Tuned, highly bright fluorescent materials composed of small molecule ionic lattices

Abstract

The present disclosure provides a charged dye of formula (I): m+ ) x (counter ion n- ) y (counterion receptor) z and formula (VI): (charged dye m- ) x (counter ion n+ ) y (counterion receptor) z The present invention relates to the design, formulation, preparation and optical properties of compounds of formula (I), m+ is a cationic dye and has a counterion n- is the anion and the counterion receptor is the counterion n- In the formula (VI), m, n, x, and y are integers equal to or greater than 1, and the product of x·n is equal to the product of m·y. m- is an anionic dye and the counterion n+ is the cation and the counterion receptor is the counterion n+ where m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

Description

[Technical field]

[0001] This application claims priority under 35 U.S.C. 119 to U.S. Provisional Application No. 62 / 641,281, entitled “COLOR MATCHED AND BRIGHT FLUORESCENT MATERIALS COMPOSED OF SMALL-MOLECULE IONIC LATTICES,” filed March 10, 2018, the contents of which are incorporated herein by reference in their entirety.

[0002] This invention was made with Government support under 1412401 awarded by the National Science Foundation. The Government has certain rights in this invention.

[0003] The present invention relates to the design and preparation of materials containing ionic dyes having their counterions bound in counterion-receptor complexes, and their use in optical materials. [Background technology]

[0004] Organic dyes with color and high brightness were discovered in 1848. Since their discovery, those skilled in the art have produced paints and pigments attempting to replicate the color and high brightness light emission of these dyes in solution. Despite their color and brightness properties in solution, the ability to prepare solid state forms of the organic dyes that retain these properties has been met with technical difficulties and unpredictability. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, a need exists for compositions and formulations that allow for the preparation of solid-state forms of organic dyes that reproduce the bright color and fluorescent attributes of their solution state. [Means for solving the problem]

[0006] Summary of the Invention In a first embodiment, the compound of formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) The compound is provided as follows: m+ is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n- The values ​​of m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0007] In a second aspect, a formulation is provided, comprising the compound of formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) A formulation is provided that includes the compound of formula: m+ is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n- The values ​​of m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0008] In a third aspect, a method for producing a material having high brightness light emission properties is provided, the method comprising the steps of: a first step of mixing a solution of a cationic dye and a counteranion with an anion receptor to form a compound of formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) forming a first mixture comprising a compound of the formula: m+ is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n-The values ​​of m, n, x, and y are integers equal to or greater than 1, and the product of x·n is the same as the product of m·y. The second step is concentrating the first mixture to form a material having light-emitting units in a solid state. The materials thus produced can be powders, amorphous solids, thin films, crystals, microparticles, polymer composites, nanoparticles, and colloids of microparticles and nanoparticles.

[0009] In a fourth embodiment, the compound of formula (VI): (Charged dyes m- ) x (Counter ion n+ ) y (Counterion receptor) z (VI) The compound is provided as follows: m- is an anionic dye and the counterion n+ is a cation and the counterion receptor is a counterion n+ m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0010] In a fifth embodiment, the compound of formula (VI): (Charged dyes m- ) x (Counter ion n+ ) y (Counterion receptor) z (VI) A formulation is disclosed that includes the compound of formula (I). m- is an anionic dye and the counterion n+ is a cation and the counterion receptor is a counterion n+ m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0011] In a sixth aspect, a method for producing a material having high brightness light emission properties is disclosed. The method includes several steps. The first step includes preparing a first mixture including a compound according to the fourth aspect or a formulation according to the fifth aspect. The second step includes concentrating the first mixture to form a material having light emitting units in a solid state.

[0012] In a seventh aspect, a method of detecting a substance is disclosed. The method includes several steps. The first step includes contacting the substance with any of the compounds, formulations or materials according to any of the previous aspects. The second step includes measuring a change in at least one spectral property in any of the compounds, formulations or materials of the substance alone or the mixture as a result of the contacting step with the compound, formulation or material alone. The substance is detected by a change in at least one spectral property in any of the compounds, formulations or materials as a result of the measuring step of the mixture.

[0013] In an eighth aspect, a method for adding light absorption and emission to a polymer is disclosed. The method includes several steps. The first step includes providing a polymer. The second step includes contacting the polymer with a SMILES material.

[0014] In a ninth aspect, a method for staining a biological material is provided. The method comprises several steps. A first step comprises providing a biological material. A second step comprises contacting the biological material with microparticles or nanoparticles comprising a SMILES material.

[0015] In a tenth aspect, a method for improving the photostability of an ionic dye is provided. The method includes several steps. A first step includes providing an ionic dye. A second step includes converting the ionic dye into a SMILES material.

[0016] In an eleventh aspect, a method for improving the solubility and miscibility of an ionic dye with a polymer and a non-polar solvent is provided. The method includes several steps. The first step includes providing an ionic dye. The second step includes converting the ionic dye into a SMILES material.

[0017] In a twelfth aspect, a method for making a SMILES material with programmable light absorption and emission properties is provided. The method includes several steps. A first step includes providing an ionic dye. The ionic dye includes specific light absorption and emission properties. A second step includes converting the ionic dye into a SMILES material.

[0018] In a thirteenth aspect, a method for making a SMILES material with a programmable Stokes shift is provided. The method includes several steps. The first step includes providing a first ionic dye and a second ionic dye. The second step includes mixing the first ionic dye and the second ionic dye together to form a first mixture. The third step includes converting the first mixture into a SMILES material, in which the first ionic dye is an energy donor and the second ionic dye is an energy acceptor, allowing light emission by the first ionic dye and light absorption by the second ionic dye.

[0019] In a fourteenth aspect, a method is provided for making a SMILES material with programmable absorption and emission at different wavelengths with different relative intensities. The method includes several steps. A first step includes providing at least two ionic dyes. A second step includes mixing the at least two ionic dyes together to form a first mixture. A third step includes converting the first mixture into a SMILES material, the at least two ionic dyes having programmable absorption and emission at different wavelengths with different relative intensities.

[0020] In a fifteenth aspect, a method for making a SMILES material with a programmable light emission decay rate is provided. The method includes several steps. The first step includes providing a plurality of ionic dyes. The second step includes mixing the plurality of ionic dyes together to form a first mixture. The third step includes converting the mixture into a SMILES material. The plurality of ionic dyes includes a first ionic dye acting as a light absorbing energy donor in the SMILES material, any intermediate dyes acting simultaneously as an energy acceptor and an energy donor, and a final ionic dye acting as an energy accepting light emitter, allowing light absorption by the first ionic dye, pass energy through any intermediate dyes, and light emission by the final ionic dye. [Brief description of the drawings]

