WO2009010947A1

WO2009010947A1 - New donor-acceptor-donor-acceptor compounds for non-linear applications

Info

Publication number: WO2009010947A1
Application number: PCT/IL2007/000905
Authority: WO
Inventors: Andrew Shipway; Moshe Greenwald
Original assignee: Mempile Inc.
Priority date: 2007-07-18
Filing date: 2007-07-18
Publication date: 2009-01-22

Abstract

The present invention is directed to compounds having strong 2-photon absorbance for the manufacture of polymers suitable for various electro-optic applications.

Description

NEW DONOR-ACCEPTOR-DONOR-ACCEPTOR COMPOUNDS FOR NONLINEAR APPLICATIONS

FIELD OF THE INVENTION This invention relates to donor-acceptor-donor-acceptor (DADA) compounds for non-linear applications.

BACKGROUND OF THE INVENTION

The employment of compounds having strong 2-photon absorbance has been reported specifically with respect to the storage of data. The ever-growing need for the storage of large amounts of data brought about an evolution in the field. While three- dimensional data storage offers the possibility of holding terabytes of data on media similar in size to today's optical media (CD, DVD), in order to access the data points in the media 3D addressing is required. This can be achieved by one light beam or by the interaction of two or more light beams in the substance. As an example, two focused, crossing laser beams are able to define a specific point. In order to write data to the 3D media, there needs to be a chemical species within the media that is able to adopt two different forms.

Furthermore, this species must be switchable between the two forms by the multiple light interactions, and not by any of the light beams independently. In the past, such devices have been developed based on two-photon absorption by known photoisomerizable molecules. These molecules have low two-photon cross-sections, so relatively high-powered light sources are required, leading to expensive devices, slow data access, and danger of damage to the media.

US Patent No. 5,592,462 to Beldock et al, describes a three dimensional system for optical data storage and retrieval. According to this publication, the data is stored and retrieved by irradiating the storage medium with two interfering light beams, which allows the definition of a particular portion of the volume being written or read at every instance.

US Patent No. 5,268, 862 to Rentzepis et al., describes an active medium for use in a system of the kind describe by Beldock et al. The medium makes use of two forms of a spirobenzopyran derivative to represent the two binary states. However, the memory is maintained at a temperature lower than room temperature, typically at -78⁰C with the writing, storing of the written information and the reading thereof are all preformed at the low temperature. Raising the temperature erases the entire stored information, as one of the states is stable at room temperature for only 150 seconds.

International Publication no. WO 01/73^{^},779 describes the use of stilbene diethanol and substituted and non-substituted stilbene diethylacetate in a 3-D memory.

Stilbenes and bis-donor-disubstituted stilbenes in particular, have excited states that are characterized by strong charge-transfer from the donors to the central double bond. Resonance forms that can be drawn by "pushing electrons" for example in a diaminostilbene compound, such as the one shown below, give structures that correspond to predicted excited-states (Wang et al. J. Mater. Chem. (2001) 11_, 1600).

This charge transfer gives the molecule strong third-order nonlinear optical activity, since it causes a significant second harmonic component in the perturbance of the chromophore's electrons upon interaction with a fluctuating electric field. In addition, it should be noted that in the charge-transferred form, the central double-bond is weakened or does not exist. This observation explains the efficient photoisomerization of the molecule, and the reason for the increased isomerization with stronger charge-transfer donors. Applications that benefit from utilization of chromophores having strong 2- photon absorbance include optical limiting, data storage, 3D microfabrication and telecommunications. Chromophores having a general structural formula consisting of a "Donor-Acceptor-Donor" (DAD) structure such as those disclosed in International Publication no. WO 03/070,689, tend to have a strong 2-photon absorbance.

International Publication no. WO 06/07532 relates to diphenylstilbene compounds having improved 2-photon absorbance for non-linear applications.

SUMMARY OF THE INVENTION

The inventors of the present invention, have now suprisingly determiend that when extending the backbone of a stilbene derivative such as dimethoxy dicyano stilbene improved charge transfer properties, specifically those associated with 2-photon allowed transitions (S0→S2) may be achieved. Energy analysis of geometrically minimized coformations [B3LYP, 6-31G(d,p)] demonstarted the effcet, indicating that such compounds may be reagrded as improved systems for the use in 2-photon absorption processes.

The inventors have thus embarked on the development and synthesis of such extended compounds having emproved charge transfer properties for use in various in 2-photon absorption processes, compounds herein refered to as compounds (or isomers thereof) of the invention.

Thus, in one aspect of the present invention, there is provided a compound of the formula (I) or an isomer thereof:

wherein each of Q and M, independently of each other, is a two-ring fused conjugated system selected from:

and wherein Z₁ is a conjugated ring being fused to the phenyl ring P, said Z₁ being selected from a benzene or a Q-Cs-membered heteroaryl ring system, said heteroaryl ring system containing at least one heteroatom selected from N, O and S;

Q and M, independently of each other, being connected to the double bond via an atom vicinal to the fusing bond of the two-ring conjugated system, said Q and M, independently of each other, being optionally substituted by at least one donor group, e.g., D₁ and/or D₂ as detailed below;

X and Y, independently of each other, may be absent or a conjugating group selected from -Cs-Cio-arylene or heteroarylene having one or more heteroatoms selected from N, O and S; -C₂-C₄-alkenylene; -C₂-C₄-alkynylene; and -C₄-C₆-alkenylalkynylene; wherein each of -C₂-C₄-alkenylene, -C₂-C₄-alkynylene and -C₄-C₆-alkenylalkynylene, independently of each other, optionally having at least one of the carbon atoms replaced by at least one N atom;

X being substituted by at least one A₂; Y being substituted by at least one A₁; wherein said substitution by A₁ or A₂ may be along the Y or X chain and/or at the terminal positions; where Y is absent, A₁ is substituted on the double bond; and where X is absent, A₂ is substituted on the double bond; and each OfA₁ and A₂, independently of each other, is at least one acceptor group.

In one embodiment, in a compound of general formula (I) or an isomer thereof said Q and M are identical.

In another embodiment, said X and Y are identical.

In another embodiment, said X and Y are absent. As stated above, the substitution of A₁ or A₂ may be along the Y or X chain and/or at the terminal positions. For example, where Y is a -C₂-C₄-alkenylene such as -CH=CH-CH=CH-, A₁ may be substituted at the terminal position (one or both) as is the case in -CH=CH-CH=CH-A₁ and -CH=CH-CH=C-(AO₂ or along the chain replacing one or more of the hydrogen atoms, such as in -CH=CH-C(A₁)=CH- and -CH=C(A₁)- C(AO=CH-. A₁ may also be substituted on two or more such positions along the chain and/or at a terminal position, for example as

The groups A₁ may or may not be the same. As stated above, each of Q and M, independently of each other, is a two-ring fused conjugated system selected from:

with Z₁ being a conjugated ring fused to the phenyl ring P, and being selected from a benzene or a C₄-C₅-membered heteroaryl ring system. The "two-ring fused conjugated system" is a two-ring structure which is fully conjugated and may or may not contain a heteroatom such as N, O or S. The two rings, one of which being always a benzene ring, labeled P, and the other being either a benzene ring or a heteroaryl ring, as defined, share two atoms, preferably being carbon atoms. The bond between the two atoms shared by both rings is fusing bond of the two rings. When Z₁ is a benzene ring fused to ring P₅ the two-ring system is a naphthyl having position 1 as a point of connectivity to the double bond and the fused bond is between carbons 2 and 3 of ring P:

When Z₁ is a heteroaryl, e.g., pyridine, the two-ring system is, in general terms, a benzoheteroaryl, e.g., a quinolinyl or isoquinolinyl. The connectivity of the two-ring system, i.e., Q or M, to the central double bond may be via any atom of the Q or M system which is vicinal to the fusing bond of Q or M. When Q and/or M are each

Z₁ is always fused to ring P through carbons 2 and 3 (or at 5 and 6). When Q and/or M are each

the connectivity via Z₁ is at the atom immediately bonded to the carbons of the fusing bond (labeled with arrow).

