Nonlinear optical chromophores containing 3-methyl-2-cyclopenten-1-one based bridge structures, and methods of making and using the same

Abstract

The present disclosure is directed, in general, to (1) nonlinear optical (NLO) chromophores containing 3-methyl-2-cyclopenten-l- one based Fl-bridge groups, including (2) compositions / materials / resistive layers comprising NLO chromophores containing 3-methyl-2- cyclopenten-l-one based ll-bridge groups, and the methods of making the compositions / materials / resistive layers comprising NLO chromophores containing 3-methyl-2-cyclopenten-l-one based H- bridge groups (e.g., methods of drying and / or poling, and the like), (3) uses of NLO chromophores containing 3-methyl-2-cyclopenten-l-one based ll-bridge groups in electro-optic devices (e.g., EOMs). The nonlinear optical (NLO) chromophores have the following formula (II), wherein X is a cyclopenten-based Π-bridge having formula Π1 or Π2.

Description

Nonlinear Optical Chromophores Containing 3-Methyl-2-cyclopenten-l-one Based Bridge Structures, and Methods of Making and Using the SameCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of United States Provisional Application No. 63 / 710,799 filed on October 23, 2024, the entire contents of which is incorporated herein by reference.BACKGROUND

[0002] The rise of silicon photonics has led to renewed interest in the use of electro-optic (EO) materials in next generation device applications. Materials with a strong EO response and high-speed phase modulation in thin fdm form are essential for low power and small footprint devices, including devices used in data acquisition systems, analog I / O modules, field transmitters, lab and field instrumentation, servo drive control modules, direct current (DC) power supply, alternating current (AC), and / or electronic load.

[0003] EO response reflects the change in a material’s optical properties (e.g., refractive index) in response to an electrical field, and the strength of an EO response is correlated with the strength of the material’s Pockels effect. Generally, the higher the refractive index in response to an electric field the less voltage that is required to modulate an optic signal propagated through the EO material.

[0004] EO materials generally fall into three categories: (1) liquid crystals, including ferroelectric liquid crystals, and / or organic liquid crystals having a linear structure with a central core that contains several collinear rings, a linear unsaturated linkage and two terminal chains, and the like; (2) inorganic crystals characterized by a lack of inversion symmetry, such as KH2PO4 (KDP), KD2PO4 (KD*P or DKDP), lithiumniobate (LiNbCh), beta-barium borate (BBO), barium titanate (BTO), and (3) EO polymers, including non-linear optic (NLO) chromophore-polymer composite materials.

[0005] EO materials containing liquid crystals generally have desirable EO coefficient but exhibit inherently low phase modulation speeds due to the parasitic effect of the crystal metastructure. Conversely, EO materials containing lithium niobate and / or other inorganic crystals generally achieve desirable modulation speeds but their EO effects are inherently limited by optically active point defects invariably formed in the crystals during growth.

[0006] NLO chromophore-polymer materials can provide both high EO coefficient and high modulation speeds. A material with a high EO coefficient is characterized by strong electro-optic activity and thus can be suitable for use in highspeed optic phase shifters such as waveguides. The EO coefficient reflects the polarizability of a material under an electric field. Generally, a material with a relatively high EO coefficient, and thus high polarizability, is more likely to be poled under a lower external electric field than a material with a relatively low EO coefficient. In that regard, a material with high EO coefficient can operate at a lower voltage and, thus, a more economical power budget.

[0007] In addition, stability (e.g., thermal stability and photostability) of the NLO chromophore and polymer constituents is a key challenge to the development of EO polymer materials for practical use in commercial high-speed optic phase shifters. To satisfy the stringent requirements for such devices, NLO chromophores in particular should be resistant to thermal decay under long duration use processing temperatures and be resistant to light under long duration of light exposure.

[0008] Accordingly, a need exists for the development of NLO chromophores with not only high electro-optic activity and high polarizability, but also robust thermal stability and photostability under environmental conditions.BRIEF SUMMARY

[0009] The present disclosure is directed, in general, to (1) nonlinear optical (NLO) chromophores; (2) compositions / materials / resistive layers comprising NLO chromophores, and the methods of making the compositions / materials / resistive layers comprising NLO chromophores (e.g., methods of poling and / or drying, and the like); and (3) uses of NLO chromophores in electro-optic devices (e.g., electro-optic modulators (EOMs)). NLO chromophores disclosed herein not only have large EO effect, but also have fast modulation speed. In addition, NLO chromophores disclosed herein have superior photostability and thermal stability compared to other EO Materials. As a consequence, NLO chromophores herein are particularly suited for use as EO materials in connection with waveguide-based devices, e.g., slot modulators, for use in low power and small footprint devices, including microprocessors such as PIC microcontrollers and devices used in data acquisition systems such as analog I / O modules, field transmitters, fiber optic connectors, microcontrollers, power sensors, lab and field instrumentation, servo drive control modules, direct current (DC) power supply, alternating current (AC), and / or electronic load.

[0010] In one aspect, NLO chromophores containing 3-methyl-2-cyclopenten-l-one based II-bridge groups are disclosed. In one example, various embodiments of the present disclosure can include nonlinear optical chromophores of the general formula (I):D-n-A (I)wherein D can represent an organic electron-donating group; A can represent an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and 77 can represent a 77-bridge between the organic electron-accepting group and the organic electron-donating group.

[0011] In various preferred embodiments, the 77 is a 3-methyl-2-cyclopenten-l-one based II-bridge group having the following formula (II1):(n1)wherein R4, R5, R6, and R7can each independently represent a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7can together form a five-membered ring or a six-membered ring, and wherein R1can represent a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10, and wherein each a and b can independently represent an integer of 0 to 3; and z can represent an integer of 1 to 3. Asused herein,represents a point of bonding to another portion of a larger molecular structure. In various preferred embodiments, R1can represent a phenyl moiety. In various preferred embodiments, halogen-substituted can refer to mono-, di-, tri- and higher degrees of substitution.

[0012] In various preferred embodiments, the II is a 3-methyl-2-cyclopenten-l-one based II-bridge group having the following formula (II2):wherein R14, R15, R16and R17can each independently represent a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10, and wherein R13can represent a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10, and wherein each a and b can independently represent an integer of 0 to 3; and z can represent an integer of 1 to 3. As used herein,represents a point of bonding to another portion of a larger molecular structure. In various preferred embodiments, R13can represent a phenyl moiety. In various preferred embodiments, halogen-substituted can refer to mono-, di-, tri- and higher degrees of substitution.

[0013] In various preferred embodiments, nonlinear optical chromophores according to general formula (I) of the present invention include those of the general formula (II):wherein R2and R3can each independently represent a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10;wherein R8can represent a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein R8together with R11or R12can form a five-membered ring or a six-membered ring;wherein R11and R12can each be H or form a five-membered ring or a six-membered ring with R8;wherein R9can represent a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linearor branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-0-(CH2)n where n is 1-10;wherein R10can represent a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl; wherein X can represent a Il-bridge group having a formula (II1)(n1)or a formula (n2):IV7R" / VR / )= / K Ri <11 >wherein in the formula (II1), R1can represent a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstitutedalkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; R4,R5, R6, and R7can each independently represent a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted cyclohexyl, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7can together form a fivemembered ring or a six-membered ring; and wherein each a and b can independently represent an integer of 0 to 3; and z can represent an integer of 1 to 3;wherein in the formula (If2), R13can represent a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; R14, R13, R16and R17can each independently represent a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2),i-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b can independently represent an integer of 0 to 3; and z can represent an integer of 1 to 3.

[0014] In some embodiments, preferably a nonlinear optical chromophore can have a thermal decay less than or equal to about 10% under about 180 °C in about 90 minutes.

[0015] In some embodiments, preferably a nonlinear optical chromophore can have a decomposition temperature (Ta) greater than or equal to about 245 °C.

[0016] In some embodiments, preferably a nonlinear optical chromophore can have an electro-optic (EO) coefficient r?3 greater than or equal to about 120 pm / V.

[0017] In some embodiments, preferably a nonlinear optical chromophore can have a photostability less than or equal to about 5%.

[0018] In some embodiments, preferably a nonlinear optical chromophore can have a polarizability greater than or equal to about 200x1030m3.

[0019] Various embodiments of the nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based II-bridge groups may exhibit high EO coefficient 133. The EO coefficient rn is one of the more important EO properties and represents the relationship between the change in applied electric potential versus the change in the refractive index of the material. A high r33 exhibited in the various embodiments of the present disclosure may be strongly related to high polarizability. A higher EO coefficient r33 may indicate that the nonlinear optical chromophore has better EO properties and better potential usage.