[0021] [Figure 1A] FIG. 1 shows exemplary cationic dyes and their counterions (anions, X−) that are densely packed in the solid, distorting absorption and quenching light emission. [Figure 1B] FIG. 1 illustrates an example separation grating that provides an opportunity to salvage optical properties. [Figure 1C] FIG. 1 shows that exemplary small molecule separated lattices (SMILES) can be generated using anion-binding macrocycles, such as cyanostars, for spatial and electrical separation of cationic dyes. [Figure 2A] FIG. 1 shows an exemplary absorption spectrum of Rhodamine B perchlorate in solution phase (dashed line, 1 μM, CH2Cl2). [Figure 2B] FIG. 1 shows an exemplary excitation and light emission spectrum of Rhodamine B perchlorate in solution phase (dashed line, 1 μM, CH 2 Cl 2 ). [Figure 2C] FIG. 1 shows exemplary solid-state absorption spectra for Rhodamine B perchlorate alone (dotted line) and configured as a FL-SMILES thin film (solid line). [Figure 2D]FIG. 1 shows exemplary solid-state excitation and photoemission spectra for Rhodamine B perchlorate alone (dotted line) and configured as a FL-SMILES thin film (solid line). Thin film conditions: 20 μL of 2 mM CH2Cl2 solution, 2000 RPM, glass slide for 15 seconds. [Figure 2E] 1A-1C are exemplary images of rhodamine 3B perchlorate (left) and FL-SMILES (right) under ambient conditions. [Figure 2F] 1 is an exemplary image of rhodamine perchlorate 3B complexed with FL-SMILES under UV light. [Figure 3A] FIG. 1 is a solution absorption spectrum of ethyl violet (CH2Cl2). [Figure 3B] FIG. 1 shows the absorption spectra of ethyl violet in a thin film (dotted line) and in an AB-SMILES material (solid line). [Figure 3C] Thin films of ethyl violet in AB-SMILES with spatially homogeneous coloration. [Figure 3D] This is a thin film of ethyl violet alone. [Figure 4] Charge packing as seen in the crystal structure of the FL-SMILES compound [(cyanostar)2(PF6)(DIOC2)]. Crystals grown from solution contain a 2:1 ratio of cyanostar to DIOC2·PF6. [Diagram 5] FIG. 1 is a diagram of exemplary fluorophores used to generate SMILES materials with cyanostars. [Figure 6] FIG. 2 is a diagram of an exemplary control compound. [Figure 7] FIG. 11. Exemplary cyano star analogs that also form FL-SMILES materials with Rhodamine 3B·ClO4. [Figure 8] 1 is an energy content plot outlining the electrical windows defined by various anion receptor complexes. The energies are estimated from the redox potential and optical band gap. [Figure 9A]1 is an exemplary micrograph of microparticles of FL-SMILES[(cyanostar)2(BF4)(DAOTA)]. [Figure 9B] 1 is an exemplary micrograph of microparticles of FL-SMILES [(cyanostar)2(BF4)(oxazine 720)]. [Figure 10A] 1 is an exemplary photographic image showing polystyrene material stained with Rhodamine 3B perchlorate and with the corresponding FL-SMILES [(Cyanostar)2(ClO4)(Rhodamine 3B)]. [Figure 10B] An exemplary photographic image under UV light illumination showing fluorescence emerging only from the sample stained with FL-SMILES [(cyanostar)2(ClO4)(rhodamine 3B)] (right). [Figure 11] Polymer stained with FL-SMILES [(cyanostar)2(ClO4)(rhodamine 3B)] prepared according to Method I in the Examples. [Figure 12] Polymer stained with FL-SMILES [(cyanostar)2(ClO4)(rhodamine 3B)] prepared according to Method II in the Examples. [Figure 13-1] FIG. 1 is a schematic diagram of FL-SMILES materials. [Figure 13-2] FIG. 1 is a schematic diagram of FL-SMILES materials. [Figure 13-3] FIG. 1 is a schematic diagram of FL-SMILES materials. [Figure 14-1] FIG. 1 is a schematic diagram of AB-SMILES materials. [Figure 14-2] FIG. 1 is a schematic diagram of AB-SMILES materials. [Figure 14-3] FIG. 1 is a schematic diagram of an AB-SMILES material. Note that formula (I-15) is a SMILES material that contains a dicationic dye [(cyanostar)2(HSO4)2(tetramethoxy-aminorhodamine))]). [Figure 15]Absorbance (left) and excitation and emission spectra (right) of FL-SMILES nanoparticles of [(cyanostar)2(ClO4)(rhodamine 3B)] present as colloids in aqueous solution stabilized by Triton X. [Figure 16] FIG. 2 is an exemplary reaction diagram for converting a neutral dye to a cationic dye by addition of acid (HX). [Figure 17A] FIG. 2 is an exemplary reaction diagram for converting a neutral dye to a cationic dye carrying one positive charge by alkylation. [Figure 17B] FIG. 1 is an exemplary reaction diagram for converting a neutral dye to a cationic dye having one and two positive charges by alkylation. [Figure 18] FIG. 2 is an exemplary reaction diagram for converting a neutral dye to an anionic dye by addition of a base (MOH). [Figure 19-1] FIG. 1 is a diagram of exemplary SMILES materials with anionic dyes: (VI-1) ([(dibenzo-18-crown-6)2(Cs+)(sulforhodamine B)]), (VI-2) ([(dibenzo-18-crown-6)2(Cs+)(BODIPY FL)]), (VI-3) ([(dibenzo-18-crown-6)2(Cs+)(fluorescein)]), (VI-4) ([(dibenzo-18-crown-6)2(Cs+)(7-diethylamino)coumarin-3-carboxylate)]), and (VI-5) ([(dibenzo-18-crown-6)2(Ca2+)(uranine)]), note that (VI-5) is a SMILES material that includes a dianionic dye. [Figure 19-2]FIG. 1 is a diagram of exemplary SMILES materials with anionic dyes: (VI-1) ([(dibenzo-18-crown-6)2(Cs+)(sulforhodamine B)]), (VI-2) ([(dibenzo-18-crown-6)2(Cs+)(BODIPY FL)]), (VI-3) ([(dibenzo-18-crown-6)2(Cs+)(fluorescein)]), (VI-4) ([(dibenzo-18-crown-6)2(Cs+)(7-diethylamino)coumarin-3-carboxylate)]), and (VI-5) ([(dibenzo-18-crown-6)2(Ca2+)(uranine)]), note that (VI-5) is a SMILES material that includes a dianionic dye. [Figure 20] FIG. 1 is an exemplary dynamic light scattering plot showing the hydrodynamic size distribution of SMILES nanoparticles using cationic dye R12 with 2 equivalents of cyanoster, counterion PF6-. [Figure 21] FIG. 1 shows an exemplary fluorescence spectrum of a SMILES nanoparticle containing cationic dye R12 mixed with two equivalents of a cyanostar and its PF6-counterion. [Figure 22] Images of exemplary organisms with SMILES nanoparticles: Fluorescence microscopy image of HeLa cells incubated with R12 nanoparticles (panel (a)); Fluorescence microscopy image of HeLa cells incubated with R-12-based SMILES nanoparticles (panel (b)); Image of the vasculature of a zebrafish larva with R-12-based SMILES nanoparticles (panel (c)); Image of the vasculature of a zebrafish larva with GFP fluorescence (panel (d)); Whitefield image of a zebrafish larva (panel (e)); and Image of the vasculature of a zebrafish larva with R-12-based SMILES nanoparticles and GFP fluorescence overlay (panel (f)). [Diagram 23] FIG. 1 shows exemplary spectral data demonstrating the improved photostability of dyes when incorporated into SMILES materials. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The present disclosure is based on the discovery of a new type of optical material named SMILES materials (Small Molecule Isolation LatticES), illustrated in FIG. 1. SMILES materials include formulations that have the high fluorescence intensity and / or toning properties of isolated ionic organic dyes, measured under dilute conditions, e.g. in solution or at low concentration in polymer complexes. When SMILES materials exhibit the high fluorescence intensity and toning properties of isolated organic dyes, they are named fluorescent SMILES (FL-SMILES), illustrated in FIG. 2. When SMILES materials only exhibit the toning properties of isolated organic dyes, they are named light absorbing SMILES (AB-SMILES), illustrated in FIG. 3. SMILES materials are obtained by mixing ionic dyes and their counterions with suitable chelator ligands to form ionic lattices (FIG. 4). SMILES materials can be rapidly prepared from many cationic dyes (FIG. 5) and dye classes with known solution-state spectral color and / or light emission properties to provide formulations with tuned solid-state materials and / or fluorescent solid-state materials. In the resulting ionic lattice of the material (FIG. 4), the ionic dyes are spatially separated from one another. Without being limited to any particular theory of operation or mechanism of action, the use of control compounds (FIG. 6) suggests that this spatial separation in the material formulation is believed to aid in creating materials with tuned light absorption and / or enhanced light emission. SMILES materials can be from a range of suitable chelator ligands (FIGS. 6 and 7). Without being limited to any particular theory of operation or mechanism of action, the electrical separation of ionic dyes defined by energy content is believed to aid in creating materials with tuned light absorption and / or enhanced light emission (FIG. 8). Light emission in the FL-SMILES materials is seen to be orders of magnitude larger than for the solid-state preparation of the ionic dye alone, as exemplified by the 25-fold increase in intensity seen in FL-SMILES constructed from the cationic dye rhodamine 3B (Figure 2D).SMILES materials are powders (FIG. 9), amorphous solids (FIGS. 2E and 2F), thin films (FIG. 3C), crystals (FIG. 4), microparticles (FIG. 9), polymer composites (FIGS. 10, 11, and 12), nanoparticles, and colloids of microparticles and nanoparticles (FIG. 15). A range of materials are shown that exhibit the properties of FL-SMILES (FIG. 13) and AB-SMILES (FIG. 14). Ionic dyes can be generated by adding an acid (FIG. 16) and by alkylating (FIG. 17) to create cationic dyes, and by adding a base (FIG. 18) to create anionic dyes, for the purpose of creating SMILES materials. Anionic dyes can be used to create SMILES materials (FIG. 19) by mixing the anionic dye and its counterion with an appropriate chelator ligand. These and other preferred embodiments that provide robust SMILES materials with high fluorescence intensity and / or toning properties are disclosed herein. SMILES materials in any form can be used to add color to polymers (Figures 10, 11 and 12) simply by dissolving the SMILES material and the polymer to be colored in a good solvent and then removing the solvent. Another simple way to add color to polymers with SMILES materials (Figures 10, 11 and 12) is by simply dissolving the SMILES material in a heated polymer melt and cooling the resulting colored polymer. SMILES nanoparticles made using a cationic dye mixed with two equivalents of a cyanostar can be made on the order of 20 nm in size (Figure 20) and show a fluorescence spectrum (Figure 21) that can be used for biological imaging (Figure 22). Incorporation of the dye into the SMILES material is seen to improve the photostability of the dye (Figure 23).

[0023] <Definition> When introducing elements of aspects of the disclosure or specific embodiments, the articles "a," "an," "the," and "said" are intended to mean that there are one or more elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements. The term "or" means any one member of a particular list, and also includes combinations of any members of that list, unless otherwise specified.

[0024] As intended herein, the terms "substantially," "approximately," and "about," as well as similar terms, are intended to have a broad meaning in keeping with common and accepted usage in the art to which the subject matter of this disclosure pertains. It should be understood by those of skill in the art who review this disclosure that these terms are intended to enable the description of certain features as described and claimed without limiting the scope of these features to the precise numerical ranges given. Thus, these terms should be interpreted such that insubstantial or insignificant modifications or variations of the subject matter as described and claimed are considered to be within the scope of the invention as recited in the appended claims.

[0025] The compounds described herein may exhibit asymmetry and may be separated in optically active or racemic forms. Methods for preparing optically active forms include, for example, resolution of racemic forms or synthesis from optically active starting materials. Many geometric isomers of olefins, C=N double bonds, and the like may also exist in the compounds described herein, and all such stable isomers are contemplated herein. All chiral, diastereomeric, racemic forms, and all geometric isomeric forms of structures are contemplated, unless a specific stereochemistry or isomeric form is specifically indicated.