Within the scope of the present invention, the term "heteroaryl" refers in its broadest definition to a monocyclic or multicyclic conjugated ring system of 4 to 9 carbon atoms with 1 to 3 heteroatoms, selected from N, O and S. Within the context of Z₁, the heteroaryl is a C₄-C₅ monocyclic conjugated ring, having at least one heteroatom selected from N, O and S, and being selected, in a non-limiting manner from furyl, imidazolyl, pyrimidinyl, thienyl, pyridyl, and pyrrolyl.

Thus, when Z₁ is a C₄-C₅-membered heteroaryl, the two-ring system Q and/or M may be selected, in a non-limiting manner, from indazolyl, indolyl, purinyl, benzopyrimidinyl, benzofuranyl, benzoimidazolyl, benzothienyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, benzoisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, and cinnolinyl.

In one embodiment, Z₁ is a substituted or unsubstituted benzene ring and thus each of Q and M is naphthyl, which may or may not be substituted. As stated above, in some embodiments, Q and/or M are each, independently of each other, substituted by at least one donor group D₁ and/or D₂. Thus, in some embodiments where Q and M are each naphthyl, the naphthyl may be substituted by at least one D₁ or D₂, wherein each of said D₁ and D₂, independently of each other, is a donor group.

As used herein, the term "donor group" refers in its broadest definition to an atom or a group of atoms which through either mesomeric or inductive mechanisms forces charge density away from itself along the bond which connects it to the central double bond.

In one embodiment, the donor group is selected in a non-limiting manner from

-Ci-Gj-alkyl; "OH; -SH; -[O,N,S]-Cj-C₄-alkyl; -[O,N,S]-C₁-C₄-alkylene-[O^I,S]-R or -OR, wherein R is a polymerizable residue; -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-CO- alkenylenealkylj -tO^^Sj-CrC^alkylene-tO^Sl-CO-alkylenealkene; -[0,N₅S]-C₁-C₄- alkylene-[O,N,S]-CO-polyene; -C₁-C₄-alkylene-[O,N,S]-C₁-C₄-alkyl; -NR¹R", wherein each of R' and R" is selected from hydrogen, -Ci-C^alkyl, -Cs-Cto-aryl or heteroaryl having at least one heteroatom selected from N, O and S.

The term "acceptor group" as used herein, in its broadest definition, refers to an atom or a group of atoms which through either mesomeric or inductive mechanisms brings electron density towards itself through the bond which connects it to the molecule's central double bond.

In one embodiemnt, the acceptor group is selected in a non-limiting manner from -CN; -NO₂; -C₆-C₁₀-aryl; -Cs-C_δ-heteroaryl, having at least one heteroatom selected from N₅ O and S; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, said heteroarylene having at least one N atom; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; and halides (Br, I, Cl, F).

Within the scope of the present invention, the following terms are defined as follows:

-"aiyl" refers to aromatic monocyclic or multicyclic groups containing from 6 to 10 carbon atoms. Aryl groups include, but are not limited to, groups such as unsubstituted or substituted phenyl and unsubstituted or substituted naphthyl. The term "arylene" refers to an aryl substituted at both ends or mid-chain substituted aryl.

-"heteroaryl" is as defined above. The term "heteroarylene" refers to a heteroaryl which is substituted at both ends or mid-chain substituted heteroaryl. ~"-C₂-C₄~alkenylene" refers to a straight or branched hydrocarbon group, having from 2 to 4 carbon atoms and at least one double bond. Alkenylene groups include for example -CH=CH-CH=CH-, -CH=CH-CH₂- and -CH=CH-.

-"-C₂-C₄~alkynylene" refers to a straight or branched hydrocarbon group, having from 2 to 4 carbon atoms and at least one triple bond. Alkynylene groups include, but are not limited to, -C≡C-C≡C-, -C≡C- and -C≡C-CH₂-.

-"-C_f-Cβ-alkenylalkynylene" refers to a straight or branched hydrocarbon group, having from 4 to 6 carbon atoms, at least one double bond and at least one triple bond. Alkenylalkynylene groups include, but are not limited to, -C≡C-C≡C-CH=CH₂-, -C≡C- CH=CH-CH₂-CH₂- and -C=C-CH₂-CH=CH₂-. -"-[O,N,S}-Ci-C₄-alkyl" refers to any one of-O-C₁-C₄-alkyl, -N-C₁-C₄-alkyl and

-S-Ci-C₄-alkyl, wherein the "-Ci-C^alkyV is a straight or branched aliphatic hydrocarbon group, having from 1 to 4 carbon atoms. -ⁿ-[O,N,S]-C_rC₄-alkylene-[O,N,S]-R" refers to any one of -O-CrQ-alkylene- O-R, -O-Ci-C^alkylene-N-R, -O-CrQ-alkylene-S-R, -N-C₁-C₄-alkylene-O-R, -N-C₁- C₄-alkylene-N-R, -N-C₁-C₄-alkylene-S-R, -S-C₁-C₄-alkylene-O-R₅ -S-C₁-C₄-alkylene- N-R, and -S-CrC₄-alkylene-S-R, wherein "-Cι-C₄-alkylene" is an aliphatic hydrocarbon group having between 1 and 4 carbon atoms. R is as defined. Non-limiting examples of such groups are: -0-CH₂-CH₂-S-R, =N-CH₂-CH₂-CH₂-O-R, -N=CH-CH₂- NH-R₅ and -N=CH-CH₂-N=R.

-"-[O^SJ-CrC^alkylene-lO^SJ-CO-alkenylenealkyr refers to any one of -O-C₁-C₄-alkylene-O-CO-alkenylenealkyl, -O-CrQ-alkylene-N-CO-alkenylenealkyl, -O-CrQ-alkylene-S-CO-alkenylenealkyl, -N-C₁-C₄-alkylene-O-CO-alkenylenealkyl, -N-C₁-C₄-alkylene-N-CO-alkenylenealkyl, -N-C₁-C₄-alkylene-S-CO-alkenylenealkyl, -S-Ci^-alkylene-O-CO-alkenylenealkyl, -S-CrC₄-alkylene-N-CO-alkenylenealkyl, and -S-C₁-C₄-alkylene-S-CO-alkenylenealkyl, wherein "-Ci-C₄-alkylene" is an aliphatic hydrocarbon group having between 1 and 4 carbon atoms and "-CO- alkenylenealkyl" refers to a carbonyl group (-C(=O)-) bonded to an alkenylenealkyl. The term "alkenylenealkyl" refers to a hydrocarbon having between 2 and 10 carbon atoms, at least one double bond connected to the carbonyl group and an end-of-chain alkyl. Non-limiting examples of such are -O-CH₂-CH₂-NH-CO-CH=CH-CH₃, and -0-CH₂-CH₂-NH-CO-CH=CH-CH=CH-CH₃. -"-[O,Η,S]-Ci-C₄-alkylene-[O^,S]-CO-alkylenealkene" refers to any one of

-O-C₁-C₄-alkylene-O-CO-alkylenealkene, -O-C₁-C₄-alkylene-N-CO-alkylenealkene, -O-C]_.-C₄-alkylene-S-CO-ahcylenealkene, -N-CrQ-alkylene-O-CO-alkylenealkene, -N-CrQ-alkylene-N-CO-alkylenealkene, -N-C₁-C₄-alkylene-S-CO-alkylenealkene, -S-C₁-C₄-alkylene-O-CO-alkylenealkene_> -S-C₁-C₄-alkylene-N-CO-alkylenealkene, and -S-Ci-Q-alkylene-S-CO-alkylenealkene, wherein "alkylene" is as defined above, "-CO-alkylenealkene" refers to a carbonyl group (-C(=O)-) bonded to an alkylenealkene. The term " alkylenealkene" refers to a hydrocarbon having between 2 and 10 carbon atoms, at least one end-of-chain double bond and an alkylene connected to the carbonyl group. Non-limiting examples of such are -0-CH₂-CH₂-NH-CO-CH₂- CH=CH₂, and -0-CH₂-CH₂-NH-CO-CH₂-CH₂-CH=CH₂.

-"-[ONSJ-Q-C^alkylene-fONSJ-CO-polyene" refers to a -[0,N^J-C₁-C₄- alkylene-[O,N,S]-CO- as defined above bonded to a polyene. The polyene is a hydrocarbon chain of 4 to 10 carbons having alternating double bonds. Non-limiting examples of such polyenes are -CH=CH-CH=CH-CH=CH₂, -CH=CH-CH=CH- CH=CH-CH=CH₂.