[0020] Various embodiments of the present disclosure may include nonlinear electro-optic materials that include both the nonlinear optical chromophores described above and one or more matrix material, also referred to as host polymer, in which the one or more nonlinear optical chromophore may be incorporated. The nonlinear optical chromophore may generally be incorporated within the matrix material in virtually any amount, or can be used with no matrix material (i.e., “neat” or 100% chromophore).

[0021] In the same or another example, various embodiments of the present disclosure may include compositions that include both the nonlinear electro-optic material described above and solvents. Solvents which are suitable for use in the various embodiments may include regular solvents and / or high boiling point solvents. High boiling point solvents may include solvents having a boiling point greater than or equal to 100° C (at 1 atm). The glass transition temperature (Tg), in general, is the temperature atwhich an amorphous polymer changes from a hard / glassy state to a soft / rubbery state, or vice versa.

[0022] Meanwhile, a high photostability ensures the nonlinear optical chromophore will not degrade under illumination in an air atmosphere. The photostability of a nonlinear optical chromophore may be evaluated based on a photo decay. For example, the photo decay may be the percentage of degraded chromophore after exposing the nonlinear optical chromophore under UV-Vis in a given period of time.

[0023] In the same or another example, various embodiments of the present disclosure include resistive layers formed from the compositions described above through one or more procedures. The one or more procedures may include, but not limited to, drying and / or poling.

[0024] During the drying and / or poling process, an electro-optic material may be dispersed in a suitable solvent in virtually any amount that provides a homogenous solution and suitable properties for resistive layer formation. The resistive layers may be poled by applying a suitable voltage across the material at a suitable temperature.

[0025] In the same or another example, various embodiments of the present disclosure may include electro-optic devices with electro-optical functions that contain one or more resistive layers described above. The electro-optic devices may include electro-optic modulators (EOMs), which are optical devices in which a signal-controlled element exhibiting an electro-optic effect is used to modulate a beam of light. In EOMs, the nonlinear electro-optic material may be spun onto silicon wafers, and standard microfabrication techniques may be used to deposit and pattern metal electrodes and optical waveguides.

[0026] EOMs comprising various embodiments of nonlinear optical chromophores with 3-methyl-2-cyclopenten-l-one based II-bridge groups may include modulators applied in, for example, slot modulators (e.g., slot modulators for wafer-level poling), photonic integrated circuits (e.g., polymer photonic integrated circuits), datacenter switching, high voltage sensing equipment relevant to electric power industry,electrical-to-optical signal transduction equipment which transmits multiple television signals relevant to cable television (CATV) or satellite television, broad bandwidth acoustic spectrum analyzers, optical gyroscopes, phased array radar (e.g., integrated antenna / electro-optic modulator or w-band optical modulator), photonically detected radar, time stretching and ultrafast analog-to-digital conversion equipment, components for fiber optical and satellite telecommunications, generation equipment and detection equipment of ultrafast electrical fields, electric field sensor (e.g., electro-optic E-field sensor), land mine detection equipment, device related to wavelength division multiplexing, optical switching, devices related to spatial light modulation (e.g., devices related to beam steering), and / or augmented reality (AR) / virtual reality (VR) equipment (e.g., full-spectrum visible electro-optic modulator).

[0027] For example, the photonic integrated circuit (PIC) may be a chip that performs optical signal processing. The chip may contain two or more photonic components (e.g., resistive layer with nonlinear electro-optic materials) which form a functioning circuit to utilize photons to detect, generate, transport, and process light. The PICs have demonstrated huge potentials in delivering the performance (e.g., speed, size and efficiency) required for upcoming applications, such as 6G, automotive light detection and ranging (LiDAR), consumer healthcare, artificial intelligence (Al), optical computing, virtual reality (VR), and / or augmented reality (AR).BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

[0028] The foregoing summary, as well as the following detailed description of preferred embodiments of the disclosure, will be better understood when read in conjunction with the appended drawings. The embodiments of the drawings are shown for illustration. It should be understood, however, that the disclosure is not limited to the precise arrangements and instrumentalities shown.

[0029] In the drawings:

[0030] FIG. l is a depiction of a degenerate four wave mixing (DFWM) testing procedure for evaluation of third-order NLO properties of thin film composites.

[0031] FIG. 2 illustrates an example poling process of a nonlinear electro-optic material.

[0032] FIG. 3A is a partial side sectional diagram of an integrated electro-optic circuit.

[0033] FIG. 3B is a partial cross-sectional diagram of the integrated electro-optic circuit of FIG. 3 A.

[0034] FIG. 4 is an end view of a slot modulator with highly doped silicon slab and rail.DETAILED DESCRIPTION

[0035] Nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based II-bridge groups, as well as compositions having nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based II-bridge groups described herein exhibit high photostability and / or high polarizability.Terms and Concepts

[0036] As used herein, the following terms have the following meanings unless expressly stated to the contrary.

[0037] As used herein, the term “about”, in the context of concentrations of components of the formulations or in property values, typically means + / -5% of the stated value, more typically + / -4% of the stated value, more typically + / -3% of the stated value, more typically, + / -2% of the stated value, even more typically + / - !% of the stated value, and even more typically + / - 0.5% of the stated value.

[0038] When values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another example.

[0039] All ranges are inclusive and combinable. In addition, when a range is recited, it is contemplated that all values within the range, including end points, are combinable in all possible combinations.

[0040] As used herein, the singular forms "a," "an," and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) include plural references unless the context clearly dictates otherwise. For example, reference to "a substituent" encompasses a single substituent as well as two or more substituents, and the like. It is understood that any term in the singular may include its plural counterpart and vice versa, unless otherwise indicated herein or clearly contradicted by context.

[0041] Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0042] As used herein, the terms "for example," "for instance," "such as," or "including" are meant to introduce examples that further clarify more general subject matter.

[0043] As used herein, the term “ring-locked heteroatom” refers to a cyclic substituent comprising at least one heteroatom. In some embodiments, the heteroatom may be O, N, or S.

[0044] As used herein, the term "nonlinear optical chromophore" (NLO chromophore) refers to molecules or portions of a molecule that create a nonlinear electro-optic effect when irradiated with light.

[0045] As used herein, the term “electron-donating group” refers to an atom and / or a functional group that donates some of its electron density into a conjugated II system via resonance and / or inductive effects.

[0046] As used herein, the term “electron-accepting group” refers to an atom and / or a functional group that accepts some of the electron-donating group’s electron density in a conjugated II system via resonance and / or inductive effects.

[0047] As used herein, the term “bridging group” refers to a functional group that bridges between the electron-donating group and the electron-accepting group in a conjugated II system.

[0048] As used herein, the term “substituted compound” refers to an organic compound with one or more atoms or groups each replaced by a substituent. In various embodiments, the organic compound includes a Ci-Cio alkyl, a C2-C10 alkenyl, a C2-C10 alkynyl, an aryl, an alkylaryl, a carbocyclic, and / or a heterocyclic. In some embodiments, the substituent includes a halogen, a cyano group, a sulfonyl group, and / or a trifluoromethyl group.

[0049] As used herein, the term “four-wave mixing” (FWM) refers to an interaction of four spatially or spectrally distinct fields.

[0050] As used herein, the term “r.33” refers to an electro-optic coefficient, a function of a first-order hyperpolarizability, that represents the relationship between the change in applied electric potential versus the change in the refractive index of the material. The “ra” is expressed in units of pm / V. The “raa” is the principal element of the Pockels EO effect tensor and is a function of first-order hyperpolarizability (P) which denotes the magnitude of refractive index shift (Aq) obtained for an applied low-frequency electric field that represents the relationship between the change in applied electric potential versus the change in the refractive index of the material.

[0051] As used herein, the term “e” refers to a dielectric constant, which is also known as permittivity. The dielectric constant is a measure of the extent to which a substance is polarized under an applied (external) electric field. Polarization amounts to net separation of charge across the substance.

[0052] As used herein, the term “susceptibility” refers to the degree to which a material can be polarized by an external electric field. There are different orders of susceptibility such as linear susceptibility (%(1)), second-order susceptibilitythird-order susceptibility ((3)) and other higher-order susceptibilities. Second-order susceptibility describes the material's response to two electric fields of differentfrequencies. The electro-optic effect occurs when an electric field is applied to a material with a non-zero second-order susceptibility. When an electric field is applied to such a material, the polarization of the material changes, resulting in a change in the refractive index. The change in the index of refraction and the magnitude of the externally applied electric field is proportional. Third-order susceptibility (%(3)) describes the material’s response to three electrical fields of different frequencies. The third-order susceptibility coefficient associated with each electrical field will be different due to the ever-present dispersion (i.e. frequency dependence) of the susceptibilities.

[0053] As used herein, the terms “optic nonlinearity,” “nonlinearity,” and “nonlinear” refer to the behavior of light in nonlinear media, that is, media in which the polarization density P responds non-linearly to the electric field (E) of the light. The nonlinearity is typically observed only at very high light intensities (when the electric field of the light is >108 V / m and thus comparable to the atomic electric field of -1011 V / m) such as those provided by lasers.