[0026] The compounds of the compositions and formulations disclosed herein may exist as salts. The term "salt" refers to a salt of a compound that is soluble or dispersible in water or oil. The salt may be prepared during the final isolation and purification of the compound, or may be prepared separately by reacting the amino group of the compound with a suitable acid. For example, the compound may be dissolved in a suitable solvent, such as, but not limited to, methanol and water, and treated with at least one equivalent of an acid, such as hydrochloric acid. The resulting salt may be precipitated, separated by filtration, and dried under reduced pressure. Alternatively, the solvent and excess acid may be removed under reduced pressure to provide the salt. Representative salts include acetate, adipate, alginate, citrate, aspartate, benzoate, benzenesulfonate, hydrogensulfate, butyrate, camphorate, camphorsulfonate, digluconate, glycerophosphate, hemisulfate, heptanoate, hexanoate, formate, isethionate, fumarate, lactate, maleate, methanesulfonate, naphthylenesulfonate, nicotinate, oxalate, pamoate, pectinate, persulfate, 3-phenylpropionate, picrate, oxalate, maleate, pivalate, propionate, succinate, tartrate, trichloroacetate, trifluoroacetate, glutamate, para-toluenesulfonate, undecanoate, hydrochloride, hydrobromide, sulfate, phosphate, and the like. The amino groups of the compounds may also be quaternized with alkyl chlorides, bromides, iodides, such as methyl, ethyl, propyl, isopropyl, butyl, lauryl, myristyl, stearyl, and the like.

[0027] Base addition salts may be prepared during the final isolation and purification of the compounds by reaction of a carboxyl group with a suitable base such as the hydroxide, carbonate, or bicarbonate of a metal cation, such as lithium, sodium, potassium, calcium, magnesium, or aluminum, or an organic primary, secondary, or tertiary amine. Quaternary amine salts derived from methylamine, dimethylamine, trimethylamine, triethylamine, diethylamine, ethylamine, tributylamine, pyridine, N,N-dimethylaniline, N-methylpiperidine, N-methylmorpholine, dicyclohexylamine, procaine, dibenzylamine, N,N-dibenzylphenethylamine, 1-ephenamine, and N,N'-dibenzylethylenediamine, ethylenediamine, ethanolamine, diethanolamine, piperidine, piperazine, and the like, are contemplated as being within the scope of the invention.

[0028] The term "substituted" as used herein means that any one or more hydrogens on the specified atom are replaced with a selection from the specified group, provided that the normal valence of the specified atom is not exceeded and that the substitution results in a stable compound. When the substituent is oxo (i.e., =O), two hydrogens on the atom are replaced. Oxo substituents do not occur on aromatic moieties. When a ring system (e.g., carbocyclic or heterocyclic) is said to be substituted with a carbonyl group or a double bond, it is intended that the carbonyl group or double bond is part of the ring (i.e., within the ring).

[0029] When a bond to a substituent is shown to bridge a bond connecting two atoms in a ring, such substituent may be bonded to any atom on the ring. When substituents are listed without indicating the atom through which such substituent is bonded to the remainder of the compound of a given formula, such substituent may be bonded through any atom in such substituent, provided that the resulting bond exists in a stable compound.

[0030] The term "hydroxy" as used herein refers to an -OH group. The term "oxo" as used herein refers to a =O group. The term "oxy" as used herein refers to an -O- group. The term "sulfonyl" as used herein refers to a -S(O)2- group. The term "carbonyl" as used herein refers to a -C(O)- group. The term "carboxy" as used herein refers to a -C(O)-OH group. The term "halo" or "halogen" as used herein refers to -Cl, -Br, -I or -F.

[0031] The term "alkenyl" as used herein refers to a straight or branched chain hydrocarbon group containing 2 to 10 carbons and containing at least one carbon-carbon double bond formed by the removal of two hydrogens. Representative examples of alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-1-heptenyl, and 3-decenyl.

[0032] The term "alkoxy" as used herein refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, trisdecyloxy, tetradecyloxy, and pentadecyloxy.

[0033] The term "alkyl" as used herein refers to a straight or branched chain hydrocarbon group containing 1 to 18 carbon atoms (eg, illustrative carbon numbers). Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0034] The term "alkyl-NH," as used herein, refers to an alkyl group, as defined herein, appended to the parent molecular moiety through a nitrogen atom.

[0035] The term "alkyl-NH-alkyl," as used herein, refers to an alkyl-NH group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein.

[0036] The term "aryl" as used herein means a phenyl group, or a bicyclic or tricyclic fused ring system. A bicyclic fused ring system is exemplified by a phenyl group attached to a parent molecular moiety and fused to a monocyclic cycloalkyl group, a phenyl group, a monocyclic heteroaryl group, or a monocyclic heterocycle, as defined herein. A tricyclic fused ring system is exemplified by an aryl bicyclic fused ring system, as defined herein, fused to a monocyclic cycloalkyl group, a phenyl group, a monocyclic heteroaryl group, or a monocyclic heterocycle, as defined herein. Representative examples of aryl include, but are not limited to, anthracenyl, azulenyl, fluorenyl, indanyl, indenyl, naphthyl, phenyl, and tetrahydronaphthyl.

[0037] The term "cycloalkyl" as used herein refers to a monocyclic, bicyclic or tricyclic ring system. Monocyclic ring systems are exemplified by saturated cyclic hydrocarbon groups containing 3 to 8 carbon atoms. Examples of monocyclic ring systems include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Bicyclic fused ring systems are exemplified by a cycloalkyl group attached to a parent molecular moiety, which is fused to an additional cycloalkyl group as defined herein, a phenyl group as defined herein, a heteroaryl group as defined herein, or a heterocycle as defined herein. Tricyclic fused ring systems are exemplified by a cycloalkyl bicyclic fused ring system fused to an additional cycloalkyl group as defined herein, a phenyl group as defined herein, a heteroaryl group as defined herein, or a heterocycle as defined herein. Bicyclic ring systems are also exemplified by bridged monocyclic ring systems in which two non-adjacent carbon atoms of a carbon atom of a monocyclic ring are connected by an alkylene bridge between one carbon atom and three additional carbon atoms. Representative examples of bicyclic ring systems include, but are not limited to, bicyclo[3.1.1]heptane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, and bicyclo[4.2.1]nonane. Tricyclic ring systems are also exemplified by bicyclic ring systems in which two non-adjacent carbon atoms of the bicyclic ring are joined by a bond or by an alkylene bridge between one carbon atom and three carbon atoms. Representative examples of tricyclic ring systems include, but are not limited to, tricyclo[3.3.1.03,7]nonane and tricyclo[3.3.1.13,7]decane (adamantane).

[0038] The term "haloalkyl" as used herein refers to at least one halogen, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein. Representative examples of haloalkyl include, but are not limited to, chloromethyl, 2-fluoroethyl, trifluoromethyl, pentafluoroethyl, and 2-chloro-3-fluoropentyl.

[0039] The term "heteroaryl" as used herein refers to an aromatic monocyclic ring or aromatic bicyclic ring system. An aromatic monocyclic ring is a 5- or 6-membered ring containing at least one heteroatom independently selected from the group consisting of N, O, and S. A 5-membered aromatic monocyclic ring has two double bonds, and a 6-membered aromatic monocyclic ring has three double bonds. A bicyclic heteroaryl group is also exemplified by a monocyclic heteroaryl ring attached to a parent molecular moiety and fused to a monocyclic cycloalkyl group, as defined herein, a monocyclic aryl group, as defined herein, a monocyclic heteroaryl group, as defined herein, or a monocyclic heterocycle, as defined herein. Representative examples of heteroaryl include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiazolyl, benzothienyl, benzoxazolyl, furyl, imidazolyl, indazolyl, indolyl, indolizinyl, isobenzofuranyl, isoindolyl, isoxazolyl, isoquinolinyl, isothiazolyl, naphthyridinyl, oxadiazolyl, oxazolyl, phthalazinyl, pyridinyl, pyridazinyl, pyridyl, pyrimidinyl, pyrazinyl, pyrazolyl, pyrrolyl, quinolinyl, quinolidinyl, quinoxalinyl, quinazolinyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, triazolyl, and triazinyl.

[0040] The term "heterocycle" as used herein refers to a non-aromatic monocyclic ring or a non-aromatic bicyclic ring. Non-aromatic monocyclic rings are 3-, 4-, 5-, 6-, 7-, and 8-membered rings that contain at least one heteroatom independently selected from the group consisting of N, O, and S. Representative examples of monocyclic ring systems include, but are not limited to, azetidinyl, aziridinyl, diazepinyl, dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, oxazolinyl, oxazolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydro-2H-pyranyl, tetrahydro-2H-pyran-2-yl, tetrahydro-2H-pyran-4-yl, tetrahydrothienyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1-dioxidothiomorpholinyl (thiomorpholinesulfone), and thiopyranyl. A bicyclic heterocycle is exemplified by a monocyclic heterocycle attached to a parent molecular moiety and fused to a monocyclic cycloalkyl group, a monocyclic aryl group, a monocyclic heteroaryl group, or a monocyclic heterocycle, as defined herein. Bicyclic ring systems are also exemplified by bridged monocyclic ring systems in which two non-adjacent atoms of a monocyclic ring are joined by a bridge between one atom and three atoms selected from the group consisting of carbon, nitrogen, and oxygen. Representative examples of bicyclic ring systems include, but are not limited to, benzopyranyl, benzothiopyranyl, benzodioxinyl, 1,3-benzodioxolyl, cinnolinyl, 1,5-diazocanyl, 3,9-diaza-bicyclo[4.2.1]non-9-yl, 3,7-diazabicyclo[3.3.1]nonane, octahydropyrrolo[3,4-c]pyrrole, indolinyl, isoindolinyl, 2,3,4,5-tetrahydro-1H-benzo[c]azepine, 2,3,4,5-tetrahydro-1H-benzo[b]azepine, 2,3,4,5-tetrahydro-1H-benzo[d]azepine, tetrahydroisoquinolinyl, and tetrahydroquinolinyl.

