc-tyl-1,7-dibromoperylene tetracarboxylic acid diimide (3b; 175 mg,0.23 mmol, 1 equiv.), 3-cyanophenylboronic acid (166 mg,1.13 mmol, 5 equiv.), anhydrous potassium carbonate (82 mg,0.59 mmol, 2.6 equiv.) and tetrakis(triphenylphosphine)palladium(26 mg, 0.023 mmol, 10 % equiv.). The flask was evacuated andbackfilled with argon three times. Toluene (10 mL), ethanol (2 mL)and distilled water (5 mL) were degassed with a flow of argon dur-ing 20 min. Then the solvents were added subsequently. The reac-tion mixture was stirred overnight at 85 °C under argon and, aftercooling to room temperature, the mixture was filtered to removethe catalyst, extracted with dichloromethane and washed threetimes with water. The organic phases were then recombined anddried with magnesium sulfate. The solvent was removed under re-duced pressure and the crude product was recrystallised twice(chloroform–hexane, 30:70). The pink-purple solid was washedwith methanol to give the product (144 mg, 78%); m.p. � 350 °C.1H NMR (500 MHz, CD2Cl2, 25 °C): δ = 8.51 (s, 2 H), 8.17 (d, J
duced N,N�-di(2,6-diisopropylphenyl)-1,6,7,12-tetrachloroperylenetetracarboxylic acid diimide (5a; 303 mg, 0.35 mmol, 1 equiv.),potassium phenyltrifluoroborate (1.3 g, 7.07 mmol, 20.1 equiv.),anhydrous potassium carbonate (1 g, 7.23 mmol, 20.7 equiv.) andtetrakis(triphenylphosphine)palladium (42 mg, 0.036 mmol,10% equiv.). The flask was evacuated and backfilled with argonthree times. Toluene (10 mL), ethanol (2 mL) and distilled water(5 mL) were degassed with a flow of argon during 20 min. Thenthe solvents were added subsequently. The reaction mixture wasstirred overnight at 80 °C under argon and, after cooling to roomtemperature, the mixture was filtered to remove the catalyst, ex-tracted with dichloromethane and washed three times with water.The organic phases were then recombined and dried with magne-sium sulfate. The solvent was removed under reduced pressure andthe crude product was purified by silica gel column chromatog-raphy (toluene–dichloromethane, 60:40). The resulting blue-purplesolid was washed with petroleum ether to give the product (264 mg,74 %); m.p. � 350 °C. 1H NMR (600 MHz, CD2Cl2, 25 °C): δ =8.34 (s, 4 H), 7.53 (t, J = 8 Hz, 2 H), 7.38 (d, J = 8 Hz, 4 H), 7.25(t, J = 7.5 Hz, 4 H), 7.15 (br. s, 8 H), 6.82 (br. s, 8 H), 2.86 (sept,J = 7 Hz, 4 H), 1.22 (d, J = 7 Hz, 12 H), 1.14 (d, J = 7 Hz, 12H) ppm. 13C NMR (151 MHz, CD2Cl2, 25 °C): δ = 164.3, 146.6,143.4, 141.0, 134.4, 132.8, 132.2, 131.6, 131.0, 129.9, 128.9, 128.1,127.1, 124.5, 122.6, 29.5, 24.2, 24.2 ppm. HRMS (ESI): m/z calcd.for C72H58N2O4Na+ [M + Na]+ 1037.4294; found 1037.4301. IR(KBr): ν = 3059, 3029, 2963, 2929, 2869, 1707, 1671, 1591, 1449,1409, 1313, 1227, 1198, 1056, 1031, 985, 931, 843, 814, 747,696 cm–1.
