Compound for uses in optical and electrooptical devices

Abstract

A compound having the following formula: ##STR00001##
which can also be embedded into a conjugated oligomeric of polymeric backbone, is proposed for optical and electro optical applications.

Claims

1. A compound having the following formula: ##STR00013## wherein Q.sub.1, Q.sub.2 are one or a mixture of ?-conjugated aromatic cores; R.sub.1 and R.sub.2 are selected, independently from each other, from the following group: H, halogen, methyl, Sn(R.sub.R,1).sub.3, B(OH).sub.2, OR.sub.R,2, NR.sub.R,3R.sub.R,4, NO.sub.2, COOR.sub.R,5, COR.sub.R,6, SR.sub.R,7, CN, CCR.sub.R,8, SO.sub.3H, CH?C(CN).sub.2, CH?C(CN)(COOR.sub.R,9), C(CN)?C(CN).sub.2, substituted and unsubstituted ferrocene and derivatives thereof, substituted and unsubstituted pyridine and derivatives thereof, pentafluorophenol, and substituted and unsubstituted fullerene and derivatives thereof; with the residues R.sub.R,1,-R.sub.R,9 selected, independently from each other, from the group consisting of: methyl, ethyl, propyl, isopropyl, phenyl, benzyl, and primary, secondary, and tertiary amines; V.sub.1 and V.sub.2 are selected, independently from each other, from the following group: CH.sub.2, S, O, NH, COO, CO, CONR.sub.V,1, and NR.sub.V,2CO, with the residues R.sub.V,1 and R.sub.V,2 selected, independently from each other, from the group consisting of H, methyl, ethyl, propyl, isopropyl, phenyl and benzyl; X.sub.1 and X.sub.2 are selected, independently from each other, from the following group: N, and CH; Z.sub.1 and Z.sub.2 are selected, independently from each other, from the following group: halogen, methyl, ethyl, propyl, isopropyl, phenyl, benzyl, SR.sub.Z,1, OR.sub.Z,2, COOR.sub.Z,3, NR.sub.Z,4R.sub.Z,5 NO.sub.2, CN, and SO.sub.3H, with the residues R.sub.Z,1-R.sub.Z,5 selected, independently from each other, from the group consisting of H, methyl, ethyl, propyl, isopropyl, benzyl, primary amines, secondary amines, and tertiary amines; L is a hydrocarbon chain with 5-15 carbon atoms in which up to 3 hydrocarbon moieties (CH.sub.2) can be replaced by one of the following moieties: O, NR.sub.L,1, S, and/or in which there can be up to 3 double or triple bonds, in which pairs of the type CH.sub.2CH.sub.2 are replaced by C?C, R.sub.L,2C?CR.sub.L,3-, or N?CR.sub.L,4-, with the residues R.sub.L,1-R.sub.L,4 selected, independently from each other, from the group consisting of H, methyl, ethyl, propyl, isopropyl and benzyl; W is selected from the group consisting of: H, halogen, SR.sub.W,1, methyl, ethyl, OR.sub.W,2, and COOR.sub.W,3, with the residues R.sub.W,1-R.sub.W,3 selected, independently from each other, from the group consisting of H, methyl, ethyl, propyl, isopropyl, phenyl and benzyl; S.sub.1S.sub.9 are selected, independently from each other, from the group consisting of: H, halogen, methyl, ethyl, phenyl, benzyl, OR.sub.S,1, SR.sub.S,2, COOR.sub.S,3, C(?O)R.sub.S,4, NR.sub.S,5R.sub.S,6, NO.sub.2, and SO.sub.3H, with the proviso that pairs of S.sub.1-S.sub.4, S.sub.5 and S.sub.6, pairs of S.sub.7-S.sub.9 can be given by bridging conjugated structural elements selected from the group consisting of: ortho (CH).sub.2-benzene, (CR.sub.S,9)(CR.sub.S,10)(CR.sub.S,11), (CR.sub.S,12)(CR.sub.S,13)(CR.sub.S,14)(CR.sub.S,15), and (CR.sub.S,16)(CR.sub.S,17)(CR.sub.S,18)(CR.sub.S,19)(CR.sub.S,20), in which CR.sub.S,N moieties can be replaced by N, NH, O, and/or S, with the residues R.sub.S,1-R.sub.S,20 selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, phenyls and benzyl P.sub.1, P.sub.2 are one or a mixture of ?-conjugated aromatic cores l is selected to be an integer in the range of 0-10 m is selected to be an integer in the range of 1-10 n is selected to be an integer in the range of 0-10 x is selected to be an integer in the range of 1-10,000 with the proviso that 1+n is at least 1.