-"-d-C^alkylene-lONSJ-Ci-C^alkyl" refers to any one of -CrQ-alkylene-O- Ci-Gj-alkyl, -C₁-C₄-alkylene-N-C₁-C₄-alkyl, and -C₁-C₄-alkylene-S-C₁-C₄-alkyl, wherein said "alkylene" and "alkyl" are as defined before. -"halide" refers to any one of Br, I, Cl or F.

Within the context of the present invention, the term "polymerizable residue" refers to a group which is capable of undergoing polymerization under controlled conditions as may be known to a person skilled in the art. Non-limiting examples of such polymerizable residues or groups are isocyanates (such as -C₁-C₄ alkylene-NCO), epoxides (such as -C₁-C₄ alkylene-epoxide or -CO-epoxide), maleimides, styryls (such as -C₁-C₄ alkylene-CH=CH-phenyl) , acrylates and methacrylates as known to a person skilled in the art.

When a group is said of being substituted, unless otherwise indicated, there may be one or more substituents present.

As stated above concerning -C₂-C₄-alkenylene, -C₂-C₄-alkynylene, and -C₄-C₆- alkenylalkynylene, at least one of said carbon atoms may be optionally replaced by at least one N atom. Where applicable, the replacement may be of a carbon atom or a CH group. For example, a replacement of a carbon atom in a -C₂-C₄-alkenylene such as -CH=CH-CH=CH- may result in, e.g., -CH=N-CH=CH- or -N=CH-CH=CH- (replacement of a CH). Preferably, the replacement of one or more of the carbon atoms or a CH group is with the same number of nitrogen atoms, maintaining the number of atoms in the chain, and without affecting the conjugation along the chain.

In some embodiments of the present aspect of the invention, the compounds of general formula (I) are those having the structure of formula (II) or isomers thereof:

(H)

wherein X, Y, A₁, A₂, D₁ and D₂ are as defined above.

In one embodiment, in the compound of formula (II), each of X and Y, independently of each other, may be absent or selected from -C₂-C₄-alkenylene, optionally having at least one of the carbon atoms replaced by at least one N atom; and -C₂-C₄-alkynylene, optionally having at least one of the carbon atoms replaced by at least one N atom; each of A₁ and A₂, independently of each other, being substituted along the X or Y chain and/or at the terminal positions, is at least one acceptor group, as defined, preferably selected from -CN; -NO₂; and -Cs-Q-heteroaryl, having at least one heteroatom selected from N, O and S; and wherein each of said D₁ and D₂, independently of each other, is selected from -OC₁-C₄- alkyl, -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R, and -OR, wherein R is a polymerizable residue.

In one embodiment, each of Ai and A₂ is -CN, being substituted at the terminal atom of Y or X, respectively.

In another embodiment, each of D₁ and D₂, independently of each other, is selected from -OCi-C₄-alkyl, -[O,N,S]-CrC₄-alkylene-[O,N,S]-R and -OR, wherein R is a polymerizable residue.

The moieties D₁ and D₂, independently of each other, represent within the scope of the present invention at least one substituent on the respective Q and M rings, e.g, naphthyl rings. In other words, each of Q and M, e.g., the naphthyl rings, may be substituted with one or more OfD₁ or D₂. For example, the D^substituted naphthyl may be substituted with two or more D₁ groups, e.g., D^a), D₁(TD) and D₁(C), each of which may be the same or different. Similarly, the D₂-substituted naphthyl may be substituted with one or more D₂ groups. The at least one D₁ and at least one D₂ substituents, may be the same or different.

Additionally, the Di-substituted Q or M, e.g., naphthyl or benzoheteroaryl, may be substituted with a different number of D₁ substituents as compared to the D₂- substituted naphthyl. For example, the Di -substituted naphthyl may have a single Di substitution, e.g., Di(a), while the D₂-substituted naphthyl may have z number of D₂ substituents, e.g., D₂(a), D₂(b)... D₂(z). D₂(a), D₂(b)... and D₂(z) may or may not be the same. In some embodiments, D₁ is substituted at position 2 and/or 3 and/or 4 and /or 5 and/or 6 and/or 7 and/or 8 of the D^substituted naphthyl ring and D₂, independently of Di, is substituted at position 2' and/or 3' and/or 4' and/or 5' and/or 6' and/or 7' and/or 8 of the D₂-substituted naphthyl ring. In a specific embodiment, D₁ is substituted at position 2 or 3 or 4 or 5 or 6 or 7 or 8 of the Drsubstituted naphthyl ring and D₂, independently of D₁, is substituted at position 2' or 3' or 4' or 5' or 6' or T or 8' of the D₂-substituted naphthyl ring.

In one preferred embodiment, in a compound of formula (II), D₁ is substituted at position 5 of the Di-substituted naphthyl and D₂ is substituted at position 5" of the D₂- substituted naphthyl and the compound is of the formula (III) or an isomer thereof:

wherein X, Y₅ A₁, A₂, D₁ and D₂ are as defined above. In some embodiments of the formula (III), there are provided compounds wherein each of X and Y, independently of each other, may be absent or selected from -C₂-C₄-alkenylene, optionally having at least one of the carbon atoms replaced by at least one N atom; and -C₂-C₄-alkynylene, optionally having at least one of the carbon atoms replaced by at least one N atom; each of A₁ and A₂, independently of each other, is at least one acceptor moiety, as defined, preferably selected from -CN; -NO₂; -C₅-C₆- heteroaryl, having at least one heteroatom selected from N, O and S; and each of said D₁ and D₂, independently of each other, are selected from -OCi-Q-alkyl, -[0,N₅S]-C₁- C₄-alkylene-[O,N₅S]-R and -OR, wherein R is a polymerizable residue.

In one such embodiment, X and Y are both acetylene groups or are both absent. In another embodiment, independently of whether X and Y are both acetylene groups or are both absent, each OfA₁ and A₂ is -CN.

In still another embodiment, independently of whether X and Y are both acetylene groups or are both absent, and independently of whether each of A₁ and A₂ is -CN, D₁ and D₂, independently of each other, are selected from -OCrQ-alkyl, -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R, and -OR, wherein R is a polymerizable residue.

In another aspect of the present invention, there is provided a compound or an isomer thereof selected from:

(a) and (b)

wherein each of the L, L₁, L₂, and L₃, independently of each other, may be different, or same, and may be selected from H₅ -C^Q-alkyl; -C₁-C₄-alkylene-[O,N,S]- R, or -OR, wherein R is a polymerizable residue; -C₁-C4-alkylene-[O,N,S]-CO- alkenylenealkyU-Ci-C^alkylene-tO^^l-CO-alkylenealkene; -C₁-C₄-alkylene-[O,N,S]- CO-polyene; -Ci-C₄-alkylene-[0,N,S]-d-C₄-alkyl.

In one embodiment, each of L, L₁, L₂ and L₃ is different from H.

In another embodiment, each of L, L₁, L₂ and L₃ is selected from -C₁-C₄-alkyl.

In still another embodiment, each of L, L₁, L₂ and L₃ is selected from -CH₃, and -CH₂CH₃.

In another embodiment, the compound of general formula (I) is herein designated Compound 1 or an isomer thereof:

Compound 1

In another embodiment, the compound of general formula (I) is herein designated Compound 2 or an isomer thereof:

Compound 2

In another embodiment, in the compounds of formula (III) each of said D₁ and D₂, independently of each other, is -OR or a -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R, wherein R is a polymerizable residue, as defined hereinbefore. In one embodiment, each of the compounds of formula (III) is substituted by a single D₁ and D₂, one of which being -OR or a -[O,N₅S]-C₁-C₄-alkylene-[O,N,S]-R, and the second Of D₁ and D₂ being different from -OR or a -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R, wherein R is a polymerizable residue. Thus, the present invention further provides a compound or an isomer thereof selected from:

wherein one or both of L and L₁ is -C₁-C₄-alkylene-[O ,N₅S]-R or -OR; and one or both ofL₂ and L₃ is -Ci-C₄-alkylene-[O,N,S]-R or -OR; wherein R is a polymerizable residue selected from isocyanates, epoxides, maleimides, styryls, acrylates and methacrylates.