N,N�-Di(2,6-diisopropylphenyl)-1,6,7,12-tetra(4-methoxyphenyl)-perylenetetracarboxdiimide (15a): In a 100 mL round-bottom flaskwere introduced N,N�-di(2,6-diisopropylphenyl)-1,6,7,12-tetra-chloroperylene tetracarboxylic acid diimide (100 mg, 0.12 mmol,1 equiv.), 4-methoxyphenylboronic acid (358 mg, 2.35 mmol,19.6 equiv.), anhydrous potassium carbonate (1.5 g, 10.85 mmol,90.4 equiv.) and tetrakis(triphenylphosphine)palladium (40 mg,0.035 mmol, 29% equiv.). The flask was evacuated and backfilledwith argon three times. Toluene (10 mL), ethanol (2 mL) and dis-tilled water (5 mL) were degassed with a flow of argon during20 min. Then the solvents were added subsequently. The reactionmixture was stirred overnight at 85 °C under argon and, after cool-ing to room temperature, filtered to remove the catalyst, extractedwith dichloromethane and washed three times with water. The or-ganic phases were then recombined and dried with magnesium sulf-ate. The solvent was removed under reduced pressure and the crudeproduct was purified by silica gel column chromatography (di-chloromethane–petroleum ether, 70:30). The resulting dark-blue so-lid was washed with petroleum ether to give the product (74 mg,55%); m.p. � 350 °C. 1H NMR (600 MHz, CD2Cl2, 25 °C): δ =8.29 (s, 2 H), 8.29 (s, 2 H), 7.52 (t, J = 7.8 Hz, 2 H), 7.37 (d, J =7.8 Hz, 4 H), 6.80 (br. s, 8 H), 6.69 (br. s, 8 H), 3.84 (s, 6 H), 3.83(s, 6 H), 2.85 (sept, J = 6.6 Hz, 4 H), 1.21 (d, J = 7.2 Hz, 12 H),1.14 (d, J = 7.2 Hz, 12 H) ppm. 13C NMR (151 MHz, CD2Cl2,25 °C): δ = 164.4, 160.0, 146.6, 142.4, 134.0, 133.7, 132.7, 132.5,131.8, 130.3, 129.8, 126.8, 124.5, 122.2, 55.8, 29.5, 24.2, 24.2 ppm.HRMS (ESI): m/z calcd. for C76H67N2O8
Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
4.90 mmol, 10.5 equiv.) and tetrakis(triphenylphosphine)palladium(37 mg, 0.032 mmol, 7 % equiv.). The flask was evacuated andbackfilled with argon three times. Toluene (10 mL), ethanol (2 mL)and distilled water (5 mL) were degassed with a flow of argon dur-ing 20 min. Then the solvents were added subsequently. The reac-tion mixture was stirred overnight at 80 °C under argon and, aftercooling to room temperature, filtered to remove the catalyst, ex-tracted with dichloromethane and washed three times with water.The organic phases were then recombined and dried with magne-sium sulfate. The solvent was removed under reduced pressure andthe crude product was recrystallised twice in dichloromethane-eth-anol. The resulting green-purple solid was washed with petroleumether, to give the product (167 mg, 39%); m.p. � 350 °C. 1H NMR(500 MHz, CD2Cl2, 25 °C): δ = 8.24 (s, 4 H), 7.21 (t, J = 7.5 Hz,4 H), 7.08 (br. s, 8 H), 6.69 (br. s, 8 H), 4.18 (t, J = 7.5 Hz, 4 H),1.76 (quint, J = 7.5 Hz, 4 H), 1.31–1.47 (m, 20 H), 0.89 (t, J =7 Hz, 6 H) ppm. 13C NMR (125 MHz, CD2Cl2, 25 °C): δ = 163.9,142.8, 140.9, 133.6, 132.3, 131.7, 129.1, 127.9, 126.4, 122.8, 40.9,32.3, 29.8, 29.7, 28.6, 27.6, 23.1, 14.3 ppm. HRMS (ESI): m/z calcd.for C64H59N2O4 [M + H]+ 919.4475; found 919.4465. IR (KBr): ν= 3056, 3030, 2952, 2924, 2853, 1699, 1661, 1590, 1517, 1490, 1448,1413, 1351, 1312, 1226, 1170, 1079, 1049, 1000, 930, 911, 811, 781,747, 696 cm–1.