2. The compound according to claim 1, wherein at least one of P.sub.1 and P.sub.2 is selected from the group consisting of at least one of: 2,1,3-benzothiadiazole, azole, diazole, triazole, tetrazole, thiophene, pyrrole, furane, selenophene, vinylene, selenazole, thiazole, thiadiazole, oxazole, oxadiazole, pyridine, diazine, triazine, tetrazine, selenazine, thiazine, azepine, diazepine, phenyl based cores, biphenyl based cores, arylamine derivatives, tetraphenylbenzidine, carbazole, pyrrole-based macrocycles, boron derivatives, difluoroboradiaza indacene, ethylenedioxythiophene, phosphorus derivatives, perylene derivatives, N,N dialkyl perylene dicarboximide, N,N dibenzyl perylene dicarboximide, naphthalene derivatives, N,N dialkyl naphthalene dicarboximide, N,N dibenzyl naphthalene dicarboximide, polycyclic aromatic hydrocarbons, thienothiophene and its derivatives, benzodithiophene and its derivatives, and tetrathiafulvalene and its derivatives.

3. The compound according to claim 1, wherein at least one of P.sub.1 and P.sub.2 is selected to be thiophene or a bridged ?-conjugated biphenyl.

4. The compound according to claim 1, wherein one of Q.sub.1 and Q.sub.2 is given by one of the following structural moieties: ##STR00014## wherein R is R.sub.1 or R.sub.2, respectively, A.sub.1, A.sub.2, and A.sub.3 are selected, independently from each other, from the following group: S, O, NH, NR.sub.A,1, BH, BR.sub.A,1, PR.sub.A,1, PR.sub.A,1R.sub.A,2, Se, CH?CH, CH?N, CH?PR.sub.A,1, CH?PR.sub.A,1R.sub.A,2, CH.sub.2, C?O, C?CH.sub.2, and C?CR.sub.A,1R.sub.A,2, with the residues R.sub.A,1 and R.sub.A,2 selected, independently from each other, from the group consisting of H, methyl, ethyl, propyl and benzyl; S.sub.11 and S.sub.13 are selected, independently from each other, from the group consisting of: H, halogen, methyl, ethyl, phenyl, benzyl, OR.sub.S,21, SR.sub.S,22, COOR.sub.S,23, C(?O)R.sub.S,24, NR.sub.S,25R.sub.S,26, NO.sub.2, and SO.sub.3H, with the residues R.sub.S,21-R.sub.S,26 selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, phenyl and benzyl.

5. The compound according to claim 4, wherein S11 and S13 are each selected to be H.

6. The compound according to claim 1, wherein Q.sub.1-Q.sub.2 are each selected to be thiophene.

7. The compound according to claim 1, wherein X.sub.1 and X.sub.2 are each selected to be N.

8. The compound according to claim 1, wherein V.sub.1 and V.sub.2 are each selected to be O.

9. The compound according to claim 1, wherein Z.sub.1 and Z.sub.2 are each selected to be methyl.

10. The compound according to claim 1, wherein W is selected from the group consisting of methyl and methoxy.

11. The compound according to claim 1, wherein L is selected to be a hydrocarbon chain with 8-12 carbon atoms, in which up to 2 hydrocarbon moieties can be replaced by one of the following moieties: O, NH, S, and in which there can be up to 2 carbon-carbon double or triple bonds.

12. The compound according to claim 1, wherein L is selected to be a (CH.sub.2) chain with 8-12 carbon atoms, and two of the (CH.sub.2) moieties are replaced by (CH) to form a double bond.

13. The compound according to claim 1, wherein L is selected to be a (CH.sub.2) chain with 10 carbon atoms, and two of the (CH.sub.2) moieties are replaced by (CH) to form a double bond at the position of the fifth carbon atom of the chain of L.