[0041] The term "macrocycle" refers to a cyclic ring system that includes at least three cyclic rings covalently linked together.

[0042] The term "heteromacrocycle" refers to a macrocycle having at least one non-carbon atom included in the macrocycle structure.

[0043] The term "light absorbing unit" refers to a chromophore having an atom or group of atoms whose presence determines the absorption of light in the UV, visible and / or near infrared regions of the electromagnetic spectrum.

[0044] The term "light emitting unit" refers to a fluorophore having an atom or group of atoms whose presence affects absorption of light in the UV, visible and / or near infrared regions of the electromagnetic spectrum.

[0045] The terms "light absorbing and light emitting units" refer to fluorophores that have an atom or group of atoms whose presence determines the absorption of light in the UV, visible and / or near infrared regions of the electromagnetic spectrum.

[0046] Chemical structures described herein are named according to IUPAC nomenclature rules, including common names and abbreviations that are acceptable in the art, where appropriate. IUPAC nomenclature can be derived from software programs for drawing chemical structures, such as ChemDraw® (PerkinElmer, Inc.), ChemDoodle® (iChemLabs, LLC) and Marvin (ChemAxon Ltd.). Chemical structures are controlling in this disclosure to the extent that a chemical name is a misnomer or otherwise inconsistent with the chemical structures disclosed herein.

[0047] <Class of ionic dyes> The present invention uses ionic dyes that are naturally occurring or from certain dye classes of neutral dyes, including styryl, xanthene, triangulenium, oxazine, triarylmethane, cyanine, acridine, fluoroone, phenanthridine, polyaromatic hydrocarbon, imide, BODIPY, coumarin and squaraine, or combinations thereof, which can be converted to cationic or anionic dyes under appropriate conditions as disclosed herein.

[0048] For example, a neutral dye can be converted to a cationic dye with the addition of an acid, HX, where X is an anionic counterion (Figure 16). In another example, a neutral dye can be converted to a cationic dye by introducing one or more cationic sites into the neutral dye (Figures 17A, 17B).

[0049] Similarly, a neutral dye can be converted to an anionic dye with the addition of the base MOH, where M is an anionic counterion (Figure 18). In another example, a neutral dye can be converted to an anionic dye by introducing one or more anionic moieties into the neutral dye.

[0050] For example, an anionic dye can be converted to a cationic dye by introducing two or more cationic sites into the anionic dye.

[0051] For example, a cationic dye can be converted to an anionic dye by introducing two or more anionic sites into the cationic dye.

[0052] <SMILES compounds from cationic dyes> In a first embodiment, the compound of formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) The compound is provided as follows: m+is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n- The values ​​of m, n, x, and y are integers of 1 or greater.

[0053] In the first respect, the compounds of formula (I) are prepared with a natural cationic dye, or with a neutral dye that has been initially converted to a cationic dye, or with an anionic dye that has been converted to a cationic dye. Thus, the charged dyes of formula (I) m+ (i.e., cationic dyes) can be prepared by one of the following methods: In one method, neutral dyes are prepared by reacting an acid, HX, where X is the counter ion in the compound of formula (I), with n- The addition of m+ In some preferred embodiments, the neutral dye can be converted to a charged dye. m+ by converting the charged dye of formula (I) m+ The preparation of comprises adding an acid HX, where the acid HX is selected from the group consisting of HPF6, HBF4 and HClO4, to a neutral dye.

[0054] In another method, the neutral dye is converted to a charged dye by introducing a cationic moiety into the neutral dye. m+ In some preferred embodiments, the neutral dye is converted to a charged dye by introducing a cationic moiety into the neutral dye. m+ by converting the charged dye of formula (I) m+ The preparation of the neutral dye is carried out by converting the free base moiety of the dye to RY, where R is an alkyl moiety and Y is a counter ion in the compound of formula (I). n- The alkyl moiety R can be any alkyl moiety known in the art. Preferably, the alkyl moiety R is an alkyl (e.g., C1-C 18 ), alkyl-substituted phenyl derivatives, substituted glycol derivatives, alkenyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, -OR 6 , -N(R 7 R8 ), -CO2R 9 , -C(O)-N(R 10 R 11 )(wherein, R 6 , R 7 , R 8 , R 9 , R 10 and R 11 may each in particular be selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen) or a combination thereof.

[0055] In another method, anionic dyes can be converted to cationic dyes by two acid additions, or two alkylations, or combinations thereof, such as acid addition and alkylation.

[0056] In a second respect, the counterion receptor is a heteromacrocycle. In a second respect, the heteromacrocycle is represented by formulas (II), (III), (IV), and (V):

[0057] [ka] is selected from.

[0058] R in formula (II), R, R′ and R″ in formula (III), R in formula (IV) 1 , R 2 , R 3 , R 4 and R 5 and R1, R2, R3 and R4 in formula (V) are each independently an alkyl group (e.g., C1 to C 18 ), alkyl substituted phenyl derivatives, and substituted glycol derivatives, alkenyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, -OR 6 , -N(R 7 R 8 ), -CO2R 9 , -C(O)-N(R 10R 11 )(wherein, R 6 , R 7 , R 8 , R 9 , R 10 and R 11 R in formula (II) and R in formula (IV) are each in particular selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen) or combinations thereof. 1 , R 2 , R 3 , R 4 and R 5 R, R', and R'' in formula (III), and R1, R2, R3, and R4 in formula (V) can be selected independently of each other.

[0059] As regards the above aspect of the first embodiment, the anion can be any anion, provided that the anion is capable of forming a chelate complex with the counterion receptor of formula (I). Preferably, the anion is BF4 - , ClO4 - , PF6 - , N(SO2CF3)2 - , N(SO2C2F5)2 - , CH3SO3 - , CF3SO3 - , AsO4 3- , HAsO4 2- , H2AsO4 - , AsF6 - , AlCl4 - , PO4 3- , HPO4 2- , H2PO4 - , SO4 2- , HSO4 - , Cl - , Br - , I - , Cyanide, BrO4 - , IO4 - , F - , HF2 - , TcO4 - , RPO4 2- , R2PO4- , RSO3 - , SCN - , N3 - , I3 - , CO3 2- , HCO3 - , P2O7 4- , HP2O7 3- , H2P2O7 2- , H3P2O7 - , R.B.F.3 - (wherein R includes a substituent). Certain anions excluded from the anion-containing formula (I) are selected from the group consisting of F5-TPB - , tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate, Ar4B - (wherein Ar is aryl), TRISPHAT - , BINPHAT - is selected from the group consisting of:

[0060] In a further respect, the possibility of partial, complete or photoinduced electron transfer between the cationic dye and the counterion receptor sacrifices the retention of the toning and spectral light emission properties of the cationic dye when present in the composition of formula (I).Without being limited to any particular theory of operation or mechanism of action, it is believed that partial or complete electron transfer between the cationic dye and the counterion receptor from the resulting composition of formula (I) is possible when energetically favorable as predicted by the principles of orbital mixing as defined by Marcus electron transfer theory or quantum mechanics. An example of such a phenomenon is disclosed in Bo Qiao, Brandon E. Hirsch, Semin Lee, Maren Pink, Chun-Hsing Chen, Bo W. Laursen and Amar H. Flood, "Ion-Pair Oligomerization of Chromogenic Triangulenium Cations with Cyanostar-Modified Anions That Controls Emission in Hierarchical Materials", J.Am.Chem.Soc. 2017, 139:6226-6233, the contents of which are hereby incorporated by reference in their entirety. In this case, partial or complete electron transfer is believed to occur between the highest occupied molecular orbital in the cationic dye and the highest occupied molecular orbital in the counterion receptor. Thus, in the third respect, the cationic dye of the compound of formula (I) includes a cationic dye having a light absorbing unit, or a cationic dye having both a light absorbing unit and a light emitting unit.

[0061] In a fourth respect, the compound of formula (I) comprising a cationic dye is selected from the group of dye classes consisting of cationic styryl, cationic xanthene, cationic triangulenium, cationic oxazine, triarylmethane, cationic cyanine, cationic acridine, cationic fluoronone, cationic phenanthridine, cationic polyaromatic hydrocarbon, cationic imide, cationic BODIPY, cationic coumarin and cationic squaraine, or combinations thereof. Exemplary cationic dyes include those having the structure:

[0062] [ka] Examples of the compound include those having the following structure:

[0063] According to a still further aspect, the compound of formula (I) is represented by the formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11), formula (I-12), formula (I-13) and formula (I-14):

[0064] [ka] TIFF0007608170000004.tif149162TIFF0007608170000005.tif150158TIFF000760 8170000006.tif149168TIFF0007608170000007.tif145163TIFF0007608170000008. TIFF0007608170000009.tif199163TIFF0007608170000010.tif200164TIFF0007608170000011.tif201163TIFF0007608170000012.tif67164.

[0065] <Cationic dye SMILES blend> In a second aspect, a formulation is provided. The formulation has formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) The compounds include: m+ is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n- The values ​​of m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0066] In a first respect, the counterion receptor is a heteromacrocycle. In a second respect, the heteromacrocycle is represented by formulas (II), (III), (IV), and (V):

[0067] [ka] Or a combination thereof.