N,N�-Di(2,6-diisopropylphenyl)-1,12-diphenylperylenetetracarboxdi-imide (17): In a 100 mL round-bottom flask were introduced N,N�-di(2,6-diisopropylphenyl)-1,12-dichloroperylene tetracarboxylicacid diimide (6a; 484 mg, 0.62 mmol, 1 equiv.), phenylboronic acid(758 mg, 6.21 mmol, 10 equiv.), anhydrous sodium carbonate(339 mg, 3.2 mmol, 5.1 equiv.) and tetrakis(triphenylphosphine)palladium (37 mg, 0.032 mmol, 5% equiv.). The flask was evacu-ated and backfilled with argon three times. Toluene (10 mL), eth-anol (2 mL) and distilled water (5 mL) were degassed with a flowof argon during 20 min. Then the solvents were added sub-sequently. The reaction mixture was stirred overnight at 85 °C un-der argon and, after cooling to room temperature, filtered to re-move the catalyst, extracted with dichloromethane and washedthree times with water. The organic phases were then recombinedand dried with magnesium sulfate. The solvent was removed underreduced pressure and the crude product was obtained after silicagel column chromatography (dichloromethane–petroleum ether,50:50 to dichloromethane). The dark green-purple solid waswashed with petroleum ether to give the product (334 mg, 62%);m.p. � 350 °C. 1H NMR (600 MHz, CD2Cl2, 25 °C): δ = 8.78 (d,J = 7.8 Hz, 2 H), 8.71 (d, J = 7.8 Hz, 2 H), 8.31 (s, 2 H), 7.52 (t,J = 7.8 Hz, 2 H), 7.39 (dd, J = 7.8, 1.2 Hz, 2 H), 7.34 (dd, J = 7.8,1.2 Hz, 2 H), 7.25 (t, J = 7.2 Hz, 2 H), 7.18 (br. s, 2 H), 7.13 (br.s, 2 H), 6.93 (br. s, 2 H), 6.70 (br. s, 2 H), 2.91 (sept, J = 6.6 Hz, 2H), 2.67 (sept, J = 6.6 Hz, 2 H), 1.24 (d, J = 6.6 Hz, 6 H), 1.22 (d,J = 6.6 Hz, 6 H), 1.12 (d, J = 6.6 Hz, 6 H), 1.05 (d, J = 7.2 Hz, 6H) ppm. 13C NMR (151 MHz, CD2Cl2, 25 °C): δ = 164.3, 164.1,146.6, 146.4, 144.1, 141.1, 135.9, 135.4, 133.3, 131.5, 131.4, 130.0,129.9, 129.2, 128.8, 128.5, 128.1, 124.5, 124.5, 123.9, 123.1, 123.1,29.5, 29.5, 24.3, 24.2, 24.0, 24.0 ppm. HRMS (ESI): m/z calcd. forC60H50N2O4Na+ [M + Na]+ 885.3668; found 885.3658. IR (KBr):ν = 3060, 3030, 2962, 2928, 2868, 1707, 1669, 1589, 1446, 1397,1341, 1239, 1193, 1145, 1056, 971, 935, 839, 811, 745, 697 cm–1.
N,N�-Di(2,6-diisopropylphenyl)-1,12-di(4-methoxyphenyl)perylene-tetracarboxdiimide (18): By using the same conditions described forthe synthesis of 12a, N,N�-di(2,6-diisopropylphenyl)-1,12-di(4-methoxyphenyl)perylene tetracarboxylic acid diimide (18) was ob-tained after silica gel column chromatography (ethyl acetate–petro-leum ether, 10:90). The first fraction afforded monosubstitutedcompound 21 with a yield of 46%, as a red solid. This product
Methoxynaphthoperylenetetracarboxdiimide Derivative (26): Com-pound 21 in dichloromethane was fully converted into the cyclisedderivative 26 after very short exposure to visible light. After wash-ing with methanol and petroleum ether, the pure product was iso-lated as a red solid (m.p. � 350 °C).
Optical Resolution of Inherently Chiral Perylene Derivatives 14a,15a, 17 and 18: The separation of the enantiomers was performedby HPLC with WhelkO1(R,R) 5 μm chiral columns (250�4.6 mmfor analytical and 250�10 mm for semipreparative separations).The semipreparative separations were performed with the followingparameters: Flow rate: 4.5 mL/min; eluent: hexane/CH2Cl2: 70:30(14a, 15a), 78:22 (17) and 75:25 (18).
Supporting Information (see footnote on the first page of this arti-cle): 1H and 13C NMR spectra of 10a, 11a, 12a, 13a, 10b, 13b, 14a,15a, 14b, 17, 18, 19, 20, 22, 25 and 26. UV/Vis and fluorescencespectra of 3a, 3b, 5a, 5b, 6, 10a, 11a, 13a, 10b, 13b, 14a, 14b, 22and 25. Cyclic voltammograms of 3a, 3b, 5a, 5b, 6, 10a, 11a, 13a,10b, 13b, 14a, 14b, 22 and 25. HRMS of monodeuterated benzene.HRMS of benzene. CD spectra after optical resolution of com-pounds 14a, 15a, 17 and 18.
Acknowledgments
The authors are grateful to Dr. Cyril Cadiou for his help with cyclicvoltammetry measurements, and to Sylvie Lanthony for particularGC/MS spectroscopic experiments and for the help with opticalresolution using HPLC. The authors also acknowledge the helpof Agathe Martinez with recording of CD spectra. The RégionChampagne-Ardenne (FEDER, CPER, projects PEPIT andPEPITA) is thanked for funding. Support from BASF SE is alsoacknowledged.
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Characterization of Arylperylenetetracarbox-3,4:9,10-diimides
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Received: May 23, 2014Published Online: July 15, 2014
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