14. The compound according to claim 1, wherein S.sub.1-S.sub.9 are each selected to be H.

15. The compound according to claim 1, wherein x is selected to be an integer in the range of 10-1000.

16. The compound according to claim 1, wherein at least one of P1 and P2 is selected from the group consisting of at least one of: 2,1,3-benzothiadiazole, azole, imidazole and pyrazole, triazole, tetrazole, thiophene, pyrrole, furane, selenophene, vinylene, selenazole, thiazole, thiadiazole, oxazole, oxadiazole, pyridine, pyrimidine, triazine, tetrazine, selenazine, thiazine, azepine, diazepine, phenyl based cores, biphenyl based cores, triphenylamine, tetraphenylbenzidine, carbazole, porphyrin, phthalocyanine, triphenylborane, difluoroboradiaza indacene, ethylenedioxythiophene, triphenylphosphine, triphenylphosphine oxide, perylene tetracarboxylic dianhydride, N,N dialkyl perylene dicarboximide, N,N dibenzyl perylene dicarboximide, naphthalene tetracarboxylic dianhydride, N,N dialkyl naphthalene dicarboximide, N,N dibenzyl naphthalene dicarboximide, anthracene, tetracene, pentacene, pyrene, thienothiophene and its derivatives, benzodithiophene and its derivatives, and tetrathiafulvalene and its derivatives.

17. An optical, electronic or electro-optics device comprising a compound according to claim 1.

18. The device according to claim 17, wherein the device is a photochromic photovoltaic device, a multicolour organic light emitting diodes device, or a photo tuneable organic field effect transistor.

19. An optical, electronic or electro-optics device comprising a compound according to claim 1, wherein the device comprises a substrate and at least one layer on said substrate, said layer including at least one said compound.

20. A method for making an optical, electronic or electro-optics device comprising: making at least one layer including at least one compound according to claim 1 on a substrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,

(2) FIG. 1 shows optimized geometries of 1.trans (left) and 1.cis (right) identified from Molecular Mechanics computation;

(3) FIG. 2 shows in (a) an absorption spectrum of 1.trans (solid), 1.cis (dotted), and the photostationary state PSS254 (dashed) in tetrahydrofuran (THF) solution; the inset shows the S0.fwdarw.S1 band of the phenylene-bithiophene segment on an enlarged scale, in (b) measured absorbance at ?=363 nm of 1 in THF solution alternating irradiation at ?=350 and ?=254 nm in repeated switching cycles, and in (c) measured absorbance at ?=363 nm of 1.cis in THF solution during the thermal relaxation;

(4) FIG. 3 shows the aromatic region of the .sup.1H-NMR spectrum of compound 1 in tetrahydrofuran-d8; before (a) and after 1 h of irradiation at 350 nm (b).

DESCRIPTION OF PREFERRED EMBODIMENTS

(5) A molecular architecture is presented that can reversibly change the geometric conformation of its ?-system backbone via irradiation with two different wavelengths. The proposed molecular actuator consists of a photoswitchable azobenzene laterally connected to a ?-conjugated bithiophene by both direct and aliphatic linker-assisted bonding. Upon exposure to 350 nm light, the trans azobenzene moiety isomerizes to its cis form, causing the bithiophene to assume a semiplanar anti conformation (high ?-conjugation). Exposure to 254 nm light promotes the isomerization of the azobenzene unit back to its initial extended trans conformation, thus forcing the bithiophene fragment to twist out of coplanarity (poor ?-conjugation). The molecular conformation of the bithiophene was characterized using steady-state UV-Vis and nuclear magnetic resonance spectroscopy, as well as molecular modeling. The proposed molecular design could be envisaged as a ?-conjugation modulator, which has potential to be incorporated into extended linear ?-system, i.e. via the terminal ?-thiophene positions, and used to modulate their optical and electronic properties.

(6) The ability to control mechanical motion at the molecular level is pivotal for development of novel responsive materials able to translate the functionality of molecules into work. In the last 20 years, a large variety of molecular actuators able to convert thermal, chemical, and photochemical energy into operating motion have been successfully employed to perform tasks at the meso- and macroscopic levels. The restrained mechanistic action of these molecular actuators is commonly correlated with thoughtful design of their dynamic molecular structure. In order to provide different functions, various molecular architectures have been proposed, e.g. shuttles, rotors, scissors, cars, chemical valves, and artificial molecular-based muscles. A number of these molecular actuators have also been successfully engineered to undergo controlled molecular motion and to undertake work on their environment, e.g. cargo lifting, transporting and rotating systems. Despite the large variety of synthetic responsive architectures reported in literature, examples of design conceived to exploit the molecular motion as a means to tune the conjugation length of linear ?-systems remain scarce. Molecular actuators designed for the dynamic tuning of ?-conjugated molecules are usually limited by the possibility to switch the orientation of their constituents between only two thermodynamically stable semiplanar conformations, syn and anti. The restricted modus operandi of these actuators does not make it possible to obtain highly twisted ?-orbital geometries, which if achieved would allow for the full exploitation of the physical properties of ?-conjugated systems. The ability to modulate the ?-bond geometry of an extended conjugated system offers the possibility to tailor the effective conjugation length of the ?-system, thus, allowing for the tuning of its optical and electronic properties.