[0054] As used herein, the term “nonlinear electro-optic material” refers to materials that include both the nonlinear optical chromophore and one or more matrix material, also referred to as host polymer, in which the one or more nonlinear optical chromophore may be incorporated. EO materials can exhibit a nonlinear EO effect. Suitable matrix materials can include polymers, such as, for example: poly(methylmethacrylate)s (PMMA); polyimides; polyamic acid; polystyrenes; poly(urethane)s (PU); and amorphous polycarbonates (APC). NLO materials are anisotropic in the presence of electromagnetic radiation. When the intensity of the electric field is very high, it creates a very large displacement of the electrons in the material from their equilibrium position. As a result of this, anharmonic behavior comes into the picture of electronic oscillation. So the general linear relationship becomes nonlinear. The polarization (P) of the medium is a nonlinear function of the electric field (E) and it could be expressed as follows:P =ZEHerein, is the electrical susceptibility. x(n)is the tensor quantity and n is the order of the process. (1)=linear polarizability, x(2), X(3)-=the first, second ... hyperpolarizability coefficient, etc.). The nonlinearity is observed only at very high light intensities such as those provided by lasers.

[0055] As used herein, the term “compositions” refers to one or more mixed composition(s) that may include both a nonlinear electro-optic material and solvents.

[0056] As used herein, the term “resistive layer” refers to one or more layer(s) that may be formed from the compositions defined above through one or more procedures.

[0057] As used herein, the term “electro-optic devices” refers to devices with electro-optical function that contain one or more resistive layer(s) described above. For example, the electro-optic devices may include electro-optic modulators (EOMs), which are optical devices in which a signal-controlled element exhibiting an electro-optic effect is used to modulate a beam of light.

[0058] As used herein, the term “refractive index” of an optical medium is a dimensionless number that gives the indication of the light bending ability of that medium. The refractive index may determine how much the path of light is bent, or refracted, when entering a material, as described by Snell's law of refraction, m sin Oi = n2 sin 02, where 0i and 02 are the angle of incidence and angle of refraction, respectively, of a ray crossing the interface between two media with refractive indices m and n2. The refractive indices also determine the amount of light that is reflected when reaching the interface, as well as the critical angle for total internal reflection, their intensity (Fresnel's equations) and Brewster's angle. The refractive index may also reflect the factor by which the speed and the wavelength of the radiation are reduced with respect to their vacuum values: the speed of light in a medium is v = c / n, and similarly the wavelength in that medium is X = Xo / n, where Ao is the wavelength of that light in vacuum. This implies that vacuum has a refractive index of 1 and assumes that the frequency (f = v / X) of the wave is not affected by the refractive index.

[0059] As used herein, the term “electro-optic (EO) effect” is the modification of the optical phase delay (i.e., refractive index) of a medium, caused by an electric field. The strength of an EO effect is correlated with the strength of the material’s Pockels effect. The Pockels effect (or linear EO effect) is a directionally dependent linear variation in the refractive index of an optical medium that occurs in response to the application of an electric field. Macroscopically, the Pockels coefficient r relates the change in the index of refraction to an applied electric field as:n(E) --where no is the index of refraction under no field and n is the index of refraction under a given electrical field with the voltage equals to E. The applied electrical field shifts the electron cloud to the excited-state molecular orbitals, which alters the refractive index of the EO materials. In optical media, the Pockels effect causes changes in birefringence that vary in proportion to the strength of the applied electric field.Nonlinear Optical Chromophore

[0060] An electro-optic (EO) effect is a change in the optical properties of a material in responses to an electric field that varies slowly compared with the frequency of light. For example, the electro-optic effect may indicate that a refractive index changes under an electric field. The refractive index change under the electric field may be explained through Pockels effect. Under Pockels effect, the electric field may shift the electron cloud to excited-state molecular orbitals and alter the refractive index of the material, which in turn may cause a phase change to any transiting optical signal.

[0061] Materials having the electro-optic effect may include liquid crystals, lithium niobate and / or other inorganic crystals, and / or organic nonlinear optical chromophores. Liquid crystals may have large EO effect but may be slow in modulation speed. Lithium niobate and / or other inorganic crystals may be fast in modulation speed but may have small EO effect. By comparing organic nonlinear optical chromophoreswith liquid crystals and lithium niobate and / or other inorganic crystals, organic nonlinear optical chromophores may have both large EO effect and fast modulation speed.

[0062] As used herein, the term "nonlinear optical chromophore" (NLO Chromophore) refers to molecules or portions of a molecule that create a nonlinear electro-optic effect when irradiated with light. The chromophores are any molecular unit whose interaction with light gives rise to the nonlinear optical effect. The desired effect may occur at resonant or nonresonant wavelengths. The activity of a specific chromophore in a nonlinear electro-optic material is stated as its electro-optic coefficient (r33), which is related to the molecular dipole moment and hyperpolarizability. The various embodiments of NLO chromophores of the present disclosure are useful structures for the production of NLO effects.

[0063] Nonlinear optical chromophores in accordance with the various embodiments of the disclosure have the general formula (T):D-77-A (I)wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and / / represents a / / -bridge between A and D. The terms electron-donating group (donor or “D”), / / -bridge (bridging group or “ / / ’), and electron-accepting group (acceptor or “A”), and general synthetic methods for forming D- / / -A chromophores are well known in the art.

[0064] A donor is an atom or group of atoms that has a low oxidation potential, wherein the atom or group of atoms can donate electrons to an acceptor through a 17-bridge. The donor (D) has a lower electron affinity than the acceptor (A), so that, at least in the absence of an external electric field, the chromophore is generally polarized, with relatively less electron density on the donor (D). Typically, a donor group contains at least one heteroatom that has a lone pair of electrons capable of being in conjugation with the p-orbitals of an atom directly attached to the heteroatom such that a resonance structure can be drawn that moves the lone pair of electrons into a bond with the p-orbitalof the atom directly attached to the heteroatom to formally increase the multiplicity of the bond between the heteroatom and the atom directly attached to the heteroatom (i.e., a single bond is formally converted to double bond, or a double bond is formally converted to a triple bond) so that the heteroatom gains formal positive charge. The p-orbitals of the atom directly attached to the heteroatom may be vacant or part of a multiple bond to another atom other than the heteroatom. The heteroatom may be a substituent of an atom that has 71 bonds or may be in a heterocyclic ring. Exemplary donor groups include but are not limited to R2N- and, RnX1— , where R is alkyl, aryl or heteroaryl, X1is O, S, P, Se, or Te, and n is 1 or 2. The total number of heteroatoms and carbons in a donor group may be about 30, and the donor group may be substituted further with alkyl, aryl, or heteroaryl.

[0065] In some embodiments of the present disclosure, D can represent any organic electron donating group, so long as D is bound to the core at two atomic positions on the core other than the two atomic positions at which A is bound to the core such that at least a portion of D forms a ring fused to the core.

[0066] Examples of organic electron donating groups suitable for incorporation into the chromophores of Formula (I) include, but are not limited to, the following structures, wherein the dashed lines represent the two atomic positions at which D formswherein each R independently represents a pendant spacer group.

[0067] In various nonlinear optical chromophores in accordance with various embodiments of the present disclosure, suitable electron-donating group include those according to general formula (Da):R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein R8together with R11or R12form a five-membered ring or a six-membered ring.R11and R12are H or form a five-membered ring or a six-membered ring with R8.R9represents a moiety selected from the group consisting of a moiety selected from the group consisting ofH, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10.R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl.

[0068] An acceptor is an atom or group of atoms that has a low reductive potential, wherein the atom or group of atoms can accept electrons from a donor through a 77-bridge. The acceptor (A) has a higher electron affinity than the donor (D), so that, at least in the absence of an external electric field, the chromophore is generally polarized in the ground state, with relatively more electron density on the acceptor (D). Typically, an acceptor group contains at least one electronegative heteroatom that is part of a K bond (a double or triple bond) such that a resonance structure can be drawn that moves the electron pair of the 7t bond to the heteroatom and concomitantly decreases the multiplicity of the 7i bond (i.e., a double bond is formally converted to single bond or a triple bond is formally converted to a double bond) so that the heteroatom gains formal negative charge. The heteroatom may be part of a heterocyclic ring. Exemplary acceptor groups include but are not limited to -NO2, — CN, — CHO, COR, CO2R, — PO(OR)s, — SOR, - SO2R, and — SO3R where R is alkyl, aryl, or heteroaryl. The total number of heteroatoms and carbons in an acceptor group is about 30, and the acceptor group may be substituted further with alkyl, aryl, and / or heteroaryl.

