Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
  • A01G7/00—Botany in general
  • A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
  • A01G7/045—Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
  • H01L33/50—Wavelength conversion elements
  • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
  • H01L33/502—Wavelength conversion materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
  • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms

Definitions

• perylene-BODIPY triad compounds for use in wavelength converting films, backlighting units and horticulture applications.
• LED Light-emitting diodes
• Plants use the process of photosynthesis to convert light, CO2 and H2O into carbohydrates (sugars). These sugars are used to fuel metabolic processes. Most of the sugars are utilized for biomass formation, which includes stem elongation, increase in leaf surface area, flowering, fruit formation, etc. Two important absorption peaks of plant chlorophyll a and b are in the blue and red regions, especially from 425-475 nm and 625-675 nm respectively. The daily duration of light is important for many plants. The ratio of light and dark periods in a 24-hour cycle influences the flowering responses in many plants. Due to a decrease in light to dark ratio, most plants only produce fruit in the summer months. The use of supplemental lighting during the autumn, winter and spring in indoor farming can increase worldwide productivity.
• perylene-BODIPY triad compounds for use in photoluminescent complexes.
• Perylene-BOIDPY triads described herein may be used with a wavelength converting film for the conversion of blue LED light to a red-light wavelength which has a high quantum yield and is durable to withstand heat and moisture and increase light outcoupling.
• the perylene-BODIPY triad compounds of the present disclosure provide novel color converting compounds with good blue light absorbance and a red light emission bandwidth, with the full width half maximum [FWHM] of emission band of greater than 40 nm.
• the perylene-BODIPY triad compound absorbs light of a first wavelength and emits light of a second wavelength longer than the first wavelength.
• the perylene-BODIPY triad compounds disclosed herein can be utilized with a wavelength conversion film for use in artificial horticulture lighting.
• Some embodiments include a photoluminescent complex comprising a perylene- BODIPY triad compound comprising: a first optionally substituted perylene covalently linked to a boron-dipyrromethene (BODIPY) moiety by a first linker moiety and a second optionally substituted perylene covalently linked to the BODIPY moiety by a second linker moiety.
• the first optionally substituted perylene and the second optionally substituted perylene absorb blue light of a first excitation wavelength and transfer part of the energy from the absorbed blue light to the BODIPY moiety, and the BODIPY moiety emits part of the transferred energy as light of a second longer wavelength.
• the difference between the first excitation wavelength and the second longer wavelength is greater than 35 nm.
• the photoluminescent complex may have a quantum yield of at least 85%.
• the present disclosure provides photoluminescent complexes for converting blue light energy to a red light wavelength with excellent luminescent properties. These and other embodiments are described in greater detail below.
• FIG. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
• FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
• FIG. 3 is a graph depicting a White LED spectrum.
• Perylene-BODIPY triad compounds have a broader full width at half maximum (FWHM), high fluorescent efficiency, stability to both moisture, heat, and low production cost relative to conventional photoluminescent compounds.
• Conventional BODIPY- containing materials may have some drawbacks, such as very low absorption of blue LED light, e.g., 400-475 nm, resulting in inefficient conversion of blue LED light to red light.
• the current disclosure describes perylene-BODIPY triad compounds for use in shifting (or upscaling) blue light to red light.
• the perylene-BODIPY triad compounds may be used to improve and enhance the transmission of one or more desired emissive bandwidths within a wavelength conversion film.
• a substituted group is related to the unsubstituted parent structure in that one or more hydrogen atoms on the parent structure are independently replaced by one or more substituent groups.
• a substituent group may have one or more substituent groups on the parent group structure.
• the substituent groups may independently be F, Cl, Br, I, C0-7H1-15O1-2N0-2, C0-7H1-15O0-2N1-2, optionally substituted alkyl (e.g., unsubstituted alkyl, such as methyl, ethyl, C3 alkyl, C4 alkyl, etc.), fluoroalkyl (e.g. -CF3, etc.), alkenyl, or a C3-C7 heteroalkyl.
• optionally substituted alkyl e.g., unsubstituted alkyl, such as methyl, ethyl, C3 alkyl, C4 alkyl, etc.
• fluoroalkyl e.g. -CF3, etc.
• alkenyl e.g. -C7 heteroalkyl.
• the alkyl moiety may be branched, straight chain, or cyclic.
• the alkyl moiety may have 1 to 6 carbon atoms. Where it appears herein, a numerical range such as “1 to 6" refers to each integer in the given range. For example, “1 to 6 carbon atoms” means that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designated.
• the alkyl group of the compounds designated herein may be designated as "Ci-Ce alkyl" or similar designations.