(7) The dynamic modulation of optoelectronic properties is particularly desirable for the development of novel smart materials that can be used as active components in optoelectronic devices such as organic light emitting diodes (OLEDs), solar cells, field effect transistors (OFETs), etc.

(8) In this line a novel molecular design is proposed here, referred to as a Photochromic Torsional Switch (PTS), able to mechanically change planarity of its ?-conjugated backbone, in response to light. PTS actuators are a chemical motif that can be incorporated into the backbone of linear ?-systems to reversibly modulate their conjugation length. The design of PTS 1 is illustrated as follows:

(9) ##STR00012##

(10) The PTS actuator according to the specifically worked example consists of an azobenzene-switch laterally connected to a bithiophene unit by both direct and aliphatic linker-assisted bonding. Two methyl units in the meta position of the azobenzene guarantees its orientation in an orthogonal arrangement to the bithiophene fragment, thus suppressing significantly the communication between the ?-orbitals of the two constituents.

(11) A ten-carbon alkene chain connected with an alkoxy benzene unit transfers mechanically the motion of the azobenzene to the bithiophene backbone. The described PTS actuator 1 was synthetized as the pure trans conformer by intra-molecular cross metathesis of the two terminal alkenes of its open precursor.

(12) The geometrical conformations of both 1.trans and 1.cis, were identified by Molecular Mechanics computations. The lowest-lying structures revealed that when the azobenzene is in its extended trans conformation (1.trans), the bithiophene unit is forced to twist out of coplanarity with a dihedral angle (?) of 45? (see FIG. 1).

(13) Contrarily, when the azobenzene assumes its cis form (1.cis) the bithiophene assumes a more planar and ?-conjugated conformation with ?=?159?. The later dihedral angle is in good agreement with the literature values reported for unsubstituted bithiophenes in their anti-conformation (?=148?-152?).

(14) On the other hand, the bithiophene configuration in 1.trans has a dihedral angle that significantly differs from the values commonly observed for both anti and syn conformers (?=35-37?). The synclinal arrangement assumed by the thiophenes in 1.trans is the result of a suppressed rotation along the thiophene-thiophene bond derived by the stretching of the aryloxy alkene linker, which mechanically arrests the bithiophene in a conformation that would be energetically unfavorable for the corresponding unmodified counterparts. In order to probe any structural variations of the bithiophenes, following azobenzene isomerization, we used UV-Vis and nuclear magnetic resonance spectroscopy, and electronic structure computations.

(15) The absorption spectra of the 1.trans and 1.cis are the superposition of individual constituting components, namely the azobenzene, in its trans and cis form, and the phenylene-bithiophene segment. The absorption spectrum of 1.trans displays four distinguishable peaks: 454 nm, 363 nm, 284 nm and 245 nm (see FIG. 2a). The first two bands correspond to the typical S.sub.0.fwdarw.S.sub.1 and S.sub.0.fwdarw.S.sub.2 excitations represented respectively by the n??* and ???* transitions localized on the azobenzene. The peak centered at 284 nm is mainly the result of the S.sub.0.fwdarw.S.sub.1 excitation of the phenyl-functionalized bithiophene. In the framework of the molecular orbitals, this excitation can be describe as a HOMO.fwdarw.LUMO single particle transition involving the ? and ?* orbitals prevalently localized on the bithiophene. The last band at 245 nm, is the results of a high-energy electronic transition involving the it ???* orbitals localized on phenyl rings of the azobenzene. Upon irradiation at 350 nm around 86% of the trans isomer of azobenzene is converted to the cis form (see FIG. 2a).