In another embodiment, the compound of general formula (I) is herein designated Compound 3 or an isomer thereof:

Compound 3

In another embodiment, the compound of general formula (I) is herein designated Compound 4 or an isomer thereof:

Compound 4

In another aspect of the present invention, there is provided a compound of the general formula (TV) or an isomer thereof:

wherein each Of R₁ to R₁₀, independently of each other, is H or a donor group as defined above; each of R₁ and R₂, R₂ and R₃, R₃ and R₄, R₄ and R₅, R₆ and R₇, R₇ and R₈, R₈ and R₉, and/or R₉ and R₁₀ together with the carbon atoms to which they are bonded may form a fused conjugated ring system, optionally containing at least one heteroatom selected from N, O and S; said fused conjugated ring system optionally being substituted by at least one H or at least one donor group as defined;

Gi, G₂, G₉ and Gi₀, independently of each other, may be selected from H, -CN; -NO₂; -Cs-C_δ-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆- Cϊo-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; and halide;

G₃, G₄, G₅, G₆, G₇, and G₈, independently of each other, may be selected from -CN; -NO₂; -Cs-Ce-heteroaryl, having at least one heteroatom selected from N, O and S; -Cβ-Cio-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; and halide; n and m are integers, each being independently equal to or greater than 0, provided that when G₁ or G₂ is H, both G₉ and G₁₀ are not H, and when G₉ or G₁₀ is H, both G₁ and G₂ are not H.

As stated, each Of R₁ and R₂, R₂ and R₃, R₃ and R₄, R₄ and R₅, R₆ and R₇, R₇ and R₈, R₈ and R₉, and/or R₉ and R₁₀ together with the carbon atoms to which they are bonded may form a fused conjugated ring system, optionally containing at least one heteroatom selected from N, O and S. Such fused ring systems, are preferably two-ring conjugated systems such as naphthyl, indazolyl, indolyl, purinyl, benzopyrimidinyl, benzofuranyl, benzoimidazolyl, benzothienyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, benzoisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, and cinnolinyl.

In one embodiment, n and m, independently of each other, are each 0, 1, 2, or 3; preferably 0 or 1.

In another embodiment, one of n and m is 0 or 1 and the other of n and m is 0. In yet another embodiment, n and m are each 0 or 1 and G₁, G₂, G₉ and G₁₀, independently of each other, are different from H.

In another embodiment, at least one Of R₁ to R₁₀ is not H and G₁, G₂, G₉ and G₁₀ are each, independently of each other, selected from -CN; -NO₂; -C₅-C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -C_δ-Qo-aryl; -C₅-C₆- heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁₀-arylene-C₂-C₄-alkenyl.

In another embodiment, the compound of general formula (IV) is a compound of formula (V) or an isomer thereof:

wherein said at least one R₁ to R₁₀ being different from H is selected from -C₁- C₄-alkyl; -OH; -SH; -[O,N,S]-Ci-C₄-alkyl; -[O,N₅S]-C₁-C₄-alkylene-[O,N,S]-R or -OR, wherein R is a polymerizable residue; -[O,N,S]-C₁-C₄-alkylene-[O,N.,S]-CO- alkenylenealkyl; -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-CO-alkylenealkene; -[0,N₅S]-C₁-C₄- alkylene-[O,N,S]-CO-polyene; -C₁-C₄-alkylene-[O,N,S]-C₁-C₄-alkyl; -NR'R", wherein each of R' and R" is selected from hydrogen, -CrC^alkyl, -C₅-C₁₀-aryl or heteroaryl having at least one heteroatom selected from N₅ O and S; G₁, G₂, G₉ and G₁₀ are each -CN; and G₃ and G₈ are as defined above. In one embodiment, in a compound of formula (V), at least two of R₁ to R₅ are different from H and at least one OfR₆ to R₁₀ is different from H.

In another embodiment, at least two of R₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

In still another embodiment, at least two OfR₁ to R₅ and at least two of R₆ to R₁₀ are different from H.

In another embodiment, the compound of formula (V) is a compound herein designated Compound 5 or an isomer thereof:

Compound 5

In another embodiment, the compound of formula (V) is a compound herein designated Compound 6 or an isomer thereof:

Compound 6

In another embodiment, the compound of formula (V) is a compound herein designated Compound 7 or an isomer thereof:

Compound 7

In another embodiment, the compound of formula (V) is a compound herein designated Compound 8 or an isomer thereof:

Compound 8

In one embodiment, in a compound of formula (V) the at least one of R₁ to R₁₀ being different from H is R₃ and Rg.

Accordingly, in an additional embodiment, a compound according to the formula (V) is a compound of formula (VI) or an isomer thereof:

wherein R₃, R₈, G₃ and G₈ are as defined above.

In one embodiment of a compound of formula (VI), G₃ and G₈ are each H and each of R₃ and R₈, independently of each other, is selected from -OC^Q-alkyl; -[O ,N,S]-C₁-C₄-alkylene-[O ,N₅S]-R and -OR, wherein R is a polymerizable residue.

In another embodiment, the compound of formula (VI) is a compound herein designated Compound 9 or an isomer thereof:

Compound 9

In another embodiment, the compound of formula (VI) is a compound herein designated Compound 10 or an isomer thereof:

Compound 10

In another embodiment of the general formula (IV), n and m are each 1 and Gi, G₂, G₉ and Gi o, independently of each other, are different from H. hi still another embodiment, at least one Of R₁ to R_1O is not H and Gi, G₂, G₉ and

Gi₀ are each, independently of each other, selected from -CN; -NO₂; -C₅~C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -Cβ-Cio-aryl; -C₅-C₆- heteroarylene-C2-C₄-alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁₀-arylene-C₂-C₄-alkenyl. In still another embodiment, the compound of general formula (IV) is a compound of the formula (VII) or an isomer thereof:

wherein said at least one Ri to R₁₀ being different from H is selected from -C₁- C₄-alkyl; -OH; -SH; -[O,N,S]-Ci-C₄-alkyl; -[O^.S]-Ci-C₄-al]-ylene-[O,N_sS]-R, wherein R is a polymerizable residue; -[O,N₅S]-C₁-C₄-alkylene-[O,N,S]-CO- alkenylenealkyl; -[O,N,S]-C₁-C₄-alkylene-[O₅N,S]-CO-alkylenealkene; -[O₅N₅S]-C₁-C₄- alkylene-[O₅N,S]-CO-polyene; -C₁-C₄-alkylene-[O,N₅S]-C₁-C₄-alkyl; -NR¹R", wherein each of R¹ and R" is selected from hydrogen, -Q-Q-alkyl, -C₅-C₁₀-aryl or heteroaryl having at least one heteroatom selected from N₅ O and S; G₁, G₂, G₉ and G₁₀ are each -CN; and each of G₃ to G₈, independently of each other, are as defined above.

In one embodiment, at least two OfR₁ to R₅ are different from H and at least one ofR₆ to R_1O is different from H.

In another embodiment, at least two OfR₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

In still another embodiment, at least two Of R₁ to R₅ and at least two of R₆ to R₁₀ are different from H.

In another embodiment, said at least one or R₁ to R₁₀ being different from H is R₃ and R₈.

In another embodiment, each of G₃ to G₈ is H and the compound of formula (VII) is a compound of formula (VTII) or an isomer thereof:

wherein R₃ and R₈, are as defined above. In another embodiment, the compound of formula (VIII) is a compound herein designated Compound 11 or an isomer thereof:

Compound 11

In another embodiment, the compound of formula (VIII) is a compound herein designated Compound 12 or an isomer thereof:

Compound 12

In another aspect of the present invention, there is provided a compound of the formula (IX) or an isomer thereof:

wherein each Of R₁ to R₁₀, independently of each other, is H or a donor group selected as defined above;

T₁ and T₂, independently of each other, may be selected from -CN; -NO₂; -C₅-

C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -Cβ-Cio-aryl;

-C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; -C₂-C₅-alkenylene-T; -C₂-C₅- alkynylene-T; wherein T is T₁ or T₂; n and m are integers, each being independently equal to or greater than 1, and provided that when n and m are each 1, at least two of R₁ to R₅ and/or at least two of R₆ to R_1O, independently of each other, are donor groups as defined above and the remaining of said R₁ to R₅ and said R₆ to R₁₀ are selected from H and a donor group selected as defined above.