• Ci-Ce alkyl indicates that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or t-butyl.
• Ci-Ce alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl.
• Alkyl groups can be substituted or unsubstituted.
• Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
• heteroalkyl refers an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a nitrogen, oxygen, of a sulfur. Examples include but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH- CH 3 , -CH2-N(CH 3 )-CH 3 , -CH2-CH2-NH-CH3, -CH2-CH2-N(CH 3 )-CH 3 , -CH2-S-CH2-CH3, -CH2-CH2- S(O)-CH3. In addition, up to two heteroatoms may be consecutive, such as, by way of example, -CH2-NH-O-CH3, etc.
• aromatic refers to a planar ring having a delocalized n-electron system containing 4n+2 n-electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatics can be optionally substituted.
• aromatic includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or “heteroaryl” or heteroaromatic") group (e.g., pyridine).
• the term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
• aryl as used herein means an aromatic ring or ring system wherein each of the atoms forming the ring is a carbon atom.
• Aryl rings can be formed by five, six, seven eight, or more than eight carbon atoms.
• Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, etc.
• heteroaryl refers to an aromatic ring or ring system that includes one or more ring heteroatoms such as nitrogen, oxygen and sulfur, wherein the heteroaryl group has from 4 to 10 atoms in its ring system and with the proviso that the ring of the group does not contain two adjacent nitrogen, oxygen, or sulfur atoms. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryl rings having two or more heteroatoms, the two or more heteroatoms can be the same or different from one another. Heteroaryl rings can be optionally substituted.
• N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
• heteroaryl groups include the following moieties: pyrrole, imidazole, pyridine, etc.
• halogen as used herein means fluorine, chlorine, bromine, and iodine.
• bond means a chemical bond between two atoms or a chemical bond between two moieties when the atoms joined by the bond are considered to be part of a larger structure.
• moiety refers to a specific segment or functional group of a molecule.
• cyano or "nitrile” as used herein refers to any organic compound that contains a -CN functional group.
• esters refers to a chemical moiety with the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), or heterocyclic (bonded through a ring carbon). Any hydroxy or carboxyl side chain on the compounds described herein can be esterified. Suitable procedures and specific groups to make such esters can readily be found in reference sources.
• ether refers to a chemical moiety that contains an oxygen atom connected to: two alkyl groups; two aryl groups; or one alkyl group and one aryl group; with the general formula of R-O-R', wherein R and R' are independently alkyl or aryl, where the term alkyl and aryl is as defined herein.
• R and R' are independently alkyl or aryl, wherein the term alkyl and aryl is as defined herein.
• BODIPY refers to a chemical moiety with the general formula
• the BODIPY moiety may be composed of dipyrromethene complexed with a disubstituted boron atom, typically a BF2 unit.
• the IUPAC name for the BODIPY core is 4,4- difluoro-4-bora-3a,4a-diaza-s-indacene.
• the positive and negative charges associated with the BODIPY moiety are not displayed in some of the structures of the present disclosure.
• the optionally substituted perylene comprises:
• the optionally substituted perylene comprises:
• Novel perylene-BODIPY triads suitable for the transfer of light energy of a first wavelength for emittance of a light energy of a second wavelength are described herein. Unless otherwise indicated, conventional methods of NMR, HPLC and mass spectroscopy, within the ordinary skill of the art are employed.
• the perylene-BODIPY triad compounds described herein are suitable for converting a absorbed first light energy of about 400-475 nm to a second emitted light energy of about 570-750 nm (e.g., 612 nm, or 590 nm).
• the perylene-BODIPY triad compounds of the present disclosure comprise two absorbing luminescent moieties and an emitting luminescent moiety that are coupled via a linker such that their distance is optimized for the two absorbing luminescent moieties to transfer their energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits energy at a second wavelength that is higher (longer) than the absorbed first wavelength.
• Ri is hydrogen (H), a substituted or unsubstituted alkyl group (such as C1-12 alkyl, C1-6 alkyl, C1-3 alkyl, C3-6 alkyl, CH3, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, Ce alkyl, etc.), a fluorinated alkyl group (e.g., -CF3), an ester group (such as C1-12 ester, C1-6 ester, C1-3 ester, C3-6 ester, CH3, C2 ester, C3 ester, C4 ester, C5 ester, Ce ester, etc.), or a substituted or unsubstituted aryl group.
• a substituted or unsubstituted alkyl group such as C1-12 alkyl, C1-6 alkyl, C1-3 alkyl, C3-6 alkyl, CH3, C2 alkyl, C3 alkyl, C4 ester, C5 ester, Ce ester, etc.