(16) The resulting absorption spectrum, 1.cis, exhibits the typical signature of the azobenzene in its cis conformation, with a reduction of the oscillation strength for the it ???* transition (absorption intensity at 363 nm ?23%). However, no significant changes in the absorption profile were observed for the S0.fwdarw.S1 (n??*) transition. Conversely, bands at 284 nm and 245 nm exhibit a bathochromic shift of 13 nm and 11 nm, respectively (see FIG. 2a).

(17) Since the ?-conjugation extension of the bithiophene is directly correlated with the peak at 284 nm, any conformational change in its ?-bonds geometry will result in a spectral shift of this band. According to the spectral changes, the red-shift observed for this band is ascribable to a planarization of bithiophenic segment leading to a more efficient delocalization of its molecular orbitals along the two thiophene units. After the trans-to-cis isomerization of 1, it is possible to recover about ?55% of the initial trans isomer by irradiating at 254 nm (photostationary state (PSS), see FIG. 2a).

(18) The later wavelength was selected as an alternative excitation to the usual 430 nm due to the similar oscillator strengths of the n??* band for the two conformers. Monitoring the UV-Vis absorptions of 1 after many repeated alternating irradiation cycles at ?=350 nm and at ?=254 nm, respectively, did not result in any noticeable degradation of the compound, highlighting the robustness of the PTS architecture (see FIG. 2b). The recovery of the initial 1.trans conformer can also be obtained by thermal relaxation of the azobenzene moiety with a half-life (?.sub.1/2) of ca. 4.5 days at 25? C. (see FIG. 2c). Such long thermal stability is not common for unsubstituted alkoxy-azobenzene derivatives. Slow thermal relaxation is usually observed in azobenzenes that are functionalized in the ortho position with electron donating and withdrawing groups. The lack of electron directing functionality in the PTS azobenzene, and the faster thermal relaxation of its open precursor and pristine azobenzene suggest that the slow thermal relaxation of 1.cis can be associated to a reduced degree freedom in the isomerization motion.

(19) Finally, .sup.1H-NMR spectroscopy was conducted to investigate the rotation along the thiophene-thiophene bond on the isomerization of the azobenzene moiety. After the trans-to-cis isomerization of 1, the aromatic protons of thiophene H.sub.g (? 7.47 ppm) and H.sub.b (? 6.81 ppm) showed significant up-field shifts by 0.36 and 0.11 ppm, respectively (FIG. 3). On the other hand, aromatic signals of the phenylene of the linker, H.sub.i, H.sub.l and H.sub.h, observed respectively at 7.10, 6.36, and 6.28 ppm for 1.trans, showed downfield shifts by 0.17, 0.33, and 0.30 ppm, respectively. These spectral changes are reasonable given the different molecular geometry assumed by the two PTS conformers. In 1.trans, thiophene units assume a synclinal arrangement, orienting two phenyl fragments of the linker and azobenzene in a parallel-displaced conformation. Such arrangement leads to the lowering of the magnetic shielding effect in the thiophenes (downfield shift) while increasing that of the phenylenes due to ??? stack interactions (upfield shift). On the other end, when the azobenzene isomerizes to its cis form, the thiophenes assume a more planar conformation with concomitant edge-to-face arrangement with corresponding pseudo-orthogonal phenyl rings of the linker and azobenzene.

(20) This conformation results in an increase in the magnetic shielding of the thiophene protons (upfield shift), and a decrease in the shielding of the phenylene counterpart (downfield shift). The resulting .sup.1H-NMR spectral profile of 1.cis is in good agreement with bithiophene signature of the open analogue and with planarly constrained bithiophenes as previously reported. Hence, it can be concluded that compound 1 undergoes a rotation-like (twisted-planar) motion along the thiophene-thiophene bond upon trans-cis isomerization of the azobenzene switch. In conclusion, a novel molecular actuator has been designed capable of modulating the extension of its ?-conjugated backbone in response to light. The mechanical motion associated with the trans-cis isomerization of an azobenzene has been translated to a change in the planarity of the connected bithiophene, thus allowing for the dynamic tuning of its ?-conjugation. This provides a basis for the novel molecular actuators that can be used to tune the physical properties of extended ?-conjugated system. The the proposed PTS structure can be integrated into ?-conjugated oligomers and polymers, i.e. via the terminal ?-thiophene positions, can potentially lead to the next-generation of photochromic molecular materials with both photochromic and photoconductive behavior, and allow for the fabrication of novel light responsive optoelectronic devices.