[0069] In various nonlinear optical chromophores in accordance with various embodiments of the present disclosure, suitable electron-accepting groups include those according to general formula (A1):wherein R2and R3each independently represents a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted orunsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10. As used herein,represents a point of bonding to another portion of a larger molecular structure. In various preferred embodiments, one or both of R2and R3represent a halogen-substituted moiety. Halogensubstituted may refer to mono-, di-, tri- and higher degrees of substitution. In various preferred embodiments, one of R2and R3represent a halogen-substituted alkyl moiety and the other represents an aromatic moiety. In various preferred embodiments, one of R and R represent a halogen-substituted aromatic moiety and the other represents an alkyl moiety.

[0070] A “77-bridge” includes an atom or group of atoms through which electrons may be delocalized from an electron donor (defined above) to an electron acceptor (defined above) through the orbitals of atoms in the bridge. Such groups are very well known in the art. Typically, the orbitals will be p-orbitals on double (sp2) or triple (sp) bonded carbon atoms such as those found in alkenes, alkynes, neutral or charged aromatic rings, and neutral or charged heteroaromatic ring systems. Additionally, the orbitals may be p-orbitals on atoms such as boron or nitrogen. Additionally, the orbitals may be p, d or f organometallic orbitals or hybrid organometallic orbitals. The atoms of the bridge that contain the orbitals through which the electrons are delocalized are referred to here as the “critical atoms.” The number of critical atoms in a bridge may be a number from 1 to about 30. The critical atoms may be substituted with an organic or inorganic group. The substituent may be selected with a view to improving the solubility of the chromophore in a polymer matrix, to enhance the stability of the chromophore, or for other purposes.

[0071] In various nonlinear optical chromophores in accordance with various embodiments of the present disclosure, suitable 77-bridge include those according to general formula (n1):R4, R5, R6, and R7each independently represents a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and one of R4-R5and one of R6-R7form a fivemembered ring or a six-membered ring. R1represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10. Each a and b independently represents an integer of 0 to 3, and z represents an integer of 1 to 3. As used herein,represents a point of bonding to another portion of a larger molecular structure. In some embodiments, preferably R1represents a phenyl moiety. In some embodiments, preferably halogen-substituted refers to mono-, di-, tri- and higher degrees of substitution.

[0072] In various nonlinear optical chromophores in accordance with various embodiments of the present disclosure, suitable / / -bridge include those according to general formula (II2):R:';R,,?Xl: Xys'<"" WH R::;f> A (n2)R14, R15, R16and R17each independently represents a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10. R13represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10. Each a and b independently represents an integer of 0 to 3, and z represents an integer of1 to 3. As used herein,represents a point of bonding to another portion of a larger molecular structure. In some embodiments, preferably R13represents a phenyl moiety. In some embodiments, preferably halogen- substituted refers to mono-, di-, tri- and higher degrees of substitution.

[0073] In various preferred embodiments, nonlinear optical chromophores according to general formula (I) of the present invention include those of the general formula (II):R! ;Rs(II)R2and R3each independently represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10.R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and R8together with R11or R12form a five-membered ring or a six-membered ring.R11and R12are H or form a five-membered ring or a six-membered ring with R8.R9represents a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted orunsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10.R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl.X represents a Il-bridge group having a formula (II1)(n1)or a formula (II2):R^In the formula (II1), R1represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10. R4, R5, R6, and R7each independently represents a moiety selected from the group consistingof hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and one of R4-R5and one of R6-R7form a fivemembered ring or a six-membered ring. Each a and b independently represents an integer of 0 to 3, and z represents an integer of 1 to 3.In the formula (II2), R13represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10. R14, R15, R16and R17each independently represents a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic (e.g., substituted or unsubstituted cyclohexyl), substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)ii-CH3 where n is 1-10. Each a and b independently represents an integer of 0 to 3, and z represents an integer of 1 to 3.

[0074] Examples of chromophores with a 3-methyl-2-cyclopenten-l-one based Il-bridge groups according to the various embodiments of the present disclosure may include the following chromophores:

[0075] The first-order hyperpolarizability (0) is one of the most common and useful NLO properties. An electro-optic coefficient (ra) is a function of 0, and a sufficient value of r33 may indict a good electro-optical property in a given NLO. For example, the sufficient value of r33 may be equal to or more than 100 pm / V.

[0076] The second-order hyperpolarizability (y) or third-order susceptibility (%(3)), are the normal measures of third-order NLO activity. While there are several methods used to measure these properties, degenerate four- wave mixing (DFWM) is very common. The term four-wave mixing (FWM) is usually reserved for the interaction of four spatially or spectrally distinct fields. In most common FWM processes, some of the frequencies, wave vectors, and polarizations are degenerated. For example, FWM may reduce to most common FWM processes when two or more off the frequencies are degenerate. The most common FWM processes may include, but not limited to, coherent anti-stokes Raman spectroscopy (CARS), coherent stokes Raman spectroscopy (CSRS), stimulated Raman gain spectroscopy (SRS), the inverse Raman effect spectroscopy (TIRES), and / or Raman induced Kerr effect spectroscopy (RIKES). FWM may be used to probe either one-photon resonances or two-photon resonances in a material by measuring the resonant enhancement as one or more of the frequencies are tuned. A method of evaluating third-order NLO properties of thin films, known in the art asdegenerate four- wave mixing (DFWM), may be illustrated in FIG. 1. In FIG. 1, Beams 102 and 104 are picosecond, coherent pulses, absorbed by the NLO fdm 110 deposited on a glass substrate 112. Beam 106 is a weaker, slightly delayed beam at the same wavelength as Beams 102 and 104. Beam 108 is the resulting product of the wave mixing, diffracted off of the transient holographic grating, produced by interferences of beams 102 and 104 in the NLO material of the film 110. Beam 106 can be a "control" beam at a telecom wavelength which produces a "signal" beam at a frequency not absorbed by the NLO material.

[0077] The EO property of the poled nonlinear electro-optic material that incorporates nonlinear optical chromophore may be tested as follows. Polarized light, often from a laser, is passed through the poled material that incorporates the poled nonlinear optical chromophore, then through a polarizing filter, and to a light intensity detector. If the intensity of light received at the detector changes as the electric potential applied to the electrodes is varied, the material incorporates a nonlinear optic chromophore and has an electro-optically variable refractive index.

[0078] The relationship between the change in applied electric potential versus the change in the refractive index of the material may be represented as its EO coefficient r33. This effect is commonly referred to as an electro-optic, or EO, effect. Devices that include materials that change their refractive index in response to changes in an applied electric potential are called electro-optical (EO) devices. For compositions having nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based II-bridge groups described herein, the EO coefficient ni of 120 pm / V, or even larger, and the refractive index of 2.2 or even larger, may be achieved.

[0079] The EO coefficient 03 may be strongly related to a polarizability of the chromophore. For example, a high may be strongly related to a high polarizability. A calculation of polarizability may be conducted via density functional theory (DFT) based calculation. DFT is a computational quantum mechanical modelling method used in physics, chemistry and material sciences to investigate the electronic structure of manybody systems. Using DFT theory, the properties (e.g., a polarizability) of a many-electronsystem (e.g., a chromophore) can be determined by using functionals, which are functions that accept a function as input and output a single real number as an output. In various embodiments of the present disclosure, nonlinear optical chromophores having a 3-methyl-2-cyclopenten-l-one based II-bridge group may have a polarizability greater than or equal to about 200x1030m3via DFT based calculation.

[0080] The photostability is one of the most useful properties of the chromophores. It is important for chromophores to have high photostability because high photostability ensures the chromophores will not degrade under illumination in an air atmosphere. The degradation of chromophores under illumination in the air will happen if double bonds in the chromophores react with molecular oxygen. The molecular oxygen in the air atmosphere may be either triplet oxygen or singlet oxygen. Triplet oxygen is the electronic ground state of molecular oxygen, which means triplet oxygen is the most stable and common allotrope of oxygen and is not reactive toward the double bonds under the illumination of light. Light converts triplet oxygen molecules to singlet oxygen molecules, which are very reactive toward double bonds. In summary, singlet oxygen is the reason why the chromophores will degrade under illumination in the air atmosphere. The reaction of singlet oxygen with the double bonds of chromophores will deactivate the chromophores by disrupting the conjugation of the double bonds, therefore making the double bonds no longer optically active. Therefore, if a chromophore is resistant to the degradation by singlet oxygen, the chromophore will have high photostability and less resources have to be spent on excluding oxygen from the working device. In a photostability test, the chromophores are subjected to illumination by a 6mW broadband light source under ambient conditions. The degradation of the material is monitored by absorbance spectroscopy. For example, 5% photostability means 5% of the chromophores are decomposed or degraded while 95% of the chromophores are unchanged under a 6mW broadband light source under ambient conditions monitored by absorbance spectroscopy. In various embodiments of the current disclosure, nonlinear optical chromophores having a 3-methyl-2-cyclopenten-l-one based II-bridge group may have a photostability less than or equal to about 5%.Nonlinear Electro-Optic Material

[0081] As used herein, the term “nonlinear electro-optic material” refers to materials that include both the nonlinear optical chromophore and one or more matrix material, also referred to as host polymer, in which the one or more nonlinear optical chromophore may be incorporated. Suitable matrix materials can include polymers, such as, for example: poly(methylmethacrylate)s (PMMA); polyimides; polyamic acid; polystyrenes; poly(urethane)s (PU); and amorphous polycarbonates (APC).