[0068] R in formula (II), R, R′ and R″ in formula (III), R in formula (IV) 1 , R 2 , R 3 , R 4 and R 5 and R1, R2, R3 and R4 in formula (V) are each independently an alkyl group (e.g., C1 to C 18 ), alkyl substituted phenyl derivatives, and substituted glycol derivatives, alkenyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, -OR 6 , -N(R 7 R 8 ), -CO2R 9 , -C(O)-N(R 10 R 11 )(wherein, R 6 , R 7 , R 8 , R 9 , R 10 and R 11R in formula (II) and R in formula (IV) are each in particular selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen) or combinations thereof. 1 , R 2 , R 3 , R 4 and R 5 R, R', and R'' in formula (III), and R1, R2, R3, and R4 in formula (V) can be selected independently of each other.

[0069] In the third aspect of the formulation, the preferred anion is BF4 - , ClO4 - , PF6 - , N(SO2CF3)2 - , N(SO2C2F5)2 - , CH3SO3 - , CF3SO3 - , AsO4 3- , HAsO4 2- , H2AsO4 - , AsF6 - , AlCl4 - , PO4 3- , HPO4 2- , H2PO4 - , SO4 2- , HSO4 - , Cl - , Br - , I - , Cyanide, BrO4 - , IO4 - , F - , HF2 - , TcO4 - , RPO4 2- , R2PO4 - , RSO3 - , SCN - , N3 - , I3 - , CO3 2- , HCO3 - , P2O7 4- , HP2O7 3- , H2P2O7 2- , H3P2O7- , R.B.F.3 - (wherein R includes a substituent). Certain anions excluded from the anion-containing formula (I) are selected from the group consisting of F5-TPB - , tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate, Ar4B - (wherein Ar is aryl), TRISPHAT - , BINPHAT - In another aspect of the formulation, the cationic dye is selected from the group consisting of m+ Partial, complete or photoinduced electron transfer between the cation and the counterion receptor does not occur according to the rules governed by Marcus theory and quantum mechanics. According to yet another aspect of the formulation, the formulation comprises a cation represented by formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11), formula (I-12), formula (I-13), formula (I-14) and formula (I-15):

[0070] [ka] TIFF0007608170000015.tif153158TIFF0007608170000016.tif149164TIFF000760817 0000017.tif148163TIFF0007608170000018.tif147164TIFF0007608170000019.tif148 158TIFF0007608170000020.tif204159TIFF0007608170000021.tif198163TIFF0007608170000022.tif201163TIFF0007608170000023.tif59164.

[0071] According to yet another aspect of the formulation, cationic dyes m+ is the counter ion n-According to yet another aspect of the formulation, the cationic dye absorbs light at a wavelength longer than the absorption wavelength of the complex formed between the cationic dye and the counterion receptor. m+ is the counter ion n- The compound of formula (I) emits light at a wavelength longer than the absorption wavelength of the complex formed between the ion receptor and the counterion receptor. Still according to a further aspect of the formulation, the compound of formula (I) comprises a light-emitting unit. Still according to a further aspect of the formulation, the formulation comprises a solid-state material. In this respect, the solid-state material is preferably selected from the group consisting of powders, amorphous solids, thin films, crystals, microparticles, polymer complexes, nanoparticles, and colloids of microparticles and nanoparticles. In addition, and according to the formulation, the formulation is prepared from a solution comprising a solvent of low polarity.

[0072] <Preparation of SMILES material of cationic dye> SMILES materials can be easily prepared by mixing the correct ratios of cationic dye and counteranion with a counterion receptor to produce the material in solid state form.

[0073] Thus, in a third aspect, there is provided a method for producing a material having high brightness light emission properties, the method comprising the steps of: a first step mixing a solution of a cationic dye and a counteranion with an anion receptor to form a compound of formula (I): (Charged dyes m+ ) x (Counter ion n- ) y (Counterion receptor) z (I) forming a first mixture comprising the compound of Charged Dyes m+ is a cationic dye and the counterion n- is the anion and the counterion receptor is the counterion n- The values ​​of m, n, x, and y are integers equal to or greater than 1, and the product of x·n is equal to the product of m·y. The second step is concentrating the first mixture to form a material having light-emitting units in a solid state.

[0074] In a first respect, the counterion receptor is a heteromacrocycle. In a second respect, the heteromacrocycle is represented by formulas (II), (III), (IV), and (V):

[0075] [ka] and combinations thereof.

[0076] R in formula (II), R, R′ and R″ in formula (III), R in formula (IV) 1 , R 2 , R 3 , R 4 and R 5 and R1, R2, R3 and R4 in formula (V) are each independently an alkyl group (e.g., C1 to C 18 ), alkyl substituted phenyl derivatives, and substituted glycol derivatives, alkenyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, -OR 6 , -N(R 7 R 8 ), -CO2R 9 , -C(O)-N(R 10 R 11 )(wherein, R 6 , R 7 , R 8 , R 9 , R 10 and R 11 R in formula (II) and R in formula (IV) are each in particular selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen) or combinations thereof. 1 , R 2 , R 3 , R 4 and R 5 R, R', and R'' in formula (III), and R1, R2, R3, and R4 in formula (V) can be selected independently of each other.

[0077] In the third aspect of the method, the preferred anion is BF4 - , ClO4 - , PF6 - , N(SO2CF3)2 - , N(SO2C2F5)2 - , CH3SO3 - , CF3SO3 - , AsO4 3- , HAsO4 2- , H2AsO4 - , AsF6 - , AlCl4 - , PO4 3- , HPO4 2- , H2PO4 - , SO4 2- , HSO4 - , Cl - , Br - , I - , Cyanide, BrO4 - , IO4 - , F - , HF2 - , TcO4 - , RPO4 2- , R2PO4 - , RSO3 - , SCN - , N3 - , I3 - , CO3 2- , HCO3 - , P2O7 4- , HP2O7 3- , H2P2O7 2- , H3P2O7 - , R.B.F.3 - (wherein R includes a substituent). Certain anions excluded from the anion-containing formula (I) are selected from the group consisting of F5-TPB - , tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]borate, Ar4B - (wherein Ar is aryl), TRISPHAT - , BINPHAT - In another aspect of the formulation, the cationic dye is selected from the group consisting of m+Partial, complete or photoinduced electron transfer between the cation and the counterion receptor does not occur according to the rules governed by Marcus theory and quantum mechanics. According to yet a further aspect of the method, the formulation comprises a cation represented by formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I-6), formula (I-7), formula (I-8), formula (I-9), formula (I-10), formula (I-11), formula (I-12), formula (I-13), formula (I-14) and formula (I-15):

[0078] [ka] TIFF0007608170000026.tif146162TIFF0007608170000027.tif147162TIFF000760817 0000028.tif147156TIFF0007608170000029.tif153161TIFF0007608170000030.tif151 159TIFF0007608170000031.tif198163TIFF0007608170000032.tif199161TIFF0007608170000033.tif201165TIFF0007608170000034.tif62164.

[0079] According to yet a further aspect of the method, a cationic dye m+ is the counter ion n- According to yet a further aspect of the method, the cationic dye absorbs light at a wavelength longer than the absorption wavelength of the complex formed between the cationic dye and the counterion receptor. m+ is the counter ion n-The compound of formula (I) emits light at a wavelength longer than the absorption wavelength of the complex formed between the ion receptor and the counterion receptor. Still according to a further aspect of the method, the compound of formula (I) comprises a light-emitting unit. Still according to a further aspect of the method, the formulation comprises a solid-state material. In this regard, the solid-state material is preferably selected from the group consisting of powders, amorphous solids, thin films, crystals, microparticles, polymer composites, nanoparticles, and colloids of microparticles and nanoparticles. In addition and according to the method, the formulation is prepared from a solution containing a solvent with low polarity, or from a powder, or from a colloid. In one respect, the formulation comprises a colloid, which is a state of matter different from liquid, solution, and solid state.

[0080] <SMILES compounds from anionic dyes> In a fourth embodiment, the compound of formula (VI): (Charged dyes m- ) x (Counter ion n+ ) y (Counterion receptor) z (VI) The compound of formula (1) is provided.

[0081] Charged Dyes m- is an anionic dye and the counterion n+ is a cation and the counterion receptor is a counterion n+ m, n, x, and y are integers greater than or equal to 1, and the product of x·n is the same as the product of m·y.

[0082] In the first respect, the compound of formula (VI) is a charged dye. m- which is prepared by one of the following methods: In the first method, a neutral dye is reacted with a base MOH, where M is the counter ion in the compound of formula (VI): n+ The addition of m- In the second method, a neutral dye can be converted to a charged dye by introducing an anionic site into the neutral dye. m-In a preferred embodiment, the base MOH is LiOH, NaOH, KOH, CsOH, RbOH, Ca(OH), Ba(OH), Mg(OH), ammonium hydroxide (where ammonium is N(R) + where R is an alkyl group of the same or different composition.

[0083] In a second respect, the compound of formula (VI) comprises an anionic dye, the anionic dye being selected from a compound having a light absorbing unit and an anionic dye having both a light absorbing unit and a light emitting unit.

[0084] In a third respect, the compound of formula (VI) comprises an anionic dye, the anionic dye being selected from the group of dye classes consisting of anionic styryl, anionic xanthene, anionic triangulenium, anionic oxazine, anionic triarylmethane, anionic cyanine, anionic acridine, anionic fluorone, anionic phenanthridine, anionic polyaromatic hydrocarbon, anionic imide, anionic BODIPY, anionic coumarin and anionic squaraine, or combinations thereof.