• R4 is hydrogen (H), a substituted or unsubstituted alkyl group (such as C1-12 alkyl, C1-6 alkyl, C1-3 alkyl, C3-6 alkyl, CH3, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, Ce alkyl, etc.), a fluorinated alkyl group (e.g., -CF3), an ester group (such as C1-12 ester, C1-6 ester, C1-3 ester, C3-6 ester, CH3, C2 ester, C3 ester, C4 ester, C5 ester, Ce ester, etc.), a substituted or unsubstituted aryl group.
• R2 is an unsubstituted aryl group or a substituted aryl group. In some embodiments, R2 is optionally substituted phenyl.
• R3 is an unsubstituted aryl group or a substituted aryl group. In some embodiments, R3 is optionally substituted phenyl.
• Gi is hydrogen (H), a methyl (-CH3), or a chlorine atom (- Cl).
• Gi is hydrogen (H).
• Gi is a methyl (-CH3) .
• Gi is a chlorine atom (-CI).
• G2 is hydrogen (H), a methyl (-CH3), or a chlorine atom (- Cl). In some embodiments, G2 is hydrogen (H). In some embodiments, G2 is a methyl (-CH3) . In some embodiments, G2 is a chlorine atom (-CI).
• G3 is a hydrogen (H), a methyl (-CH3), or a fluorinated alkyl group (e.g., -CF3).
• G3 is hydrogen (H).
• G3 is a methyl (-CH3).
• G3 is or a fluorinated alkyl group (e.g., -CF3).
• n is 1, 2, 3, 4, 5, or 6.
• the n associated with Li and the n associated with L2 may be the same or different.
• Zi is a perylene derivative.
• Z2 is a perylene derivative.
• perylene-BODIPY triad compounds described herein may be represented by
• Ri is L3-Z1.
• Zi is a perylene derivative.
• R4 is l_4-Z 2 .
• the n associated with L3 and the n associated with L4 may be the same or different.
• Z 2 is a perylene derivative.
• R 2 is an unsubstituted aryl group or a substituted aryl group.
• R3 is an unsubstituted aryl group or a substituted aryl group.
• Gi is a hydrogen (H), a methyl (-CH3), or a -Cl.
• Gi is hydrogen (H).
• Gi is a methyl (-CH3).
• Gi is a chlorine atom (-CI).
• G 2 is a hydrogen (H), a methyl (-CH3), or a -Cl. In some embodiments, G 2 is hydrogen (H). In some embodiments, G 2 is a methyl (-CH3). In some embodiments, G 2 is a chlorine atom (-CI).
• G3 is a hydrogen (H), a methyl (-CH3), or a trifluoromethyl (-CF3).
• G3 is hydrogen (H).
• G3 is a methyl (- CH3).
• G3 is a fluorinated alkyl group (e.g., -CF3).
• Yi is H or C1-C10 alkyl. In some embodiments, Yi is H. In some embodiments, Yi is C1-C10 alkyl.
• Y2 is H or C1-C10 alkyl. In some embodiments, Y2 is H. In some embodiments, Y2 is C1-C10 alkyl.
• Zi and Z2 are selected from a perylene derivative of Formula (C): Formula (C).
• R 8 is hydrogen (H) or a fluorinated alkyl group (e.g., -CF3). In some embodiments, R 8 is hydrogen (H). In some embodiments, R 8 is a fluorinated alkyl group (e.g., -CF 3 ).
• R 10 is hydrogen (H) or a fluorinated alkyl group (e.g., -CF3). In some embodiments, R 10 is hydrogen (H). In some embodiments, R 10 is a fluorinated alkyl group (e.g., -CF 3 ).
• R 11 is hydrogen (H) or a fluorinated alkyl group (e.g., -CF3). In some embodiments, R 11 is hydrogen (H). In some embodiments, R 11 is a fluorinated alkyl group (e.g., -CF 3 ).
• perylene-BODIPY triad compounds described herein may be used for a wide variety of industrial uses which require the upscaling of light. These compounds will be required to perform for an extensive period and enhanced photostability will be required. It is believed that the addition of electron withdrawing groups at the Ri and R4 sites greatly enhance the photostability of the perylene-BODIPY triad compound.