In one embodiment, n and m, independently of each other, are each 1, 2, or 3. In another embodiment, one of n and m is 1 or 2 and the other of n and m is 1. In still another embodiment, n and m are each 1. In another embodiment, at least two of R₁ to R₅ and/or at least two of R₆ to R₁₀ are not H and T₁ and T₂ are each, independently of each other, selected from -CN; -NO₂; -C₅-C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆- C₁₀-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁o-arylene-C₂-C₄-alkenyl. In another embodiment, said T₁ and T₂ are -CN.

In another embodiment, the compound of general formula (IX) is a compound of formula (X) or an isomer thereof:

wherein at least two of R₁ to R5 and/or at least two of R6 to R₁₀ are different from H.

In one embodiment, at least two OfR₁ to R₅ are different from H and at least one ofR₆ to R_1O is different from H. In another embodiment, at least two of R₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

In still another embodiment, at least two OfR₁ to R₅ and at least two OfR₆ to R₁₀ are different from H.

In yet another embodiment, said at least one OfR₁ to R₁₀ being different from H, is selected from R₃ and R₄, R₃ and R₂, R₈ and R₉, and R₈ and R₇.

In another embodiment, the compound of formula (X) is a compound herein designated Compound 13 or an isomer thereof:

Compound 13 In another embodiment, the compound of formula (X) is a compound herein designated Compound 14 or an isomer thereof:

Compound 14

In another embodiment, the compound of formula (X) is a compound herein designated Compound 15 or an isomer thereof:

Compound 15

As may be known to a person skilled in the art, the compounds of the invention have each a double bond which may exist as a cis, trans, E ox Z isomer or mixtures thereof. Thus, within the scope of the present invention, the term "isomer" refers to such cis, trans, E ox Z isomers as are known to a person skilled in the art. It is to be understood that, notwithstanding, the compounds provided herein may contain chiral centers. Such chiral centers may be of either the (R) or (S) configuration, or may be a mixture thereof. Thus, the compounds provided herein may be enantiomerically pure, or be stereoisomeric or diastereomeric mixtures.

Any compound disclosed or claimed in WO 03/070,689 and WO 06/07532 in their entirety, either by chemical name or otherwise known designation, by its structural formula, by a broader generic formula, by a reference, directly or indirectly, are hereby disclaimed.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of formulae (I) to (X) may be prepared by several general routes, the one being chosen depending on the particular reactivity of the specific groups, and the availability and cost of suitable synthons. Protecting group chemistry may be required in some cases in order to allow the key reactions to take place in the presence of the donor and/or acceptor groups. In such cases, suitable protecting group chemistry can be found in "Protective Groups in Organic Synthesis" (T. W. Greene and P.G.M. Wuts, Wiley, ISBN 0-471-1601-9).

The following synthetic schemes illustrate general synthetic paths which are suitable in order to obtain compounds of the invention:

1) McMurry coupling:

Scheme 1 Compounds of the invention can be prepared following the route illustrated in

Scheme 1. McMurry coupling between substituted ketones provides the conjugated system of the compounds of the invention. Groups substituted on the Q and M moieties (typically donor groups as defined above), may optionally be protected using conventional known protecting groups known in the art, which can later be de-protected to give the corresponding donor group.

For McMurry reaction conditions, see for example Mukaiyama et al., Chem. Lett. (1973), 1041; Lenoir, Synthesis, (1977), 553; Lenoir and Burghard, J Chem. Res. (S) (1980), 396; McMurry, Chem. Rev. (1989), 89, 1513-1524; McMurry, Ace. Chem. Res. (1983) 16, 405-511; and S. Gauthier et al., J Org. Chem., (1996), 61, 3890-3893.

For an example of the synthesis of analogous of the compounds of the invention, see CW. Spangler, T. Faircloth, E.H. Elandaloussi, B. Reeves, Mat. Res. Soc. Symp. Proc. 488 (1998) 283-289.

Ketone starting materials are either commercially available or may be prepared by synthetic methods appreciated by those skilled in the art e.g., by the Friedel-Crafts reactions of a suitable Q with A₁-X-C(O)Cl.

In accordance, Compound 1 of the invention may be prepared as shown in Scheme 2, by reacting two equivalents of the corresponding cyano ketone under McMurry reaction conditions such as those specified below:

ϊound 1

Scheme 2 2) Pinacol coupling:

Scheme 3

The compounds of the invention may also be prepared using the two-step sequence as shown in Scheme 3. The pinacol coupling of ketones provides the vicinal diol which can be transformed to the olefin end product using the deoxygenation conditions that are well documented in the art.

For Pinacol coupling reactions, see T. Wirth et al. Angew. Chem. Int. Ed. Engl. (1996), 35, 61, X. Xu et al. J Org. Chem. (2005), 70, 8594 and leading references cited therein and for olefin synthesis by deoxygenation conditions, see E. Block in Organic Reactions (1984), 30, 457.

For example, compounds of general formula (IV), of the invention may be obtained by reacting two different ketones, as shown in Scheme 4 below, under pinacol coupling reaction conditions and producing at the first stage a mixture of symmetric and asymmetric diol compounds which under deoxygenation generate a mixture of symmetric and assymetric conjugated end products from which there may be separated the desired compounds of the invention: g

deoxygenation

Scheme 4 3) Suzuki coupling:

Scheme 5

Suzuki methodology [A. Suzuki, Pure Appϊ. Chem. 63 (1991) 419-422] relates to the palladium-catalysed cross coupling between organoboronic acid and halides. The broadening of the method made it possible to use this reaction beyond aryl compounds and thus may also include alkyls, alkenyls and alkynyls. Potassium trifluoroborates and organoboranes or boronate esters may be used in place of boronic acids. Some pseudohalides (e.g., triflates) may also be used as coupling partners.

Within the scope of the present invention, this synthetic procedure, briefly demonstrated in Scheme 5 above, may be used to attach the required Q and M aromatic groups to the acceptor system. In this case, the substituted unsaturated system may be synthesized first, which may be achieved by standard methods of synthesis of such polyunsaturated molecules, as known to the versed in the art.

The dibromo intermediate can be prepared from the corresponding ketone using for example the procedure reported by Corey and Fuchs (see EJ. Corey and P. L. Fuchs, Tetrahedron Lett. (1972), 3769, herein incorporated by reference). Alternatively, the dibromo compound can also be prepared using the procedure reported by V.G.Nenajdenko, et al J.Chem.Soc, Perkin Trans. I, (2002), 883, J.F.Normant et al Synthesis (2000), 109.

Dibromo alkenes can be coupled with a variety of aryl boronic acids using Suzuki reaction conditions or any metal mediated carbon-carbon bond forming reactions to afford the conjugated compound of the invention. For general Suzuki coupling reaction conditions, see, Miyaura, N., Suzuki, A. Chem. Rev. (1995), 95, 2457- 2483; Suzuki, A., J. Organometallic Chem. (1999), 576, 147-168; and Suzuki, A. in Metal- catalyzed Cross-coupling Reactions, Diederich, F., and Stang, P. J., Eds.; Wiley- VCH: New York, (1998), pp. 49-97. For Suzuki coupling reaction conditions of 1,1- dibromo-1-alkene, see M.W. Miller et al., Syn. Lett (2001), 254. The dibromo alkene can also be transformed to the corresponding diboryl intermediate, which upon reaction with aryl halides can generate conjugated compound of formula I. For related transformations, see M. Shimizu et al., J. Am. Chem, Soc, (2005), 127, 12506.

Compound 13 of the invention may, for example, be prepared from the appropriate di-bromo reactant which is treated with two equivalents of the acetylcyano boronic acid in the presence of the palladium catalyst under the Suzuki reaction conditions as specified in Scheme 6 below:

Scheme 6 4) Basic oxidative coupling:

Scheme 7

The oxidative coupling of compounds, taking advantage of the acidity of the CH₂ protons, may be accomplished as shown in Schemes 7 and 8 by the cold addition of NaOMe to an etheric solution of the starting material and molecular iodine. Both symmetrical and asymmetric compounds may be produced.

Such oxidative coupling reactions may also be controlled by heterogeneous catalysts. Suitable catalysts include, but are not limited to, PbO/MgO, lanthanide oxides, mixtures of lanthanide oxides, Ca(LVCeO₂, metal oxides, combinations of Group I-III oxides and metal oxides such as CaOyMnO₂, CaOZCr₂O₃, CaO/ZnO, combinations of metal oxides, multi-component metal oxide catalysts, supported metal oxides as described earlier such as SiO₂/Cr₂O₃, certain non metal oxides, certain non-oxide metals and combinations thereof.