[0085] In a fourth respect, the compound of formula (VI) comprises an anionic dye, the anionic dye being selected from the group consisting of the following members:

[0086] [ka] Selected from the group consisting of:

[0087] In a fifth aspect, the compound of formula (VI) includes a counterion receptor, and the counterion receptor is a heteromacrocycle. Preferred heteromacrocycles include those of formulae (VII) to (XIII):

[0088] [ka] The substituents R1, R2, R3 and R4 are all the same or different and are selected from alkyl (e.g., C1 to C 18 ), alkyl substituted phenyl derivatives, and substituted glycol derivatives, alkenyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, -OR 6 , -N(R 7 R 8 ), -CO2R 9 , -C(O)-N(R 10 R 11 )(wherein, R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is each in particular selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen) or a combination thereof.

[0089] Preferred cationic counterions of formula (VI) include Li + , Na + , K + , Cs + , ammonium cation N(R)4 + (wherein R is an alkyl group of the same or different composition), Rb + , Ca 2+ , B.A. 2+ , Mg 2+ , dicationic bis-ammonium cation (R 1 )3N + -(R 2 )-N(R 3 )3 + (In the formula, R 1 and R 3 are alkyl groups of the same or different composition, R 2In particular, the cations are selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocyclic, haloalkyl, or combinations thereof. A preferred cation is not tetra-phenylphosphonium, since a counterion must be bound to a counterion receptor. A preferred cation is not methylpyridinium, since a counterion must be inactive toward thermal or photoinduced electron transfer. Exemplary compounds of formula (VI) include those of formulas (VI-1), (VI-2), (VI-3), (VI-4), and (VI-5):

[0090] [ka] TIFF0007608170000038.tif181162 is an example.

[0091] In another aspect, the compound of formula (VI) comprises an anionic dye comprising a light absorbing unit. In this regard, a preferred embodiment comprises a counterion n+ The anionic dye comprises an anionic dye that absorbs light at a wavelength longer than the absorption wavelength of the complex formed between the anionic dye and the counterion receptor. A preferred embodiment comprises an anionic dye comprising a light absorbing unit that has light absorption characteristics that, under dilute conditions, reproduce the light absorption characteristics (position and width of the absorption band) of the anionic dye alone. In yet another further embodiment, the anionic dye comprises a light absorbing unit and a light emitting unit. In yet another further embodiment, the anionic dye comprises an anionic dye that absorbs light at a wavelength longer than the absorption wavelength of the complex formed between the anionic dye and the counterion receptor. n+ The anionic dye absorbs and emits light at a wavelength longer than the absorption wavelength of the complex formed between the anionic dye and the counterion receptor, where the electrical properties of the complex between the anionic dye and the counterion receptor do not result in partial or complete electron transfer, photoinduced electron transfer between the anionic dye and the counterion receptor, or generate new absorption or emission bands.

[0092] <Anionic dye SMILES blend> In a fifth embodiment, the compound of formula (VI): (Charged dyesm- ) x ·(Counter ion n+ ) y ·(Counter ion receptor) z (VI) A formulation comprising a compound of is disclosed. The charged dye m- is an anionic dye, the counter ion n+ is a cation, and the counter ion receptor is a binding ligand for the counter ion n+ . m, n, x, and y are integers of 1 or more, and the product of x·n is the same as the product of m·y.

[0093] In a first aspect, the formulation comprises a compound that is elucidated for each of the points disclosed for the compound of formula (VI). In a second aspect, the formulation comprises the electrical properties of a complex of an anionic dye and a counter ion receptor that do not result in partial or complete electron transfer, photoinduced electron transfer, or electrical mixing between the cationic dye and the counter ion receptor. In a third aspect, the formulation comprises a solid-state material. At this time, the solid-state material is selected from the group consisting of powders, amorphous solids, thin films, crystals, microparticles, polymer composites, nanoparticles, and colloids of microparticles and nanoparticles. In another aspect, the formulation is prepared from a solution, powder, or colloid. At this time, the formulation contains a colloid.

[0094] <Preparation of SMILES Material of Anionic Dye> In a sixth aspect, a method for producing a material having high-brightness light emission characteristics is disclosed. The method includes several steps. The first step includes preparing a first mixture comprising a compound according to the fourth aspect or a formulation according to the fifth aspect. The second step includes concentrating the first mixture to form a material having a light-emitting unit in a solid state.

[0095] <Further Methods and Applications with SMILES Materials> In a seventh aspect, a method for detecting a substance is disclosed. The method includes several steps. The first step includes contacting the substance with any of the compounds, formulations or materials according to any of the previous aspects. The second step includes measuring a change in at least one spectral property in any of the compounds, formulations or materials of the mixture as a result of the contacting step with the substance alone or the compound, formulation or material alone. The substance is detected by a change in at least one spectral property in any of the compounds, formulations or materials as a result of the measuring step with the mixture.

[0096] In an eighth aspect, a method for adding light absorption and emission to a polymer is disclosed. The method includes several steps. The first step includes providing a polymer. The second step includes contacting the polymer with a SMILES material.

[0097] In a ninth aspect, a method for staining a biological material is provided. The method comprises several steps. A first step comprises providing a biological material. A second step comprises contacting the biological material with microparticles or nanoparticles comprising a SMILES material.

[0098] In a tenth aspect, a method for improving the photostability of an ionic dye is provided. The method includes several steps. A first step includes providing an ionic dye. A second step includes converting the ionic dye into a SMILES material.

[0099] In an eleventh aspect, a method for improving the solubility and miscibility of an ionic dye with a polymer and a non-polar solvent is provided. The method includes several steps. The first step includes providing an ionic dye. The second step includes converting the ionic dye into a SMILES material.

[0100] In a twelfth aspect, a method for making a SMILES material with programmable light absorption and emission properties is provided. The method includes several steps. A first step includes providing an ionic dye. The ionic dye includes specific light absorption and emission properties. A second step includes converting the ionic dye into a SMILES material.

[0101] In a thirteenth aspect, a method for making a SMILES material with a programmable Stokes shift is provided. The method includes several steps. The first step includes providing a first ionic dye and a second ionic dye. The second step includes mixing the first ionic dye and the second ionic dye together to form a first mixture. The third step includes converting the first mixture into a SMILES material, in which the first ionic dye is an energy donor and the second ionic dye is an energy acceptor, allowing light emission by the first ionic dye and light absorption by the second ionic dye.

[0102] In a fourteenth aspect, a method for making a SMILES material with programmable absorption and light emission at different wavelengths with different relative intensities is provided. The method includes several steps. A first step includes providing at least two ionic dyes. A second step includes mixing the at least two ionic dyes together to form a first mixture. A third step includes converting the first mixture into a SMILES material. The at least two ionic dyes have programmable absorption and light emission at different wavelengths with different relative intensities.

[0103] In a fifteenth aspect, a method for making a SMILES material with a programmable light emission decay rate is provided. The method includes several steps. The first step includes providing a plurality of ionic dyes. The second step includes mixing the plurality of ionic dyes together to form a first mixture. The third step includes converting the mixture into a SMILES material. The plurality of ionic dyes includes a first ionic dye acting as a light absorbing energy donor in the SMILES material, any intermediate dyes acting simultaneously as an energy acceptor and energy, and a final ionic dye acting as an energy accepting light emitter, allowing light absorption by the first ionic dye, pass energy through any intermediate dyes, and light emission by the final ionic dye. EXAMPLES

[0104] Example 1: Method for preparation of SMILES material A.1 SMILES dyes in solution SMILES materials were made by mixing an ionic dye as the salt of its counterion (e.g., rhodamine 3B perchlorate, 1 equivalent) with the correct number of equivalents of a counterion acceptor, e.g., 2 equivalents of cyanostar (FIG. 1C, compound IV, where R1=R2=R3=R4=R5=tert-butyl). In this method, a solution of a compound of formula (I) or (VI) (depending on the charge of the ionic dye, its counterion, and the counterion acceptor) (where the values ​​of m and n are integers equal to or greater than 1) is made.

[0105] To make a representative solution of a SMILES dye, the ionic dye as its salt was weighed and added to a flask. To this flask, 2 molar equivalents of a counterion acceptor compatible with SMILES (e.g., cyanostar, FIG. 1C) were added. Different molar equivalents of the counterion acceptor can be added to vary the values ​​of x, y, and z. A volume of solvent (e.g., dichloromethane) is added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for the ionic dye).

[0106] [Example 2] Preparation of SMILES material from cyanostar and rhodamine 3B A quantity of dry Rhodamine 3B perchlorate (6.1 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, Cyanostar (19.6 mg), were weighed out and added to the flask. A volume of dichloromethane (1 mL) was added to this dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum and the resulting powder was collected. A quantity (2.4 mg) of dry FL-SMILES powder [(Cyanostar)2(ClO4)(Rhodamine 3B)] was added to the flask. This solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then secured to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of a stock solution of FL-SMILES [(cyanostar)2(ClO4)(rhodamine3B)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing.

[0107] Example 3: Preparation of SMILES material from cyanostar and pyridine 1 A quantity of dry pyridine perchlorate 1 (5.7 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, Cyanostar (27.6 mg), were weighed out and added to the flask. A volume of dichloromethane (1 mL) was added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum and the resulting powder was collected. A quantity (2.2 mg) of dry FL-SMILES powder [(Cyanostar)2(ClO4)(Pyridine 1)] was added to the flask. The solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then secured to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of a stock solution of FL-SMILES [(cyanostar)2(ClO4)(pyridine1)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing.