[0082] Glass transition temperature (Tg) is a temperature at which an amorphous polymer changes from a hard / glassy state to a soft / rubbery state, or vice versa. In various embodiments the matrix material can comprise a poly(methylmethacrylate), for example having a molecular weight of about 120,000 and a glass transition temperature Tgof about 100-165°C, or an APC having a Tgof about 150-220°C.

[0083] The nonlinear optical chromophore can generally be incorporated within the matrix material in virtually any amount, or can be used with no matrix material (i.e., “neat” or 100% chromophore). For example, suitable electro-optic material can comprise a nonlinear optical chromophore in an amount of from about 1 % to 90 % by weight, based on the entire weight of combined nonlinear optical chromophores and matrix materials. In various embodiments, suitable electro-optic compositions can comprise a nonlinear optical chromophore in an amount of from about 2 % to 80 % by weight, based on the entire weight of combined nonlinear optical chromophores and matrix materials. In various embodiments, suitable electro-optic compositions can comprise a nonlinear optical chromophore in an amount of from about 3 % to 75 % by weight, based on the entire weight of combined nonlinear optical chromophores and matrix materials. For example, one or more chromophores can be combined with an amorphous polycarbonate or mixtures of matrix materials at 70 wt% chromophore(s) / 30 wt% matrix material(s). In various embodiments, chromophores can be crosslinked with matrix materials or other polymers.Compositions

[0084] As used herein, the term “compositions” refers to one or more mixed composition(s) that may include both a nonlinear electro-optic material and solvents. Solvents which are suitable for use may include regular boiling point solvents and high boiling point solvents. As used herein, “high boiling point solvents” refers to solvents having a boiling point greater than or equal to 100° C (at 1 atm). In various embodiments, suitable solvents have a boiling point greater than or equal to 110° C, greater than or equal to 120° C, greater than or equal to 130° C, greater than or equal to 140° C, greater than or equal to 150° C, greater than or equal to 160° C, greater than or equal to 170° C, greater than or equal to 180° C, greater than or equal to 190° C, greater than or equal to 200° C, greater than or equal to 210° C, greater than or equal to 220° C, greater than or equal to 230° C, greater than or equal to 240° C, and greater than or equal to 250° C.

[0085] Nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based Il-bridge groups, as well as compositions having nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based Il-bridge groups described herein may exhibit high thermal stability. The thermal stability of a nonlinear optical chromophore may be evaluated based on a decomposition temperature (Ta) of the chromophore, and / or a thermal decay of the chromophore. The decomposition temperature (Ta) is the temperature at which the chromophore chemically decomposes. For example, the nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based Il-bridge groups described herein may have a decomposition temperature greater than or equal to 245 °C. The thermal decay is the percentage of chemically decomposed chromophore under a given temperature for a given period of time. For example, the nonlinear optical chromophore with 3-methyl-2-cyclopenten-l-one based Il-bridge groups described herein may have a thermal decay less than or equal to about 10% in 90 minutes. For example, 5% thermal decay means 5% of the chromophores are decomposed or degradedwhile 95% of the chromophores are unchanged under 180 °C in 90 minutes. Therefore, a low thermal decay and a high Ta may indicate a high thermal stability of the chromophores.

[0086] Thermal decay data, Ta, photostability as well as polarizability of various embodiments in nonlinear optical chromophores having a 3-methyl-2-cyclopenten-l-one based II-bridge group is summarized as follow:Chromophore with 3-methyl- Thermal Td Photostability Polarizability 2-cyclopenten-l-one based decayII-bridge group(180 °C)Chromophore A 2.8% 261.56 4.1% 2OO.33xlO30°C m3Chromophore B 7.4% 248.65°C 5% 212.65xlO303 mMethods of Forming Resistive Lavers

[0087] As used herein, the term “resistive layer” refers to one or more layer(s) that may be formed from the compositions defined above through one or more procedures. The one or more procedures may include, but not limited to, spin-coating and / or an atomic layer deposition (ALD) process. Spin-coating may be a procedure to deposit nonlinear electro-optic material onto flat substrates to form resistive layers. For example, a small amount of nonlinear electro-optic material may be applied on the center of the substrate. The substrate may be rotated at speeds up to 10,000 rpm to spread the nonlinear electro-optic material to form resistive layers by centrifugal force. ALD may be an ultrathin film deposition technique controlled by gas phase and sequential self-limiting chemical reactions of the precursors at the material surface.

[0088] In addition, the composition may go through drying and / or poling before the one or more procedures to achieve the desired EO effect. An electro-optic materialcan be dispersed in a suitable solvent in virtually any amount that provides a homogenous solution and suitable properties for resistive layer formation. For example, the solids content of an electro-optic material in a solvent according to various embodiments described herein can be adjusted depending upon desired resistive layer thickness and spin speed of a spin coating apparatus. As known in the art, a less viscous solution generally results in a thinner spin coated resistive layer. In various embodiments, the solids content of an electro-optic material in a solvent can be from about 1% to about 25%. In various embodiments, the solids content of an electro-optic material in a solvent can be from about 2% to about 20%. In various embodiments, the solids content of an electro-optic material in a solvent can be from about 5% to about 15%. In the poling process, the electro-optic material may obtain a high EO coefficient r33 if the chromophores are well aligned under the electrical field. Mathematically, the EO coefficient r33 can be positively correlated with a strength (e.g., voltage) of the poling electrical field below a maximum voltage. For example, the EO coefficient r33 and the voltage of the poling electrical field may have a positive relationship (i.e., the higher the voltage, the higher the poling electrical field and so too the rss) before reaching the maximum voltage. However, the r33 may decrease after the maximum voltage is reached, probably due to other mechanisms such as dielectric breakdown.

[0089] Example methods in accordance with various embodiments of the present disclosure include providing a composition as described herein, forming a resistive layer comprising the composition, drying the resistive layer (i.e., removing solvent), and poling the resistive layer.

[0090] A suitable resistive layer can be formed on a substrate using, for example, a spin-coating process or ink jet printing. Suitable substrates can include indium -tinoxide (ITO) coated surfaces, conductive materials, silicon, semi-conductors and the like. Resistive layers can be formed at various thicknesses from submicron to several microns.

[0091] FIG. 2 illustrates an example poling process of a nonlinear electro-optic material. Since the electron density is not evenly distributed inside the nonlinear optical chromophore, the electron density of the electron-accepting group is higher than theelectron density of the electron-donating group. Therefore, each nonlinear optical chromophore molecule may comprise a dipole 202, which exhibits positive charge on the electron-donating group side and negative charge on the electron-accepting group side. When no voltage 204 is applied, there is no charge on electrodes 206. The dipoles are randomly directed with no alignment. However, when voltage 204 is applied, electrodes 206 may have charges (e g., positive charges or negative charges) on them and form an electrical field in between. The dipoles 202 are poled and aligned under the electrical field to make non-centrosymmetric, nonlinear electro-optic materials.

[0092] Resistive layers prepared in accordance with various method embodiments disclosed herein can be poled by applying a suitable voltage across the material at a suitable temperature. Electrodes can be formed or positioned on opposing sides of a resistive layer, or above and below a resistive layer in various devices and structures and a suitable voltage applied across the resistive layer in such a manner. Electrodes can be formed from, for example, gold. Suitable voltages can be from about 50 V / pm to about 150 V / pm. Suitable temperatures for poling the resistive layer are generally higher than the nonlinear optical chromophore’s glass transition temperature (Tg), which is high enough to allow arrangement of the nonlinear optical chromophore within the material.

[0093] After poling the resistive layer, while still maintaining the field of applied voltage, a resistive layer in accordance with various embodiments described herein can be dried or densified by removing the remaining solvent. Solvent is generally removed until the glass transition temperature of the resistive layer approaches the Tgof the chromophore. Drying or removal of the solvent can be undertaken, for example, by slowly and slightly increasing temperature while the poling field is maintained until solvent is removed, then cooling. Drying or removal of the solvent can be undertaken, for example, by cooling while maintaining the applied poling field to a lower temperature such that de-poling does not occur at a substantial rate and then applying vacuum to remove solvent.