Scheme 8

5) Addition of acceptor groups to stilbene-type molecules via addition- elimination sequence

Scheme 9

Compounds of the invention may also be synthesized, as shown in Scheme 9, by the addition of the acceptor groups to the pre-formed substituted diarylethene molecule, or analogs substituted on the double bond. Compound 1 may be prepared also via a sequence of reactions as shown below in Scheme 10:

Compound 1

Scheme 10 Compound 9 may be prepared according to Scheme 11 shown below:

Compound 9

Scheme 11

It should be noted that the synthetic procedures described herein for the production of a conjugated system with a double bond backbone may produce either the cw or trans (or E or Z) configurations of the double bond or any mixtures thereof. It is possible to photoisomerize the cis (or Z) isomers to the desirable trans (or E) isomers which are typically more thermodynamically stable due to the relative reduction in steric hindrance. Compounds of the invention having at least one polymerizable residue appended thereto may be used as monomers in the synthesis of polymers. Thus, the present invention further provides monomers useful in the synthesis of various polymers such as homopolymers and copolymers. The monomers of the invention may be organized along the polymeric backbone regularly with alternating monomer residues, in a repeating sequence, in a random sequence of monomer residue types, according to a known statistical rule, as block copolymers having two or more subunits linked by covalent bonds or as core-shell polymers. Thus, the present invention further provides polymers made of or incorporated with one or more monomers of the present invention, said polymers may be homopolymers, copolymers, alternating copolymers, periodic copolymers, random copolymers, statistical copolymers, block copolymers, graft copolymers, and core-shell polymers.

The polymers of the invention may be prepared according to known methods, such as cationic, anionic, free-radical and condensation polymerization.

The characterization of polymers of the invention may be achieved by methods known to a person skilled in the art. Such methods may for example be wide angle X- ray scattering, small angle X-ray scattering, and small angle neutron scattering for determining the crystalline structure of polymers; gel permiation chromatography for determining the number avergae molecular weight, weight average molecular weight and polydispersity; FTIR, Raman and NMR for determening composition; and differential scattering calorimetry (DSC) and dynamic mechanical analysis for determining thermal properties such as glass transition temperature and melting point.

The polymers of the invention may be used for a variety of uses in nonlinear optics, for example as specialty dyes, reference standards, optical limiters, as components in microfabriation systems, for nano-technological devices, and for targeted medical therapeutic applications. In particular, these compounds may be used as the active medium of a 3- dimensional optical memory.

The present invention is further directed to devices or formulations comprising any one of the compounds of the invention. Examples are specialty dyes, reference standards, optical limiters, microfabriation systems, nanotechnological devices, devices or pharmaceutical compositions for use in targeted medical therapeutic applications. In particular, provided are 3 -dimensional optical memory devices comprising the compounds of the invention.

The compounds of the present invention may be utilized in applications requiring improved 2-photon absorption. One example of an application for these materials is data storage, where the compounds of the present invention may serve as more efficient switchable chromophores for data storage such as the 3 -dimensional optical data storage disclosed in WO 01/73,769 and WO 03/070,689. It is also noted that the fluorescence of these molecules tends to be highly dependant on their microenvironment, and so they may also be utilized as viscosity sensors.

The compounds of the present invention may be part of an active medium suitable for storing and retrieving data. The basis of the 3 -dimensional memory is the interaction of the compounds with incident light to interconvert the active compounds from one chemical structure to a different chemical structure. The active compounds may be regarded as chromophores.

In a 3- dimensional memory, each chemical structure represents a different mode, such as for illustration, '0' and '1' in a binary representation. The different chemical structures may be two separate geometric forms, i.e. cis and trans. An active medium should thus be understood as a plurality of molecules bound to a polymer confined within a given volume or a plurality of molecules that form part of the polymer that are capable of changing their states from one isomeric form to another upon an interaction with light. Upon irradiating a medium comprising the compounds of the invention with an appropriate radiation, whether the compounds (embedded within, bonded to, or part of the backbone of a polymer matrix) are in the cis or the trans geometry, may interconvert from one geometric structure to the other. Such a transition in the medium is the "writing" process on the memory medium. The 3-dimensional memory may be of a type of "write once" or a rewriteable memory. A precise control of each desirable type of memory may be obtained since the chemical structure of the memory-active compounds of the invention dictates its nature. For the case of cis-trans geometric forms, the chemical nature of the substituents on the double bond dictate different stability of each isomeric form and also ease or difficulty in "writing". Thus, by choosing the appropriate active compound, the nature of the memory, whether a "write once" or rewriteable memory may be controlled.

The binding to the polymer of the compounds of the invention, results in a well- structured 3-D memory. The polymer further gives physical support and durability to the memory. The chemical and physical properties of the resulting polymer vary and depend on the various active compounds (chromophores), additives and reaction parameters in the polymerization reaction. Temperature gradient, pressure, initiator, duration of polymerization and addition of plasticizer (s) or additional polymers enable a precise control of the desired polymer. In particular, it should be understood that the compounds of the invention are actually photoisomerizable donor-acceptor-donor-acceptor (DADA) molecules, which can be interconverted between isomerization states by two-photon absorption. Stilbene itself is already known to have a high two-photon cross-section but still requires substantial effort to photointerconvert its two isomers. In order to increase its nonlinear absorption characteristics, acceptor groups such as nitrile groups are attached to its central double bond (making a good acceptor), and various numbers of alkoxy or other donor groups to the phenyl, naphthyl or conjugated rings.

Claims

CLAIMS:

1. A compound of general formula (I) or an isomer thereof:

Z₁ is a conjugated ring being fused to the phenyl ring P, said Z₁ being selected from a benzene or a C₄-C₅-membered heteroaryl ring system containing at least one heteroatom selected from N, O and S; each of Q and M, independently, is connected to the double bond via an atom vicinal to the fusing bond of the two rings of the conjugated fused system, said Q and M, independently of each other, being optionally substituted by at least one donor group;

X and Y, independently of each other, is absent or a conjugating group selected from -C₅-C₁₀-arylene or heteroarylene having one or more heteroatom selected from N, O and S; -C₂-C₄-alkenylene; -C₂-C₄-alkynylene; and -C₄-C₆-alkenylalkynylene; wherein each of -C₂-C₄-alkenylene, -C₂-C₄-alkynylene and -C₄-C₆-alkenylalkynylene, independently of each other, optionally having at least one of the carbon atoms replaced by at least one N atom;

X being substituted by at least one A₂; Y being substituted by at least one A₁; wherein said substitution by A₁ or A₂ is along the Y or X chain and/or at the terminal positions; where Y is absent, A₁ is substituted on the double bond; and where X is absent, A₂ is substituted on the double bond; and each OfA₁ and A₂, independently of each other, is at least one acceptor group.

2. The compound according to claim 1, wherein said Q and M are identical.

3. The compound according to claim 1 or 2, wherein X and Y are identical.

4. The compound according to claim 1 or 2, wherein X and Y are absent.

5. The compound of any one of claims 1 to 4, wherein Z₁ is a benzene ring.

6. The compound according to claim 5, wherein said Q and M, independently of each other are substituted or unsubstituted naphthyls.

7. The compound of any one of claims 1 to 4, wherein Z₁ is a C₄-C₅ monocyclic heteroaryl, having at least one heteroatom selected from N, O and S.

8. The compound according to claim 7, wherein said heteroaryl is selected from furyl, imidazolyl, pyrimidinyl, thienyl, pyridyl, and pyrrolyl.

9. The compound according to claim 8, wherein Q and M are each independently selected from indazolyl, indolyl, purinyl, benzopyrimidinyl, benzofuranyl, benzoimidazolyl, benzothienyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, benzoisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, and cinnolinyl.