[0108] [Example 4] Preparation of SMILES material from cyanostar and DAOTA A quantity of dry DAOTA tetrafluoroborate (5.7 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, cyanostar (23.0 mg), were weighed out and added to the flask. To this dry mixture, a volume of dichloromethane (1 mL) was added to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum, and the resulting powder was collected. A quantity (2.3 mg) of dry FL-SMILES powder [(cyanostar)2(BF4)(DAOTA)] was added to the flask. The solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then secured to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of the dissolved stock solution of FL-SMILES [(cyanostar)2(BF4)(DAOTA)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing.

[0109] Example 5: Preparation of SMILES material from Cyanostar and Oxazine 720 A quantity of dried Oxazine 720 perchlorate (4.9 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, Cyanostar (20.8 mg), were weighed out and added to the flask. A volume of dichloromethane (1 mL) was added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum and the resulting powder was collected. A quantity (2.3 mg) of dried FL-SMILES powder [(Cyanostar)2(ClO4)(Oxazine 720)] was added to the flask. The solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then secured to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of a stock solution of FL-SMILES [(cyanostar)2(ClO4)(oxazine 720)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing.

[0110] [Example 6] Preparation of SMILES materials from cyanostars and cyanines A quantity of dry cyanine DIOC2 hexafluorophosphate (6.3 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand Cyanostar (24.1 mg) were weighed out and added to the flask. A volume of dichloromethane (1 mL) was added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum and the resulting powder was collected. A quantity (2.3 mg) of dry FL-SMILES powder [(Cyanostar)2(PF6)(DIOC2)] was added to the flask. The solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then fixed to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of the dissolved stock solution of FL-SMILES [(Cyanostar)2(PF6)(DIOC2)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing.

[0111] Example 7: Preparation of materials that do not show color reproduction when using Cyanostar and TOTA, which show poor energy compatibility A quantity of dry TOTA tetrafluoroborate (4.4 mg) was added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, Cyanostar (21.6 mg), were weighed out and added to the flask. A volume of dichloromethane (1 mL) was added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for cationic dyes). The solvent was then removed in vacuum and the resulting powder was collected. A quantity (2.2 mg) of dry FL-SMILES powder [(Cyanostar)2(BF4)(TOTA)] was added to the flask. The solid was then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide was then secured to a spin coater set at 2000 RPM. The spinning time was set to 30-45 seconds. The spinner was started and then 20 μL of the dissolved stock solution of FL-SMILES [(cyanostar)2(BF4)(TOTA)] was applied to the center of the slide. Once spinning was completed, the slide was removed and analyzed for optical properties without any additional processing. The absorption spectrum of the thin film does not show the same characteristics as a dilute solution of TOTA dye alone, and the light emission characteristics do not reproduce the same light emission seen from the dye in dilute solution, but instead show a new red-shifted light emission band.

[0112] [Example 8] Solid state of SMILES materials A comparison of the optical properties of rhodamine 3B perchlorate in the solid state by itself and as a SMILES material demonstrates this concept. The optical absorption spectrum of a thin film of the FL-SMILES material [(cyanostar)2(ClO4)(rhodamine 3B)] (Figure 2C, solid line) was found to match the solution spectrum of the cationic dye rhodamine 3B in dilute conditions. However, the optical absorption spectrum of rhodamine 3B perchlorate alone (Figure 2C, dotted line) did not match the solution spectrum of the cationic dye rhodamine 3B in dilute conditions (Figure 2A). Instead, the absorption spectrum from the thin film was distorted and showed a shift to longer wavelengths and a broader spectral band than in solution. Relative to the thin film of rhodamine 3B perchlorate alone (Figure 2D, dotted line), the optical excitation and emission of the FL-SMILES material (Figure 2D, solid line) was enhanced.

[0113] The enhanced light emission from the solid-state preparation of the amorphous powder of the FL-SMILES material is readily visible in the enhanced brightness of the photograph of the SMILES material (Figure 2F, right hand) versus rhodamine perchlorate 3B alone (Figure 2F, left hand).

[0114] The bright light emission obtained when using FL-SMILES can be seen in various polymer composites. Using Method I (see Examples, F.1 Polymer Composites), the following polymers have been dyed with FL-SMILES [(cyanostar)2(ClO4)(rhodamine 3B)] and are seen to show bright fluorescence when observed under UV light irradiation. See FIG. 11 for photographic images of dyed polystyrene, poly(methyl methacrylate), poly(bisphenol A carbonate), PEG5000 and poly(vinylpyrrolidone). See, for example, FIG. 12 for dyed polymers made using Method II (see Examples, F.1 Polymer Composites), i.e., poly(propylene) and poly(acrylic acid).

[0115] B.1 SMILES Powders and Amorphous Solids A SMILES dye solution is first prepared as described above in A.1, using the values ​​of x, y, and z in formula (I) and formula (VI). The solvent is then removed by evaporation under vacuum or a similar method. The resulting powder (e.g., Figures 2E and 2F) is composed of a SMILES material in the solid state of formula corresponding to compound I, where the values ​​of x, y, and z are defined by the original SMILES dye solution.

[0116] C.1 Thin film Thin films of SMILES materials can be prepared by spin-coating an appropriate solution, particle suspension, polymer solution, or any relevant SMILES formulation onto a glass slide. The values ​​of x, y, and z for the compounds of formula (I) and formula (VI) are dictated by the SMILES powder or SMILES dye solution or particle suspension or polymer solution used.

[0117] A quantity of SMILES powder (section B.1) is dissolved or suspended in a volatile organic solvent (e.g., dichloromethane or pentane) to the desired stock concentration (e.g., 2 mM). In addition, SMILES dye solutions (see A.1), microparticle suspensions (see E.1) or polymer complexes (see F.1) can be used.

[0118] In a typical preparation, a glass slide is secured to a spin coater. The spinner (2000 RPM) is started, then 20 µL of the SMILES material in solution is applied to the center of the slide. Once spinning is complete (30-45 s), the thin film can be subjected to further analysis without further processing.

[0119] D.1 Bulk crystals Crystals of the SMILES materials of compounds of formula (I) and formula (VI) are prepared using standard methods of crystal growth, including but not limited to vapor diffusion, layering of a good solvent with a poor solvent, slow evaporation of a solvent, recrystallization, seeding of a solution, and cooling of a concentrated solution.

[0120] In a typical preparation using vapor diffusion, a 5 mM solution of the SMILES material is added to a sealed vial with a pinhole aperture and placed in a chamber containing a suitable volatile anti-solvent The anti-solvent chamber is then closed and crystals are allowed to grow.

[0121] E.1 SMILES Microcrystals and Microparticles Method I: A certain amount of dry SMILES powder (section B.1) is transferred to a flask and dissolved in dichloromethane to the desired concentration (typical concentration range: 1-20 mM). Alternatively, a dye solution can be made from the components of the SMILES material described in section A.1. The SMILES components and materials must be soluble in the selected solvent. To this solution, an excess of anti-solvent (e.g. 20 volume equivalents of pentane) is slowly added. During the addition, the solution becomes opaque as small microparticles of the SMILES material are formed. The solvent is subsequently removed under vacuum to obtain the SMILES material.

[0122] Method II: A certain amount of dry SMILES powder (section A.1) is added to a flask and dissolved in dichloromethane to the desired concentration (typical concentration range: 1-20 mM). Alternatively, a SMILES dye solution (section A.1) can also be prepared at the desired concentration. The SMILES solution is then added dropwise to 20 volume equivalents of anti-solvent (typically pentane) during which the solution will become opaque. The solvent is subsequently removed under vacuum to yield the SMILES material.

[0123] F.1 Polymer composites SMILES materials can be added to polymers in one of two ways.

[0124] Method I: A certain amount of dry polymer (e.g. resin) is added to a flask. The SMILES material is then added as a powder (section B.1) in a fraction of the polymer's mass (e.g. 0.05%-20%). Solvent is then added until all solids are completely dissolved. The solution can then be used to prepare thin films (section C.1), cast into shapes using a mold, or the solvent removed to provide a dry powder composite. Representative examples include the use of poly(methyl methacrylate) (PMMA) or poly(bisphenol A carbonate). These doped polymers are prepared by dissolving a mixture of dry polymer resin and SMILES in dichloromethane and removing the solvent.

[0125] Method II: A certain amount of dry polymer (e.g. resin) is added to a flask. The flask is then heated in an oil bath until the resin is completely melted. SMILES particles are added as a powder in a fraction of the polymer's mass (e.g. 0.05%-20%) (sections B.1 and E.1) and stirred to evenly distribute the SMILES material within the liquefied polymer. A typical example is the use of polypropylene and polyacrylic acid.

[0126] Preparation of suitable SMILES Rhodamine R12 nanoparticles SMILES nanoparticles were prepared by injecting a mixture of R12 (400 μL) and Cyanostar (400 μL) in 20 mL of water in a sonicator bath. Sonication of the suspension was continued for 1 min after the end of injection to ensure homogeneous mixing. The open vial was then placed on a magnetic stirrer for 8 h to allow the contained THF to evaporate. To remove any dissolved dye, the suspension was then placed under dialysis overnight with a 10 kDa cut-off filter against 2 liters of deionized water. The suspension was then concentrated using a 10 kDa centrifugal concentrator to obtain a final volume of 4 mL.