[0094] Resistive layers in accordance with the various embodiments herein can be incorporated in various devices including electro-optic devices having open-top orcoplanar designs, and devices having permeable layers, opening or the like such that solvent can be driven off after poling. Examples of various devices may include, but not limited to, hybrid electro-optic polymer and TiCh double-slot waveguide modulators, ultrabroadband electro-optic modulator based on hybrid silicon polymer dual vertical slot waveguide, plate slot polymer waveguide modulator, electro-optic polymer / TiCh multilayer slot waveguide modulators, and / or coplanar electrode polymer modulator.

[0095] As discussed above, the first-order hyperpolarizability (0) is one of the most common and useful NLO properties. Higher-order hyperpolarizabilities are useful in other applications such as all-optical (light-switching-light) applications. To determine if a nonlinear electro-optic material, such as a compound or polymer, includes a nonlinear optic chromophore with hyperpolarizability and a sufficient electro-optic coefficient (03), which is a function of 0, the material in the form of a resistive layer is placed in an electric field to align the dipoles. This may be performed by sandwiching a resistive layer of the nonlinear electro-optic material between electrodes, such as indium tin oxide (ITO) substrates, gold films, or silver films, for example. To generate a poling electric field, an electric potential is then applied to the electrodes while the nonlinear electro-optic material is heated to its glass transition (Tg) temperature. After a suitable period of time, the temperature is gradually lowered while maintaining the poling electric field.Alternatively, the nonlinear electro-optic material can be poled by corona poling method, where an electrically charged needle at a suitable distance from the resistive layer provides the poling electric field. In either instance, the dipoles in the nonlinear electrooptic material tend to align with the field.Electro-Optic Devices

[0096] As used herein, the term “electro-optic devices” refers to devices with electro-optical function that contain one or more resistive layer(s) described above. For example, the electro-optic devices may include electro-optic modulators (EOMs), which are optical devices in which a signal-controlled element exhibiting an electro-optic effectis used to modulate a beam of light. The modulation may be imposed on the phase / frequency, amplitude, and / or polarization of the beam. One EOM may conduct one or more (e.g., one or all) modulations among the phase / frequency, amplitude, or polarization modulations.

[0097] Phase modulation (PM) is a modulation pattern that encodes information as variations in the instantaneous phase of a carrier wave. The phase of a carrier signal is modulated to follow the changing voltage level (amplitude) of the modulation signal. The peak amplitude and frequency of the carrier signal remain constant, but as the amplitude of the information signal changes, the phase of the carrier changes correspondingly.

[0098] Amplitude modulation is a process by which the wave signal is transmitted by modulating the amplitude of the signal. Mach-Zehnder (MZ) interferometer as an example. The MZ interferometer may often be used in integrated optics where the requirements of phase stability are more easily achieved. The beam splitter may divide the laser light into two paths, one of which has a phase modulator. The beams may then be recombined. Changing the electric field on the phase modulating path may then determine whether the two beams interfere constructively or destructively at the output, and thereby control the amplitude or intensity of the exiting light. In one example of the MZ interferometer, the modulator may have two arms of electro-optic material. One arm may have electrodes, where a changing voltage can be applied. The other arm may have no voltage applied.

[0099] Polarization modulation in EO materials may be used as a technique for time-resolved measurement of unknown electric fields. Depending on the type and orientation of the EO material, and on the direction of the applied electric field, the phase delay may depend on the polarization direction. For example, EOM used in antenna may conduct the polarization modulation.

[0100] In EOMs, the nonlinear electro-optic materials are spun onto silicon wafers and standard microfabrication techniques are used to deposit and pattern metal electrodes and optical waveguides. For example, one well-known EOM device is theabove-mentioned Mach-Zehnder interferometer. The light output is changed by changing the relative phase between the two arms. One common trick to double the effect for the same available drive voltage is to drive the two arms in opposite directions (push-pull mode). Nonlinear electro-optic materials have an interesting advantage over most other electro-optic materials which are crystalline. The direction of nonlinear electro-optic materials’ electro-optic activity is entirely determined by the direction of the applied poling field. By poling the two arms of the MZ in opposite directions, the resulting device automatically has push-pull operation with a single applied signal.

[0101] Each EOM may include one or more integrated polymer electro-optic semiconductor circuits. FIGs. 3A and 3B are respective side sectional and cross-sectional views of an integrated polymer electro-optic semiconductor circuit 301, according to an embodiment. A semiconductor substrate 302 includes at least one dopinglayer 304 patterned across the semiconductor substrate to form portions of semiconductor devices. At least one resistive layer 306 is patterned over the semiconductor substrate. A planarization layer 308 is disposed at least partly coplanar with the at least one conductor layer 306. A polymer optical stack 310 is disposed over the planarization layer 308.

[0102] At least one via 312 may at least partially extend through the polymer optical stack 310. The at least one via may be operatively coupled to a corresponding location on the at least one patterned conductor layer 306. A top conductor layer 314 is disposed over the polymer optical stack and in electrical continuity with the at least one via 312.

[0103] As an alternative to a via 312, other conductors may be substituted to electrically couple the top conductor layer to at least one location on the at least one patterned conductor layer 306. For example, the at least one conductor may be formed entirely or in combination from a via, a wire bond, a conductive bump, and / or an anisotropic conductive region.

[0104] The top conductor layer 314 may be formed to include a metal layer or a conductive polymer, for example. The top conductor may be plated to increase itsthickness. The top conductor layer may include at least one high speed electrode 316 formed as a pattern in the top conductor layer 314, the high speed electrode 316 being operatively coupled to receive a signal from the at least one via 312 or other conductive structure from the corresponding location on the at least one patterned conductor layer 306. Thus, the at least one via 312 or other conductive structure is configured to transmit an electrical signal from semiconductor electrical circuitry formed on the semiconductor substrate 302 to the at least one high speedelectrode 316 through or around the polymer optical stack 310.

[0105] According to embodiments, the at least one patterned conductor layer 306 is configured to form a ground electrode 318 parallel to the at least one high speed electrode 316. An active region 320 of the polymer optical stack 310 is positioned to receive a modulation signal from the high speed electrode 316 and the ground electrode 318. The active region 320 includes a poled region that contains at least one hyperpolarizable organic chromophore.

[0106] The polymer optical stack 310 is configured to support the active region 320 as well as receive and guide light 322 to and from the active region. The polymer optical stack 310 may include at least one bottom cladding layer 324 and at least one top cladding layer 326 disposed respectively below and above an electro-optic layer 328. The bottom 324 and top 326 cladding layers, optionally in cooperation with the planarization layer 308, are configured to guide inserted light 322 along the plane of the electro-optic layer 328. Light guiding structures 330 are formed in the polymer optical stack 310 to guide the light 322 along one or more light propagation paths through the electro-optic layer 328 and / or non-active core structures (not shown). In the embodiment of FIGs. 3 A and 3B, the guidance structures 330 are formed as trench waveguides that include etched paths in the at least one bottom cladding layer 324.

[0107] The integrated polymer electro-optic semiconductor circuit 301 includes a semiconductor electrical circuit formed from a complex of the doping layerpattern 304 and the at least one patterned conductor layer 306. According to an embodiment, the semiconductor electrical circuit is configured, when in operation, todrive the electrodes 316, 318 with a series of modulated electrical pulses. A resultant modulated electrical field is thus imposed across the active region 320 and results in modulated hyperpolarization of the poled organic chromophores embedded therein. A complex of electrodes 316, 318, active region 320 and light guidance structures 330. The modulated hyperpolarization may thus modulate the velocity light passed through the poled active region 320 of the polymer optical stack 310. Repeatedly modulating the velocity of the transmitted light creates a phase-modulated light signal emerging from the active region. Such an active region 320 may be combined with light splitters, combiners (not shown), and other active regions to create light amplitude modulators. Light amplitude modulators herein include MZ optical modulators. Other light amplitude modulators may include ring resonator modulator, which includes one or more ring resonators which is a set of waveguides in which at least one is a closed loop coupled to some light input and output. Other light amplitude modulators may include in-phase and quadrature (I / Q) modulator, which modulates based on the summation of two I / Q signals that are in quadrature.

[0108] A combination of at least one electro-optic active region 320, at least two electrodes 316, 318, and corresponding light guiding structures 324, 326, 330 may be considered an electro-optic device 332, 334. A two-channel electro-optic device 334 may be formed from one ground electrode 318 and corresponding pairs of activeregions 320 and high speed electrodes 316a, 316b. The two channels of a two channel electro-optic device 334 may operate in cooperation, such as in a push-pull manner to form an MZ optical modulator.

[0109] Additional devices may be formed using electrodes or resistors 336 that are not configured for high speed operation. The operation of one such illustrated device is described below in conjunction with the description of an optical phase bias device.