10. The compound according to any one of claims 1 to 9, wherein said Q and M, independently of each other, are substituted by at least one D₁ and D₂, each being selected from -Ci-C₄-alkyl; -OH; -SH; -[O,N,S]-C_rC₄-alkyl; -[O,N,S]-Ci-C₄-alkylene- [0,N₅S]-R, -OR, wherein R is a polymerizable residue; -[O,N,S]-Ci-C₄-alkylene- [O,N,S]-CO-alkenylenealkyl, -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-CO-alkylenealkene₃ -[O,N,S]-C₁-C₄-alkylene-[O,N₅S]-CO-polyene, -C₁-C₄-alkylene-[O,N,S]-C₁-C₄-alkyl and -NR¹R", wherein each of R¹ and R" is selected from hydrogen, -C₁-C₄-alkyl, -C₅- C₁₀-aryl and heteroaryl having at least one heteroatom selected from N, O and S.

11. The compound according to claim 1, wherein said A₁ and A₂, independently of each other, are acceptor groups selected from -CN, -NO₂, -C_δ-Qo-aryl, -C₅-C₆- heteroaryl, having at least one heteroatom selected from N, O and S, -C₅-C₆- heteroarylene-C₂-C₄-alkenyl, said heteroarylene having at least one N atom, -C₆-C₁₀- arylene-C₂-C₄-aIkenyl, -arylene-N₂-aryl and halides.

12. The compound according to claim 10, wherein said polymerizable residue is selected from isocyanates, epoxides, maleimides, styryls, acrylates and methacrylates.

13. A compound according to claim 1, having the structure of formula (II) or an isomer thereof:

wherein X, Y, A₁, and A₂ are as defined in claim 1 and D₁ and D₂ are as defined in claim 10.

14. The compound according to claim 13, wherein each of X and Y, independently of each other, is absent or selected from -C₂-C₄-alkenylene₅ optionally having at least one of the carbon atoms replaced by at least one N atom; and -C₂-C₄-alkynylene, optionally having at least one of the carbon atoms replaced by at least one N atom; each of A₁ and A₂, independently of each other is at least one group selected from -CN; -NO₂; and -Cs-Cβ-heteroaryl having at least one heteroatom selected from N, O and S; and wherein each of said D₁ and D₂, independently of each other, is selected from -OC₁- C₄-alkyl, -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R, and -OR, wherein R is a polymerizable residue.

15. The compound according to any one claims 13 or 14, wherein each OfA₁ and A₂ is -CN, being substituted at the terminal atom of Y or X, respectively.

16. The compound according to any one of claims 13 to 15, wherein each Of D₁ and D₂, independently of each other, is selected from -OQ-Q-alkyl, -[0,N₅S]-C₁-C₄- alkylene-[O ,N₅S]-R and -OR₅ wherein R is a polymerizable residue.

17. The compound according to any one of claims 13 to 16, wherein D₁ is substituted at position 2 or 3 or 4 or 5 or 6 or 7 or 8 of the Di-substituted naphthyl ring and D₂, independently Of D₁, is substituted at position 2' or 3' or 4' or 5' or 6' or T or 8' of the D₂-substituted naphthyl ring.

18. The compound according to claim 17, wherein D₁ is substituted at position 5 of the D₁ -substituted naphthyl and D₂ is substituted at position 5" of the D₂-substituted naphthyl.

19. The compound according to claim 18 being of the formula (III) or an isomer thereof:

wherein X, Y, A₁ and A₂ are as defined in claim 1 and D₁ and D₂ are as defined in claim 10.

20. The compound according to claim 19, wherein each of X and Y, independently of each other, is absent or selected from -C₂-C₄-alkenylene, optionally having at least one of the carbon atoms replaced by at least one N atom; and -C₂-C₄-alkynylene, optionally having at least one of the carbon atoms replaced by at least one N atom; each of A₁ and A₂, independently of each other, is at least one group selected from -CN; -NO₂; and -C₅-C₆- heteroaryl, having at least one heteroatom selected from N, O and S; and each of said D₁ and D₂, independently of each other, are selected from -OC₁-C₄- alkyl, -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-R and -OR, wherein R is a polymerizable residue.

21. The compound according to claim 19 or 20, wherein X and Y are both acetylene groups or are both absent.

22. The compound according to any one of claims 19 to 21, wherein each Of A₁ and A₂ is -CN.

23. The compound according to any one of claims 19 to 22, wherein D₁ and D₂, independently of each other, are selected from -OC₁-C₄-alkyl, -[O,N,S]-C₁-C₄-alkylene-

[O₅N₅S]-R, and -OR, wherein R is a polymerizable residue.

24. The compound or an isomer thereof according to any one of the preceding claims being selected from:

wherein each of L, L₁, L₂, and L₃, independently of each other, is different or same, and is selected from H, -Q-C^alkyl; -Ci-C₄-alkylene-[O,N,S]-R, or -OR, wherein R is a polymerizable residue; -C₁-C₄-alkylene-[O,N,S]-CO-alkenylenealkyl; -C₁-C₄-alkylene-[O,N,S]-CO-alkylenealkene; -C₁-C₄-alkylene-[O,N,S]-CO-polyene; and -C₁-C₄-alkylene-[O₅N,S]-C₁-C₄-alkyl.

25. The compound according to claim 24, wherein each of L, L₁, L₂ and L₃ is different from H.

26. The compound according to claim 24 or 25, wherein each of L, L₁, L₂ and L₃ is a -Q-Q-alkyl.

27. The compound according to claim 26, wherein said -Ci-C₄-alkyl is selected from -CH₃, and -CH₂CH₃.

28. The compound of an isomer thereof:

29. The compound or an isomer thereof:

30. The compound or an isomer thereof:

31. The compound or an isomer thereof:

32. A compound of the general formula (IV) or an isomer thereof:

wherein each OfR₁ to R₁₀, independently of each other, is H or a donor group; each of R₁ and R₂, R₂ and R₃, R₃ and R₄, R₄ and R₅, R₆ and R₇, R₇ and Rg, R₈ and R₉, and/or R₉ and R₁₀ together with the carbon atoms to which they are bonded optionally form a fused conjugated ring system, optionally containing at least one heteroatom selected from N, O and S; said fused conjugated ring system optionally being substituted by at least one H or at least one donor group; G₁, G₂, G₉ and G₁₀, independently of each other, are selected from H, -CN;

-NO₂; -Cs-Ce-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆- C₁₀-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; and halide;

G₃, G₄, G₅, G₆, G₇, and Gg, independently of each other, are selected from -CN; -NO₂; -Cs-Co-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆- C₁₀-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁o-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; and halide; n and m are independently equal to or greater than 0, provided that when G₁ or G₂ is H, both G₉ and G₁₀ are not H₅ and when G₉ or G₁₀ is H, both G₁ and G₂ are not H.

33. The compound according to claim 32, wherein said fused ring system is a two- ring conjugated system.

34. The compound according to claim 33, wherein said two-ring conjugated system is selected from naphthyl, indazolyl, indolyl, purinyl, benzopyrimidinyl, benzofuranyl, benzoimidazolyl, benzothienyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, benzoisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, and cinnolinyl.

35. The compound according to any one of claims 32 to 34, wherein n and m, independently of each other, are each 0, 1, 2, or 3.

36. The compound according to claim 35, wherein n and m are each independently 0 or l.

37. , The compound according to claim 36, wherein one of n and m is 0 or 1 and the other of n and m is 0.

38. The compound according to any one of claims 32 to 37, wherein G₁, G₂, G₉ and G₁₀, independently of each other, are different from H.

39. The compound according to any one of claims 32 to 38, wherein at least one of R₁ to R_1O is different from H and G₁, G₂, G₉ and G₁₀ are each, independently of each other, selected from -CN; -NO₂; -C₅-C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-aryl; -C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁o-arylene-C₂-C₄-aIkenyl.

40. The compound according to claim 39, having the structural formula (V) or an isomer thereof:

wherein said at least one R₁ to R₁₀ being different from H is selected from -C₁- C₄-alkyl; -OH; -SH; -[O^SJ-d-Q-alkyl; -[O^Sl-Q-Gralkylene-tO^Sl-R or -OR, wherein R is a polymerizable residue; -[OjN_jSl-CrC^alkylene-fO^jSl-CO- alkenylenealkyl; -[O,N₅S]-C₁-C₄-alkylene-[O,N₃S]-CO-alkylenealkene; -[0,N₅S]-C₁-C₄- alkylene-[O,N,S]-CO-polyene; -C₁-C₄-alkylene-[O,N,S]-C₁-C₄-alkyl; -NR¹R", wherein each of R' and R" is selected from hydrogen, -Q-d-alkyl, and -Cs-Qo-aryl or heteroaryl having at least one heteroatom selected from N, O and S; G₁, G₂, G₉ and G₁₀ are each -CN; and G₃ and G₈ are as defined in claim 32.