[0127] Particles with DSPEG surface coating DSPEPEG-wrapped SMILES nanoparticles were made by first mixing 400 μL R12, 400 μL Cyanostar, and 600 μL DSPEPEG, then injecting into 20 mL water in a sonicator bath. Sonication of the suspension was continued for 1 min after injection was finished to ensure homogeneous mixing. The vial was then placed on a magnetic stirrer to evaporate the contained THF. The suspension was then placed under dialysis with a 10 kDa cutoff filter overnight to remove excess DSPEPEG and possibly any dissolved dye. The suspension was then concentrated using a 10 kDa centrifugal concentrator to obtain a final volume of 4 mL.

[0128] SMILES nanoparticles coated with TAT-peptide conjugated DSPEPEG First, 400 μL of R12, 400 μL of Cyanostar, 300 μL of DSPEPEG, and 300 μL of DSPEPEG-malemide were mixed, and then 20 mL of water was injected in a sonicator bath to create DSPEPEG-wrapped SMILES nanoparticles. Sonication of the suspension was continued for 1 min after the end of the injection to ensure homogeneous mixing. The vial was then placed on a magnetic stirrer to allow the contained THF to evaporate. A 150 μL portion of the stock solution of TAT-peptide was then added to the nanoparticle suspension, and the vial was allowed to stir overnight to complete the conjugation reaction. The suspension was then placed under dialysis with a 10 kDa cutoff filter overnight to remove excess DSPEPEG, TAT-peptide, and possibly any dissolved dye. The suspension was then concentrated using a 10 kDa centrifugal concentrator to obtain a final volume of 4 mL.

[0129] G.1 Preparation of SMILES material from dibenzo-18-crown-6 and sulforhodamine B sodium salt A certain amount of dry Sulforhodamine B sodium (5.8 mg) is added to the flask. One molar equivalent of the cationic ligand dibenzo-18-crown-6 (3.6 mg) is weighed out and added to the flask. A volume of dichloromethane (10 mL) is added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for anionic dyes). The solvent is then removed in vacuum and the resulting powder is collected. A certain amount (18.8 mg) of dry SMILES powder [(dibenzo-18-crown-6)(Na)(sulforhodamine B)] is then added to the flask. The solid is then dissolved in a volatile organic solvent (dichloromethane) to the desired stock solution concentration (2 mM). A glass microscope slide is then secured to a spin coater set at 2000 RPM. The spinning time is set to 30-45 seconds. Start the spinner and apply 20 μL of the dissolved stock solution of SMILES [(dibenzo-18-crown-6)(Na)(sulforhodamine B)] to the center of the slide. Once spinning is complete, the slide can be removed and analyzed for optical properties without any additional processing.

[0130] G.2 Preparation of SMILES from dibenzo-18-crown-6 and fluorescein cesium salt A certain amount of dry fluorescein cesium salt (4.6 mg) is added to the flask. Two molar equivalents of dibenzo-18-crown-6 (7.2 mg) are weighed out and added to the flask. A volume of dichloromethane (10 mL) is added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for the anionic dye and 2 mM for dibenzo-18-crown-6). The solvent is then removed in vacuum and the resulting powder is collected. A certain amount (23.7 mg) of dry FL-SMILES powder [(dibenzo-18-crown-6)2(Cs)(fluorescein)] is then added to the flask. The solid is then dissolved in a volatile organic solvent (dichloromethane) to the desired stock solution concentration (2 mM). A glass microscope slide is then secured to a spin coater set at 2000 RPM. Set the spinning time to 30-45 seconds. The spinner is started and then 20 μL of the dissolved stock solution of SMILES [(dibenzo-18-crown-6)2(Cs)(fluorescein)] is applied to the center of the slide. Once spinning is complete, the slide can be removed and analyzed for optical properties without any additional processing.

[0131] G.3 Preparation of SMILES materials from cyanostars and dicationic tetramethoxy-aminorhodamines A quantity of dry tetramethoxy-aminorhodamine bis-sulfate (7.2 mg) is added to the flask. Two molar equivalents of the SMILES-compatible anionic ligand, cyanostar (18.4 mg), are weighed out and added to the flask. A volume of dichloromethane (10 mL) is added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for the dicationic dye). The solvent is then removed in vacuum and the resulting powder is collected. A quantity (5.1 mg) of dry FL-SMILES powder [(cyanostar)2(HSO4)2(tetramethoxy-aminorhodamine)] is then added to the flask. The solid is then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM in 1 mL). A glass microscope slide is then secured to a spin coater set at 2000 RPM. Set the spinning time to 30-45 seconds. The spinner is started and then 20 μL of the dissolved stock solution of FL-SMILES [(cyanostar)2(HSO4)2(tetramethoxy-aminorhodamine)] is applied to the center of the slide. Once spinning is complete, the slide can be removed and analyzed for optical properties without any additional processing.

[0132] G.4 Preparation of SMILES materials from cyanoster, aminopyrene, and hexafluorophosphonic acid A quantity of aminopyrene (2.2 mg) is added to the flask. A volume of dichloromethane (10 mL) is added to the dry mixture to obtain a solution of the desired concentration (e.g., 1 mM for the dye). One molar equivalent of hexafluorophosphonic acid is added to generate ammonium pyrene hexafluorophosphate in situ. Two molar equivalents of the SMILES-compatible anionic ligand, cyanostar (18.4 mg), are weighed out and added to the flask. The solvent is then removed in vacuum and the resulting powder is collected. A quantity (4.39 mg) of dry SMILES powder [(cyanostar)2(PF6)(ammonium pyrene)] is then added to the flask. The solid is then dissolved in a volatile organic solvent (dichloromethane) to the desired stock concentration (2 mM). A glass microscope slide is then secured to a spin coater set at 2000 RPM. Set the spinning time to 30-45 seconds. The spinner was started and then 20 μL of the dissolved stock solution of FL-SMILES [(cyanostar)2(PF6)(ammonium pyrene)] was applied to the center of the slide. Once spinning was completed, the slide was removed and can be analyzed for optical properties without any additional processing.

[0133] <Incorporated by reference> All patents, patent applications, patent application publications, other publications and appendices cited herein are hereby incorporated by reference as if set forth in their entireties.

[0134] Preferred Embodiments The present invention has been described in terms of what are currently considered to be the most practical and preferred embodiments. However, the present invention has been presented by way of example and is not intended to be limited to the disclosed embodiments. Accordingly, those skilled in the art will recognize that the present invention is intended to encompass all modifications and alternative variations within the spirit and scope of the present invention as set forth in the appended claims.

Claims

1. Formula (I): (Charged dye ｍ＋ ) ｘ (Counter ion ｎ－ ) ｙ (Hetero macrocyclic counter ion receptors) ｚ (I) (In the formula, Charged Dyes ｍ＋ is a cationic organic dye with a counterion ｎ－ is the anion, and the heteromacrocyclic counterion receptor is the counterion ｎ－ is a binding ligand of m, n, x, and y are integers of 1 or more, and the product of x and n is the same as the product of m and y. A fluorescent solid-state ionic lattice comprising a compound of the formula: Formula (I) Formula (I-1): 【Chemistry 1】 Formula (I-2): 【Chemistry 2】 Formula (I-3): 【Chemistry 3】 Formula (I-6): 【Chemistry 4】 Formula (I-7): 【Chemistry 5】 Formula (I-8): 【Chemistry 6】 Formula (I-9): 【Chemistry 7】 Formula (I-10): 【Chemistry 8】 Formula (I-11): 【Chemistry 9】 Formula (I-12): 【Chemistry 10】 Formula (I-13): 【Chemistry 11】 or Formula (I-14): 【Chemistry 12】 Selected from: Fluorescent solid-state ionic lattices.

2. Formula (I) is formula (I-1): 【Chemistry 13】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

3. The compound represented by formula (I) is represented by formula (I-2): 【Chemistry 14】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

4. The compound represented by formula (I) is represented by formula (I-3): 【Chemistry 15】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

5. Formula (I) is formula (I-6): 【Chemistry 16】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

6. Formula (I) is formula (I-7): 【Chemistry 17】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

7. Formula (I) is formula (I-8): 【Chemistry 18】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

8. Formula (I) is formula (I-9): 【Chemistry 19】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

9. Formula (I) is formula (I-10): 【Chemistry 20】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

10. Formula (I) is formula (I-11): 【Chemistry 21】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

11. Formula (I) is formula (I-12): 【Chemical 22】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

12. The compound represented by formula (I) is represented by formula (I-13): 【Chemistry 23】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

13. Formula (I) is formula (I-14): 【Chemistry 24】 2. The fluorescent solid state ionic lattice of claim 1 , wherein

14. A formulation comprising a compound according to any one of claims 1 to 13.

15. 15. The formulation of claim 14, comprising a solid state material.

16. 16. The formulation of claim 15, wherein the solid state material is selected from the group consisting of powders, amorphous solids, thin films, crystals, microparticles, polymer composites, nanoparticles, and colloids of microparticles and nanoparticles.

17. The formulation according to any one of claims 14 to 16, which is prepared from a solution, a powder or a colloid.

18. The formulation of claim 15, comprising a colloid.

19. 1. A method for producing a material having high brightness light emission properties, comprising: Preparing a first mixture comprising a fluorescent solid-state ionic lattice according to any one of claims 1 to 13, and Concentrating the first mixture to form a material having light-emitting units in a solid state. A method comprising:

20. 1. A method for detecting a substance, comprising: Contacting a substance with any of the compounds according to any one of claims 1 to 13 to form a mixture; and measuring a change in at least one spectral property in any of the compounds, formulations, or materials of the mixture as a result of the contacting step, relative to the substance alone, or the compound, formulation, or material alone. Including, A method wherein the substance is detected by a change in at least one spectral characteristic in any of the compounds, formulations or materials as a result of a measuring step on the mixture.

Images