• Ri and F may respectively comprise hydrogen (H)
• the ester group may be, for example, -CO2R, wherein R is an ethyl or a 2- ethylhexyl group
• R2 and R3 each may be an unsubstituted ary
• the substituted aryl group may comprise a phenyl with two fluorinated alkyl groups (e.g., -CF3) as substituents
• R2 and R3 each may be an unsubstituted
• the substituted akyl group may comprise a fluorinated alkyl (e.g., -CF3)
• R2 and R3 each may be an unsubstituted aryl, wherein the aryl is a phenyl, Gi,
• the ester group may be, for example, -CO2R, wherein R is an ethyl or a 2-ethylhexyl group, R2 and R3 each may be an unsubstituted
• the ester group may be, for example, -CO2R, wherein R is an ethyl or a 2-ethylhex
• perylene-BODIPY triad compounds include, but are not limited to, compounds selected from one of the following:
• the Stokes shift of the perylene-BODIPY triad compound, the difference between the first excitation wavelength and the emitted second longer wavelength of the perylene-BODIPY triad compound can be greater than 30 nm. In some alternative embodiments, the Stokes shift of the perylene-BODIPY triad compound, the difference between the first excitation wavelength and the emitted second higher wavelength of the perylene-BODIPY triad compound, can be greater than 35 nm.
• the difference between the first excitation wavelength and the emitted second higher wavelength of the perylene-BODIPY triad compound can be about 30 nm to about 35 nm, 35 nm to about 40 nm, 40 nm to about 45 nm, 45 nm to about 50 nm, about 50 nm to about 55 nm, about 55 nm to about 60 nm, about 60 nm to about 65 nm, about 65 nm to about 70 nm, about 70 nm to about 75 nm, about 75 nm to about 80 nm, about 80 nm to about 85 nm, about 85 to about 90 nm, about 90 nm to about 95 nm, about 95 nm to about 100 nm, or greater than about 100 nm, or any number bounded by this range. It is believed that increasing the Stokes shift of the BODIPY moiety will result in less self-absorption of the perylene-BODIPY Y
• the emission band of a second longer wavelength, of the perylene-BODIPY triad compound disclosed herein can have a full width half maximum (FWHM) of at least 40 nm.
• the FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band.
• the photoluminescent complex has an emission band FWHM value that is equal to or greater than about 40 nm, less than or equal to about 45nm, less than or equal about 50 nm, less than or equal to about 60 nm.
• the FWHM is about 40 nm to about 45 nm, about 45 nm to about 50 nm, about 50 nm to about 55 nm, about 55 nm to about 60 nm, or greater than 60 nm.
• the perylene-BODIDY triad compound can have a high emission quantum yield.
• the emission quantum yield can be greater than 85%, greater than 90%, or greater than 95%.
• Emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety.
• the absorbing luminescent moiety may have an emission quantum yield greater than 85%.
• the quantum yield can be greater than 0.85 (85%), greater than 0.86 (86%), greater than 0.87 (87%), greater than 0.88 (88%), greater than 0.89 (89%), greater than 0.9 (90%), greaterthan 0.91 (91%), greaterthan 0.92 (92%), greaterthan 0.93 (93%), greaterthan 0.94 (94%), and/or greater than 0.95 (95%).
• Quantum yield measurements in film can be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Hammamatsu, Inc., Campbell, CA, USA).
• the quantum yield can be about 0.85 (85%), about 0.85 (85%) to about 0.86 (86%), about 0.86 (86%) to about 0.87 (87%), about 0.87 (87%) to about 0.88 (88%), about 0.88 (88%) to about 0.89 (89%), about 0.89 (89%) to about 0.9 (90%), about 0.9 (90%) to about 0.91 (91%), about 0.91 (91%) to about 0.92 (92%), about 0.92 (92%) to about 0.93 (93%), about 0.93 (93%) to about 0.94 (94%), about 0.94 (94%) to about 0.95 (95%), about 0.85 (85%) to about 0.9 (90%), about 0.9 (90%) to about 0.95 (95%), about 0.95 (95%) to about 1 (100%), or about 0.85 (85%) to about 1 (100%).
• the perylene-BODIPY triad compounds of the current disclosure can have a tunable emission wavelength.
• the emission wavelength can be tuned between about 570 nm to about 750 nm, or any number in a range bounded by any of these values.
• the blue light absorbing moiety can have a peak absorption wavelength between about 400 nm to about 475 nm.
• the peak absorption can be between about 400-405 nm, about 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430-435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, 470-475 nm, or any value in a range bounded by any of these ranges.
• the photoluminescent complex comprising the perylene- BODIPY triad compound can have an emission peak wavelength between about 570 nm to about 750 nm.