[0110] FIG. 4 illustrates an end view of a slot modulator with highly doped silicon slab and rail. Referring specifically to FIG. 4, an end view of a slot modulator 400 is illustrated which in this example is a Mach-Zehnder modulator including two slot waveguides 412 and 414 in parallel and driven in push-pull with asingle coplanar transmission line 416. It should be understood that a single slot waveguide can be used to form a slot modulator in accordance with the present invention. In this example, a typical SiChbox 418 is formed on a silicon substrate 419. Transmission line 416 is formed of spaced apart aluminum conductors positioned onSiChbox 418 with G conductors 420 and 421 on each edge and an Sconductor 422 extending midway therebetween. Slot waveguide 412 includesa slab 424 extending inwardly from G conductor 420 and a slab 426 extending inwardly from S conductor 422. A vertically extending rail 428 is attached to the inner end of slab 424 and a vertically extending rail 430, spaced from rail 428, is attached to the inner end of slab 426. Rails 428 and 430 primarily form slot waveguide 412. The area between G conductor 420 and S conductor 422, including the slot formedbetween rails 428 and 430, is filled with EO polymer cladding material 432. Slot waveguide 414 is a mirror image of slot waveguide 412 with slabs and rails positioned and connected as described in conjunction with slot waveguide 412. In the following disclosure, only slot waveguide 412 is discussed in detail with the understanding that all of the details apply similarly to slot waveguide 414.

[0111] To aid in understanding the size of the structure being discussed, the thickness of transmission line 416 is 1 pm, slabs 424 and 426 are each 70 nm tall and 0.5 to 1 pm wide. Rails 428 and 430 are each 220 nm tall (lower surface to upper end) and 240 nm wide with a 200 nm spacing between the centers. The total length of slot waveguide 412 from G conductor 420 to S conductor 422 is 10 um long.

[0112] In the prior art, slab 424 and rail 428 are integrally formed and also integrally formed with G conductor 420. Similarly, slab 426 and rail 430 are integrally formed and also integrally formed with S conductor 422. In a similar fashion, the slabs and rails of slot waveguide 414 are integrally formed with G conductor 421 and S conductor 422. In slot modulator 400 slabs 424 and 426 and rails 428 and 430 are formed of silicon that is highly doped (N+++), to reduce resistivity and to achieve a high bandwidth.

[0113] EOMs comprising various embodiments of nonlinear optical chromophores according to the present disclosure may include modulators applied in, for example, slot modulators (e.g., slot modulators for wafer-level poling), photonic integrated circuits (e.g., polymer photonic integrated circuits), datacenter switching, high voltage sensing equipment relevant to electric power industry, electrical-to-optical signal transduction equipment which transmits multiple television signals relevant to cable television (CATV) or satellite television, broad bandwidth acoustic spectrum analyzers, optical gyroscopes, phased array radar (e.g., integrated antenna / electro-optic modulator or w-band optical modulator), photonically detected radar, time stretching and ultrafast analog-to-digital conversion equipment, components for fiber optical and satellite telecommunications, generation equipment and detection equipment of ultrafast electrical fields, electric field sensor (e.g., electro-optic E-field sensor), land mine detection equipment, device related to wavelength division multiplexing, optical switching, devices related to spatial light modulation (e.g., devices related to beam steering), and / or augmented reality (AR)Zvirtual reality (VR) equipment (e.g., full-spectrum visible electro-optic modulator).

[0114] For example, the photonic integrated circuit (PIC) is a chip that performs optical signal processing. The chip may contain two or more photonic components (e.g., resistive layer with nonlinear electro-optic materials) which form a functioning circuit to utilize photons to detect, generate, transport, and process light. The PICs have demonstrated huge potentials in delivering the performance (e.g., speed, size and efficiency) required for upcoming applications, such as 6G, automotive light detection and ranging (LiDAR), consumer healthcare, artificial intelligence (Al), optical computing, virtual reality (VR), and / or augmented reality (AR).

[0115] EO polymer materials herein may also be used with plasmonic-based devices, including semiconductor modulators and plasmonic slot modulators. A semiconductor slot modulator for use consistent with the present disclosure is a type of photonic slot modulator where the high-refractive-index materials on either side of the slot are semiconductors (e.g., silicon). Modulation is typically achieved by changing therefractive index of the semiconductor via the plasma dispersion effect, where an applied voltage alters the concentration of free charge carriers.

[0116] A plasmonic slot modulator for use consistent with the present disclosure is another type of photonic slot modulator that utilizes a slot waveguide. However, in this case, the slot is generally formed between two metallic structures, often filled with a dielectric material. The light is guided as a surface plasmon polariton (SPP), a hybrid electromagnetic wave coupled to the oscillation of free electrons at the metal-dielectric interface. This allows for extremely strong light confinement and is often used to create ultra-compact, high-speed modulators.Synthesis Example

[0117] Synthesis Example 1 : Preparation of 2-(3-cyano-4-((E)-3-((E)-3-((E)-4-(diphenylamino)styryl)-2-phenyl-lH-inden-l -ylidene)prop- 1 -en- 1 -yl)-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene)malononitrile.

[0118] Example la: Synthesis of 4-(diphenylamino)benzaldehyde.

[0119] A solution of triphenylamine in DCM was treated with DMF (10 eq). POCh (1.5 eq) was added dropwise, and the mixture was stirred at room temperature until analysis indicated full conversion. The DCM was evaporated, then the remaining solution was poured into icy 10% aqueous sodium carbonate. The slushy mixture was stirred until the ice had melted, then the resultant solids were isolated and dried by vacuum filtration to afford the title compound.

[0120] Example lb: Synthesis of 3-methyl-2-phenyl-lH-inden-l-one.O

[0121] A solution of 2-phenyl-lH-indene-l,3(2H)-dione in THF was treated with MeMgBr at 0°C under a blanket of N2. The reaction was stirred at the same temperature until analysis indicated full conversion. The reaction mixture was quenched with 6N HC1, then the resultant solids were isolated to afford the title compound.

[0122] Example 1c: Synthesis of (E)-3-(4-(diphenylamino)styryl)-2-phenyl-lH-inden-l-one.

[0123] A suspension of 4-(diphenylamino)benzaldehyde and 3 -methyl -2-phenyl-IH-inden-l-one (1.2 eq) in EtOH were treated with LiOEt (2 eq) and piperidine (2 eq). The mixture was heated to 70°C and stirred until analysis indicated full conversion. The reaction mixture was quenched with MeOH, then the resultant solids were isolated by vacuum filtration to afford the title compound.

[0124] Example Id: Synthesis of 2-((E)-3 -((E)-4-(diphenylamino)styryl)-2-phenyl-lH-inden-l-ylidene)acetonitrile.

[0125] A suspension of NaH (2 eq) in THF was stirred at room temperature. Then diethyl (cyanomethyl)phosphonate (2.2 eq) was added, and the mixture stirred. To this was added (E)-3-(4-(diphenylamino)styryl)-2-phenyl-lH-inden-l-one, and the solution was stirred at 70°C until analysis indicated full conversion. The reaction mixture was concentrated then quenched with MeOH. The resultant solids were isolated by vacuum filtration to afford the title compound.

[0126] Example le: Synthesis of 2-((E)-3-((E)-4-(diphenylamino)styryl)-2-phenyl- IH-inden- 1 -ylidene)acetaldehyde.

[0127] A solution of 2-((E)-3-((E)-4-(diphenylamino)styryl)-2-phenyl-lH-inden-l-ylidene)acetonitrile in DCM was treated with dropwise addition of DIBAL-H (1.5 eq). The mixture was stirred at room temperature until analysis indicated full conversion. The mixture was quenched by addition of sodium sulfate decahydrate, then the slurry was adsorbed onto silica gel for chromatography. The product fractions were concentrated to afford the title compound.

[0128] Example If: Synthesis of 2-(3-cyano-4-((E)-3-((E)-3-((E)-4- (diphenylamino)styryl)-2-phenyl-lH-inden- 1 -ylidene)prop- 1 -en- 1 -yl)-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene)malononitrile.

[0129] A suspension of 2-((E)-3-((E)-4-(diphenylamino)styryl)-2-phenyl-lH-inden-l-ylidene)acetaldehyde and 2-(3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene)malononitrile (El eq) in EtOEl was stirred at 60°C until analysis indicated full conversion. The reaction mixture was cooled and filtered. The solids were recrystallized from MeOH to afford the title compound.Enumerated Embodiments

[0130] The following list of enumerated embodiments presents claims with multiply dependent claims depending from multiply dependent claims for presentation in those jurisdictions where such dependencies are allowed as well as additional claims, which may be presented during the examination of the application or any divisional or continuation thereof.