41. The compound according to claim 40, wherein at least two of R₁ to R₅ are different from H and at least one OfR₆ to R₁₀ is different from H.

42. The compound according to claim 40 or 41, wherein at least two of R₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

43. The compound according to any one of claims 40 to 42, wherein at least two of R₁ to R₅ and at least two of R₆ to R₁₀ are different from H.

44. The compound or an isomer thereof:

45. The compound or an isomer thereof:

46. The compound or an isomer thereof:

47. The compound or an isomer thereof:

48. The compound according to claim 40, wherein at least one of R₁ to R₁₀ being different from H is R₃ and R₈.

49. The compound according to claim 40, having the structural formula (VI) or an isomer thereof:

wherein R₃, Rg, G₃ and G₈ are as defined in claim 40.

50. The compound according to claim 49, wherein G₃ and G₈ are each H and each of R₃ and R₈, independently of each other, is selected from -OC₁-C₄-alkyl; -[0,N₃S]-C₁- C₄-alkylene-[O,N,S]-R and -OR, wherein R is a polymerizable residue.

51. The compound or an isomer thereof:

52. The compound or an isomer thereof:

53. The compound according to claim 32, wherein n and m are each 1 and G₁, G₂, G₉ and G₁₀, independently of each other, are different from H.

54. The compound according to claim 32, wherein at least one of R₁ to R₁₀ is different than H and G₁, G₂, G₉ and G₁₀ are each, independently of each other, selected from -CN; -NO₂; -C₅-C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-aryl; -Cs-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁₀-arylene-C₂-C₄-alkenyl.

55. The compound according to claim 54, having the structural formula (VII) or an isomer thereof:

wherein said at least one R₁ to R₁₀ being different from H is selected from -C₁- C₄-alkyl; -OH; -SH; -[O₅N,S]-C₁-C₄-alkyl; -[O^Sl-Q-Q-alkylene-tO^SJ-R, wherein R is a polymerizable residue; -[O,N,S]-C₁-C₄-alkylene-[O,N,S]-CO- alkenylenealkyU -tO^SJ-CrCralkylene-tO^^J-CO-alkylenealkene; -[0,N₅S]-C₁-C₄- alkylene-[O,N,S]-CO-polyene; -C₁-C₄-alkylene-[O₅N,S]-C₁-C₄-alkyl; -NR'R", wherein each of R' and R" is selected from hydrogen, -Q-Q-alkyl, -C₅-C₁₀-aryl or heteroaryl having at least one heteroatom selected from N, O and S; G₁, G₂, G₉ and G₁₀ are each -CN; and each of G₃ to G₈, independently of each other, are as defined in claim 32.

56. The compound according to claim 55, wherein at least two of R₁ to R₅ are different from H and at least one OfR₆ to R₁₀ is different from H.

57. The compound according to claims 55, wherein at least two of R₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

58. The compound according to claim 55, wherein at least two of R₁ to R₅ and at least two OfR₆ to R₁₀ are different from H.

59. The compound according to claim 55, wherein at least one or R₁ to R₁₀ being different from H is R₃ and R₈.

60. The compound according to any one of claims 55 to 59, wherein each of G₃ to G₈ is H.

61. The compound according to claim 60 having the structural formula (VIII) or an isomer thereof:

wherein R₃ and R₈, are as defined in claim 32.

62. The compound or an isomer thereof:

63. The compound or an isomer thereof:

64. A compound of the formula (IX) or an isomer thereof:

wherein each OfR₁ to R₁₀, independently of each other, is H or a donor group; T₁ and T₂, independently of each other, may be selected from -CN; -NO₂; -C₅-

C₆-heteroaryl, having at least one heteroatom selected from N₃ O and S; -Cδ-Qo-aryl;

-C₅-C₆-heteroarylene-C₂-C₄-alkenyl, having at least one heteroatom selected from N, O and S; -C₆-C₁₀-arylene-C₂-C₄-alkenyl; -arylene-N₂-aryl; -C₂-C₅-alkenylene-T; -C₂-C₅- alkynylene-T; wherein T is T₁ or T₂; n and m are integers, each being independently equal to or greater than 1, and provided that when n and m are each I₅ at least two of R₁ to R₅ and/or at least two of R₆ to R₁₀, independently of each other, are donor groups and the remaining of said R₁ to R₅ and said R₆ to R₁₀ are selected from H and a donor group.

65. The compound according to claim 64, wherein n and m, independently of each other, are each 1, 2, or 3.

66. The compound according to claim 65, wherein one of n and m is 1 or 2 and the other of n and m is 1.

67. The compound according to claim 66, wherein n and m are each 1.

68. The compound according to any one of claims 64 to 67, wherein at least two of Ri to R₅ and/or at least two of R₆ to Ri₀ are not H and Ti and T₂ are each, independently of each other, selected from -CN; -NO₂; -C₅-C₆-heteroaryl, having at least one heteroatom selected from N, O and S; -C₆-Cio-aryl; -C₅-C₆-heteroarylene-C₂-C₄- alkenyl, having at least one heteroatom selected from N, O and S; and -C₆-C₁₀-arylene- C₂-C₄-alkenyl.

69. The compound according to claim 68, wherein said Ti and T₂ are -CN.

70. The compound according to claim 69, having the structural formula (X) or an isomer thereof:

wherein at least two Of R₁ to R₅ and at least two of R₆ to R₁₀ are different from

H.

71. The compound according to claim 70, wherein at least two of R₁ to R₅ are different from H and at least one OfR₆ to R₁₀ is different from H.

72. The compound according to claim 70, wherein at least two of R₆ to R₁₀ are different from H and at least one OfR₁ to R₅ is different from H.

73. The compound according to claim 70, wherein at least two of R₁ to R₅ and at least two OfR₆ to R₁₀ are different from H.

74. The compound according to claim 70, wherein said at least one of Ri to Rjo being different from H, is selected from R₃ and R₄, R₃ and R₂, R₈ and R₉, and R₈ and R₇.

75. The compound or an isomer thereof:

76. The compound or an isomer thereof:

77. The compound or an isomer thereof:

78. The compound according to any one of claims 1 to 77 being a monomer in the synthesis of at least one polymer.

79. The compound according to claim 78, wherein said polymer is selected from homopolymers, copolymers, alternating copolymers, periodic copolymers, random copolymers, statistical copolymers, block copolymers, and core-shell polymers.

80. The compound according to claim 79, wherein said polymer is suitable for use in nonlinear optics.

81. The compound according to claim 80, wherein said polymer is utilized as a specialty dye, reference standard, optical limiter, a component in microfabrication systems for nano-technological devices, and for a targeted medical therapeutic application.

82. The compound according to any one of claims 1 to 79 being an active medium of a 3 -dimensional optical memory.

83. The compound according to claim 82, wherein said active medium is suitable for storing and retrieving data.

84. A formulation comprising at least one compound according to any one of claims 1 to 82.

85. The formulation according to claim 84 being selected from a specialty dye, reference standard, optical limiter, microfabriation system, nanotechnological device, device or pharmaceutical composition for use in targeted medical therapeutic applications.

86. An isomer of a compound according to any one of claims 1 to 83.

87. The isomer according to claim 86 being selected from a cis, trans, E ox Z isomer.

88. A polymer constructed from at least one compound according to any one of claims 1 to 83.

89. A polymer embedded with at least one compound according to any one of claims 1 to 83.

90. The polymer according to claim 88 or 89 being selected from homopolymers, copolymers, alternating copolymers, periodic copolymers, random copolymers, statistical copolymers, block copolymers, graft copolymer and core-shell polymers.

91. The polymer according to claim .90, for use as a specialty dye, reference standard, optical limiter, a component in microfabrication systems for nano- technological devices, and for a targeted medical therapeutic application.

92. The polymer according to claim 91 being an active medium of a 3 -dimensional optical memory.

93. The polymer according to claim 92, wherein said active medium is suitable for storing and retrieving data.

94. A medium for storing and retrieving data comprising a compound according to any one of claims 1 to 82 or an isomer thereof.

95. The medium according to claim 94 being an active medium of a 3 -dimensional optical memory.