• the emission peak can be between about 570-575 nm, about 575-580 nm, about 580-585 nm, about 585-590 nm, about 590-595 nm, about 595-600 nm, about 600-605 nm, about 605-610 nm, about 610-615 nm, about 615-620 nm, about 620- 625 nm, about 625-630 nm, about 630-635 nm, about 635- 640 nm, about 640-645 nm, about 645-650 nm, about 650-655 nm, about 655-660 nm, about 660-665 nm, about 665-670 nm, about 670-675 nm, about 675-680 nm
• This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures can be implemented which achieve the same or similar functionality.
• any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms.
• the phase "A or B” will be understood to include the possibilities of "A or B” or “A and B.”
• the terms "a,” “an/' “the” and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
• a perylene-BODIPY triad compound comprising: at least two blue light absorbing moieties, wherein the at least two blue light absorbing moieties are comprise an optionally substituted perylene; at least two linker moieties that covalently link the optionally substituted perylenes to a boron-dipyrromethene (BODIPY) moiety; wherein the optionally substituted perylene absorbs light energy of a first excitation wavelength and transfers part of the absorbed light energy to the BODIPY moiety; wherein the BODIPY moiety emits part of the transferred energy as light energy of a second longer wavelength; and wherein the difference between the first excitation wavelength of the BODIPY moiety and the emitted second higher wavelength of the BODIPY moiety is greater than 35 nm.
• BODIPY boron-dipyrromethene
• Embodiment 2 The perylene-BODIPY triad compound of embodiment 1, having a full width half maximum (FWHM) at least 40nm.
• FWHM full width half maximum
• Embodiment 3 The perylene-BODIPY triad compound of embodiments 1 or 2, wherein the quantum yield is at least 85%.
• Embodiment 4 The perylene-BODIPY triad compound of embodiments 1, 2, or 3, wherein the perylene-BODIPY triad compound absorbs light in the 400-475 nm wavelength range and emitting light 570-750 nm wavelength range.
• Embodiment 5 The perylene-BODIPY triad compound of embodiments 1, 2, 3, or 4, wherein the photoluminescent cassette is represented by the following formula: wherein Ri and F are the same as or independent from one another and are each selected from a hydrogen (H), a substituted or unsubstituted alkyl group, a fluorinated alkyl group (e.g., -CF3), an ester group, or a substituted or unsubstituted aryl group;
• Ri and F are the same as or independent from one another and are each selected from a hydrogen (H), a substituted or unsubstituted alkyl group, a fluorinated alkyl group (e.g., -CF3), an ester group, or a substituted or unsubstituted aryl group;
• R2 and R3 are the same as or independent form one another and are each an unsubstituted aryl group or a substituted aryl group;
• Gi and G2 are selected from a H, a methyl, or a Cl;
• G3 is a H, a methyl (-CH3), or a fluorinated alkyl group (e.g., -CF3);
• Zi and Z2 are selected from a perylene derivative.
• Embodiment 6 The perylene-BODIPY triad compound of embodiment 5, wherein the perylene derivative is represented by the following formula: wherein R 8 , R 10 and R 11 are selected from a H, or fluorinated alkyl group (e.g., -CF3) and wherein R 9 is a H.
• Embodiment 7 The perylene-BODIPY triad compound of embodiment 1, 2, 3, 4, 5, or 6, wherein the compound comprises: Embodiment s.
• Embodiment 9 The perylene-BODIPY triad compound of embodiment 1, 2, 3, 4, 5, or 6, wherein the compound comprises: Embodiment 10.
• Embodiment 12 The perylene-BODIPY triad compound of embodiment 1, 2, 3, 4, 5, or 6, wherein the compound comprises: EXAMPLES
• benzyl bromide (36.0 mmol, 4.28 mL).
• the second neck was stoppered, and the flask placed in an aluminum heat block.
• the temperature of this heat block was set to 50 °C and the reaction mixture was stirred at this temperature under argon for 90 minutes.
• TLC shows the reaction has stalled, so more benzyl bromide (36.0 mmol, 4.28 mL) and potassium carbonate (45.0 mmol, 6.219 g) were added and stirring continued at 50 °C under argon for an additional 60 minutes.
• the heater was turned off and the reaction mixture was diluted with water (150 mL) to precipitate the product.
• the crude product was isolated by suction filtration, washing with water, then dissolving in DCM and evaporating to dryness in vacuo.
• the crude product was evaporated onto silica gel and purified by flash chromatography on silica gel (330 g, equilibrate 5% EtOAc/hexanes, elute 5% EtOAc/hexanes (1 CV) - 20% EtOAc/hexanes (10 CV)).
• the material was very insoluble, so the solvent system was switched to 2% EtOAc/DCM, then was eluted with 20% EtOAc/DCM (10 CV)).