[0131] EE 1. A nonlinear optical chromophore of a general formula (I):D-77-A (I)wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and 77 represents a 7-bridge between the organic electron-accepting group and the organic electron-donating group; wherein 77 is a 3-methyl-2-cyclopenten-l-one based Elbridge group having formula (II1):or formula (II2):A7R*V:::A / <' (II2)wherein the formula (II1) comprises R1representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl,substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R3and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

[0132] EE 2. The nonlinear optical chromophore according to EE 1, wherein the nonlinear optical chromophore has a general formula (II):wherein R2and R3each independently represents a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10;wherein R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein R8together with R11or R12form a five-membered ring or a six-membered ring;wherein R11and R12are H or form a five-membered ring or a six-membered ring with R8;wherein R9represents a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10;wherein R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl;wherein X represents a Il-bridge group having formula (II1)or formula (II2):wherein the formula (II1) comprises R1representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R3and one of R6-R7form a five-membered ring or a six-membered ring; and whereineach a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

[0133] EE 3. The nonlinear optical chromophore according to EE 1 or EE 2, wherein the nonlinear optical chromophore has a thermal decay less than or equal to about 10% under about 180 °C in about 90 minutes.

[0134] EE 4. The nonlinear optical chromophore according to any one of EEs 1-3, wherein the nonlinear optical chromophore has a decomposition temperature (Td) greater than or equal to about 245 °C.

[0135] EE 5. The nonlinear optical chromophore according to any one of EEs 1-4, wherein the nonlinear optical chromophore has an electro-optic (EO) coefficient r33 greater than or equal to about 120 pm / V.

[0136] EE 6. The nonlinear optical chromophore according to any one of EEs 1-5, wherein the nonlinear optical chromophore has a photostability less than or equal to about 5%.

[0137] EE 7. The nonlinear optical chromophore according to any one of EEs 1-6, wherein the nonlinear optical chromophore has a polarizability greater than or equal to about 200x1030m3.

[0138] EE 8. A resistive film comprising the nonlinear optical chromophore according to any one of EEs 1-7 dispersed and poled within a matrix material.

[0139] EE 9. An electro-optic device comprising one or more resistive film, wherein the one or more resistive film each comprising a nonlinear optical chromophore dispersed and poled within a host polymer matrix, wherein the nonlinear optical chromophore of a general formula (I):D-77-A (I)wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and 77 represents a 77-bridge between the organic electron-accepting group and the organic electron-donating group; wherein 77 is a 3-methyl-2-cyclopenten-l-one based Elbridge group having formula (II1):(n1)or formula (II2):wherein the formula (n1) comprises R1representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R3, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl,substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

[0140] EE 10. The electro-optic device according to EE 9, wherein the nonlinear optical chromophore has a general formula (II):wherein R2and R3each independently represents a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10;wherein R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10,and wherein R8together with R11or R12form a five-membered ring or a six-membered ring;wherein R11and R12are H or form a five-membered ring or a six-membered ring with R8;wherein R9represents a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10;wherein R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl;wherein X represents a Il-bridge group having formula (II1)(n1)or formula (II2):wherein the formula (II1) comprises R1representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)nwhere n is 1-10; wherein the formula (II2) further comprises R14, R1?, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl,substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

[0141] EE 11. The electro-optic device according to EE 9 or EE 10, wherein the nonlinear optical chromophore has a thermal decay less than or equal to about 10% under about 180 °C in about 90 minutes.

[0142] EE 12. The electro-optic device according to any one of EEs 9-11, wherein the nonlinear optical chromophore has a decomposition temperature (Td) greater than or equal to about 245 °C.

[0143] EE 13. The electro-optic device according to any one of EEs 9-12, wherein the nonlinear optical chromophore has an electro-optic (EO) coefficient r33 greater than or equal to about 120 pm / V.

[0144] EE 14. The electro-optic device according to any one of EEs 9-13, wherein the nonlinear optical chromophore has a photostability less than or equal to about 5%.

[0145] EE 15. The electro-optic device according to any one of EEs 9-14, wherein the nonlinear optical chromophore has a polarizability greater than or equal to about 200x1030m3.

Claims

CLAIMSWhat is claimed is:

1. A nonlinear optical chromophore of a general formula (I):D- / 7-A (I)wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and / 7 represents a / Abridge between the organic electron-accepting group and the organic electron-donating group; wherein 77 is a 3-methyl-2-cyclopenten-l-one based II-bridge group having formula (II1):wherein the formula (II1) comprises R1representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or un substituted alkylaryl, substituted or un substituted carbocyclic, substituted or un substituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted Ci-Cio linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

2. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a general formula (II):wherein R2and R3each independently represents a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or un substituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10;wherein R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein R8together with R11or R12form a five-membered ring or a six-membered ring;wherein R11and R12are H or form a five-membered ring or a six-membered ring with R8;wherein R9represents a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10;wherein R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl;wherein X represents a Il-bridge group having formula (II1)(n1)or formula (II2):wherein the formula (II1) comprises R1representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

3. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a thermal decay less than or equal to about 10% under about 180 °C in about 90 minutes.

4. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a decomposition temperature (Ta) greater than or equal to about 245 °C.

5. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has an electro-optic (EO) coefficient rvi greater than or equal to about 120 pm / V.

6. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a photostability less than or equal to about 5%.

7. The nonlinear optical chromophore according to claim 1, wherein the nonlinear optical chromophore has a polarizability greater than or equal to about 2OOxlO30m3.

8. A resistive film comprising the nonlinear optical chromophore according to claim 1 dispersed and poled within a matrix material.

9. An electro-optic device comprising one or more resistive film, wherein the one or more resistive film each comprising a nonlinear optical chromophore dispersed and poled within a host polymer matrix, wherein the nonlinear optical chromophore of a general formula (I):D- / 7-A (I)wherein D represents an organic electron-donating group; A represents an organic electron-accepting group having an electron affinity greater than the electron affinity of D; and 77 represents a 77-bridge between the organic electron-accepting group and the organic electron-donating group; wherein 77 is a 3-methyl-2-cyclopenten-l-one based flbridge group having formula (II1):or formula (II2): / W \ >H R1:;:X 4(1 Ijwherein the formula (II1) comprises R1representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or un substituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting of H, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

10. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has a general formula (II):wherein R2and R3each independently represents a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstitutedcarbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n where n is 1-10;wherein R8represents a moiety selected from the group consisting of H, substituted or unsubstituted linear or branched alkyl, substituted or unsubstituted linear or branched alkenyl, substituted or unsubstituted linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein R8together with R11or R12form a five-membered ring or a six-membered ring;wherein R11and R12are H or form a five-membered ring or a six-membered ring with R8;wherein R9represents a moiety selected from the group consisting of a moiety selected from the group consisting of H, halogens, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted Ci-Cio linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, substituted or unsubstituted silyloxy methyl, and CH3-(CH2)n-O-(CH2)n where n is 1-10;wherein R10represents a moiety selected from the group consisting of a moiety selected from the group consisting of H and substituted or unsubstituted alkyl;wherein X represents a II-bridge group having formula (II1)(n1)or formula (II2):wherein the formula (II1) comprises R1representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II1) further comprises R4, R5, R6, and R7each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, (CH2)n-O-(CH2)n where n is 1-10, and wherein one of R4-R5and one of R6-R7form a five-membered ring or a six-membered ring; and wherein each a and b in the formula (II1) independently represents an integer of 0 to 3; and z in the formula (II1) represents an integer of 1 to 3; andwherein the formula (II2) comprises R13representing a moiety selected from the group consisting ofH, heteroatoms, substituted or unsubstituted heteroaryl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted amino, substituted or unsubstituted alkoxy carbonyl, substituted or unsubstituted thioalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and CH3-(CH2)n-O-(CH2)n where n is 1-10; wherein the formula (II2) further comprises R14, R15, R16and R17each independently representing a moiety selected from the group consisting of hydrogen, heteroatoms, substituted or unsubstituted Ci-Cio linear or branched alkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl, substituted or unsubstituted C2-C10 linear or branched alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted heterocyclic, and (CH2)n-O-(CH2)n-CH3 where n is 1-10; and wherein each a and b in the formula (II2) independently represents an integer of 0 to 3; and z in the formula (II2) represents an integer of 1 to 3.

11. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has a thermal decay less than or equal to about 10% under about 180 °C in about 90 minutes.

12. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has a decomposition temperature (Ta) greater than or equal to about 245 °C.

13. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has an electro-optic (EO) coefficient rvi greater than or equal to about 120 pm / V.

14. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has a photostability less than or equal to about 5%.

15. The electro-optic device according to claim 9, wherein the nonlinear optical chromophore has a polarizability greater than or equal to about 2OOxlO30m3.

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