• the reaction mixture was placed in a heat block preheated to 95 °C and stirred open to air to cyclize and oxidize to the final product pyrrole.
• the reaction mixture was stirred at 95 °C for 3 hours, then at room temperature overnight.
• the reaction was diluted with ethyl acetate (300 mL), water (150 mL) and acidified with 6N HCI to pH ⁇ 1.
• the layers were separated, and the organic layer was washed with brine (25 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo.
• the crude product was dissolved in DCM and evaporated onto a 9:1 mixture of acid-washed celite and sand.
• reaction mixture was stirred for one minute at 0 0 C, then the cooling bath was removed, and the reaction mixture was placed back in the heating block set at 50 °C.
• the reaction mixture was stirred for one hour under argon at 50 °C, then additional triethylamine (2.308 mmol, 0.322 mL) and BFs.OEt? (3.460 mmol, 0.428 mL) were added and stirring continued at 50 °C an additional one hour.
• the reaction mixture was removed from the heating block and diluted with DCM (100 mL) and water (100 mL). The mixture was stirred vigorously, and the aqueous layer was acidified to pH ⁇ 1 with 6N HCI.
• the biphasic mixture was filtered through a thin layer of celite to remove a fine white precipitate.
• the layers were separated, and the aqueous layer was extracted with DCM (2 X 25 mL).
• the combined organic layers were dried over MgSC , filtered, and evaporated to dryness in vacuo.
• the crude product was dissolved in DCM and evaporated in vacuo onto a 9:1 mixture of acid-washed celite and sand.
• the reaction was again evacuated and replaced by argon and more 10% Pd/C (wet) was added (200 mg) as was ethyl acetate (50 mL).
• the vacuum/backfill hydrogen cycles were repeated three times and the reaction stirred under hydrogen atmosphere for 2 hours, at which point the reaction was complete.
• the catalyst was filtered off through a pad of celite and the solvents evaporated in vacuo to give a crude solid that was used without further purification.
• the mixture was heated at 80 °C for 16 hr.
• the resulted mixture was diluted with ethyl acetate (50 mL), then washed with water (30 mL x 3 times), 30 mL 5% sodium thiosulfate aqueous solution one time, and brine (30mL).
• the organic phase was dried with MgSO4, then the solvent was removed under reduced pressure to give a solid (50mg, in 88% yield).
• the resulted mixture was diluted with 20 mL dichloromethane, then loaded on silica gel and purified by flash chromatography using eluents of hexanes/dichloromethane (0% to 50% dichloromethane). The desired fraction was collected then concentrated under reduced pressure. The resulted solid was washed with methanol, dried in air to give a dark red solid (30mg, in 49% yield).
• Step 1 To a mixture of CuCI (50 mg, 0.5 mmol) in 1 mL anhydrous DMF was added 1 mL of 1 M solution of potassium t-butoxide in THF (1.0 mmol). The mixture was stirred for one hour at room temperature under argon atmosphere, then 2,2,2-trifluoroacetophenone (68 uL, 0.5 mmol) was added. The resulted mixture was stirred for 30 min at room temperature to have the desired CuCFs species formed.
• Step 2 To the above mixture, dry triethylamine hydrochloride salt (68 mg, 0.5 mmol) was added to neutralize excess potassium t-butoxide, then compound 3.4 (lOOmg, 0.048 mmol) was added. The whole was stirred at 50 9 C for 20 hrs, then diluted with 10 mL DCM, loaded on silica gel, and purified by flash chromatography using eluents of hexanes/DCM (0% - 80% DCM). The desired fraction was collected; and removal of solvents gave a red solid (65mg, in 65% yield).
• reaction was exothermic, so the rate of addition of DIC was controlled to keep reaction mixture below the boiling point.
• the reaction was stirred under argon for 30 minutes at room temperature, at which point TLC showed no alcohol remaining.
• the reaction mixture was diluted with hexanes (300 mL) and the reaction mixture washed with saturated NaHCOs/water solution (3 X 50 mL) and brine (50 mL). The reaction mixture was dried over MgSC , filtered and evaporated to dryness in vacuo.
• Compound 5.2 (2-ethylhexyl 2-(4'-(benzyloxy)-[l,l'-biphenyl]-4-yl)-4-phenyl-lH- pyrrole-3-carboxylate): Compound 5.2 was synthesized from Compound 5.1 (3.44 mmol, 864 mg), Zn (( ⁇ 10 pm dust), 4.59 mmol, 300 mg), Compound 5.1 (2.29 mmol, 653 mg), phenylacetylene (2.57 mmol, 0.277 mL), Pd(OAc)2 (0.230 mmol, 52 mg), Cu(OAc)2 (5.05 mmol, 917 mg), and acetic acid (4.59 mmol, 0.210 mL) in a manner similar to Compound 1.2.
• Compound 5.4 (bis(2-ethylhexyl) 3,7-bis(4'-(benzyloxy)-[l,l'-biphenyl]-4-yl)-5,5- difluoro-10-mesityl-l,9-diphenyl-5H-4A 4 ,5A 4 -dipyrrolo[l,2-c:2',l , -f][l,3,2]diazaborinine- 2,8-dicarboxylate): Compound 5.4 was synthesized from Compound 5.2 (0.287 mmol, 160 mg), mesitaldehyde (0.151 mmol, 0.0222 mL), pTsOH.FhO (0.0351 mmol, 6.8 mg), DDQ (0.215 mmol, 49 mg), followed by 2X triethylamine (0.861 mmol, 0.120 mL) and 2X BFs-OEt?
• the flask was placed in an aluminum heat block and the reaction mixture was stirred at room temperature and the headspace was flushed with argon. To the flask was added 10% Pd/C (200 mg). A hydrogen atmosphere was established by vacuum/backfill H2 (balloon) cycles (3X). The reaction mixture was stirred under a hydrogen atmosphere (balloon) at 60 0 C (block temperature) for 20 hours. TLC indicates complete consumption of starting material. The reaction mixture was filtered through a pad of Celite and evaporated to dryness in vacuo.
• Compound WLC-5 (bis(2-ethylhexyl) 5,5-difluoro-10-mesityl-l,9-diphenyl-3,7- bis(4'-((4-(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)-[l,l'-biphenyl]-4-yl)-5H- 4A 4 ,5A 4 -dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate): Compound WLC-5 was synthesized from Compound 5.5 (0.0504 mmol, 56 mg), (tris-CF3)-4-(perylen-3- yl)butanoic acid (mixture of isomers, 0.126 mmol, 68 mg), DMAP.pTsOH salt (0.0252 mmol, 7.4 mg), and DIC (0.202 mmol, 0.03
• the crude product was purified by flash chromatography on silica gel (120g, equilibrate 60% toluene/hexanes, solid load from 9:1 Celite:sand, elute 60% toluene/hexanes (2 CV) - 100% toluene (4 CV) - 3% EtOAc/toluene (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. Gives the product as a mixture of tris-CFs-perylene isomers, 42 mg (38% yield).
• Compound 6.1 was synthesized from Compound 5.2 (0.302 mmol, 168 mg), 2,6-dichlorobenzaldehyde (0.158 mmol, 27.7 mg), pTsOH-FhO (0.0377 mmol, 7.2 mg) in dry DCE at 70 ° C, then converted into Compound 6.2 in a manner similar to Compound 5.4 using DDQ, EtsN and BFs-OEt.
• WLC-6 (bis(2-ethylhexyl) 10-(2,6-dichlorophenyl)-5,5-difluoro-l,9-diphenyl-3,7- bis(4'-((4-(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)-[l,l'-biphenyl]-4-yl)-5H- 4A 4 ,5A 4 -dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate): Compound WLC-6 was synthesized from Compound 6.3 (0.0492 mmol, 56 mg), (tris-CF3)-4-(perylen-3- yl)butanoic acid (mixture of isomers, 0.123 mmol, 67 mg) , DMAP-pTsOH salt (0.0246 mmol,
• Example WLC-7 Compound 7.1. (benzyl 2-(4'-(octyloxy)-[l,l'-biphenyl]-4-yl)-4-phenyl-lH-pyrrole-3- carboxylate): Compound 7.1 was synthesized from zinc ((granules, 20 mesh), 80.0 mmol, 5.231 g), methanesulfonic acid (0.500 mmol, 0.0325 mL), 4'-(octyloxy)-[l,l'-biphenyl]-4- carbonitrile (15.0 mmol, 4.611 g), benzyl 2-bromoacetate (22.5 mmol, 3.56 mL) (added via syringe pump over 1 hour), FeCh (6.00 mmol, 973 mg) and beta-nitrostyrene (10.0 mmol, 1.491 mg) in a manner similar to Compound 2.2.
• the flask was raised out of the heat block. To the warm flask was added sodium hydride (60% in mineral oil, 9.575 mmol, 383 mg), followed by anhydrous ethylene glycol (20 mL) via syringe. Added ethylene glycol slowly at first to control outgassing of hydrogen gas. After all hydrogen evolution ceased, the flask was stoppered and placed back in the heat block. The heat block temperature was raised to 150 0 C and the reaction stirred at this temperature for 1 hour. The stirring rate was increased to high speed to help break up a puddle of melted Compound 7.1 sitting on the top of the ethylene glycol. The reaction was stirred at 150 °C for about 4 hours, then room temperature overnight.
• Compound 7.3 (bis(2-hydroxyethyl) 10-(2,6-dimethylphenyl)-5,5-difluoro-3,7- bis(4 , -(octyloxy)-[l,l , -biphenyl]-4-yl)-l,9-diphenyl-5H-4A 4 ,5A 4 -dipyrrolo[l,2-c:2 , ,l l - f][l,3,2]diazaborinine-2,8-dicarboxylate): Compound 7.3 was synthesized from Compound 7.2 (0.244 mmol, 125 mg), mesitaldehyde (128 mmol, 0.0189 mL), PTSOH.H2O (0.037 mmol, 7.0 mg), DDQ (0.159 mmol, 74 mg), BFs.OEt?
• WLC-7 bis(2-((4-(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)ethyl) 10- (2,6-dimethylphenyl)-5,5-difluoro-3,7-bis(4'-(octyloxy)-[l,l'-biphenyl]-4-yl)-l,9-diphenyl- 5H-4A 4 ,5A 4 -dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate): Compound WLC-
• the crude reaction mixture was loaded onto ⁇ 60 mL of flash silica gel in a solid load cartridge and purified by flash chromatography on silica gel (80 g, equilibrate in 100% hexanes, solid load, eluting 100% hexanes (2 CV) - 50% EtOAc/hexanes (40 CV)). Gives a quantitative yield of a dark-colored solid. Gives 33 mg (100% yield).
• Compound 9.1 (4',4'"-(5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4A 4 ,5A 4 - dipyrrolo[l,2-c:2',l , -f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-2-ol)):
• Compound 9.1 was synthesized from Compound 3.1 (0.188 mmol, 145 mg), 2-(4,4,5,5-tetramethyl-l,3,2- dioxaborolan-2-yl)phenol (0..752 mmol, 0.158 mL), K2CO3 (4.34 mmol, 600 mg), and then Pd(dppf)Cl2 (0.00470 mmol, 3.44 mg) in a manner similar to Compound 8.1 in anhydrous THF (20 mL) and water (3 mL) at 80 °C for 6 h.
• reaction mixture was loaded directly onto ⁇ 120 mL of flash silica gel in a solid loader and purified by flash chromatography on silica gel (120 g, equilibrate 100% hexanes, solid load, eluting 100% (2 CV) - 50% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness to give a purple solid. Gives 139 mg (93% yield).
• WLC-9 ((5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4A 4 ,5A 4 -dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',2-diyl) bis(4-(4,9,10- tris(trifluoromethyl)perylen-3-yl)butanoate)): WLC-9 was synthesized from Compound 9.1 (0.021 mmol, 17.3 mg), (tris-CF3)-4-(perylen-3-yl)butanoic acid (mixture of isomers, 0.0522 mmol, 28.5 mg), DMAPpTsOH salt (0.021 mmol, 6.2 mg), and EDC HCI (0.084 mmol, 16.1 mg) in anhydrous anhydrous DCM (5 mL) in a manner similar
• a glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.
• DI detergent and deionized
• DI isopropanol
• the PVB/Compound solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s. The spin-coated samples were baked on a hot plate set at 150 °C for 15 minutes to evaporate the remaining solvent.
• the 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure absorption Spectrum.
• the fluorescence spectrum (emission spectrum) of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Three wavelengths (450 nm, 500 nm, and 550 nm) were chosen as excitation wavelengths. The maximum emission and FWHM are shown in Table 1.
• the resulting absorption/emission spectrum for WLC-1 is shown in FIG.l, while the resulting absorption/emission spectrum for WLC-2 is shown in FIG.2.
• the quantum yields of spin-coated samples as described above were determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5"x 0.5" size film was taken out from glass substrate for QY measurement. Wavelengths were scanned every 15 nm from 450 nm to 600 nm (as excitation wavelengths). The QY at 450 nm are reported in Table 1.
• Photostability of the photoluminescent complexes were performed on 1-inch X 1-inch samples; comprising PVB as described above herein.
• the photoluminescent complexes were individually included with PVB film samples at a concentration of 2.5 X10 -3 M.
• the samples were then exposed to 537 ppfd White LEDs (6000K, inspired LED, Tempe, AZ, USA), 370 ppfd Blue LEDs (4.8 mW/cm 2 , 457 nm, Inspired LED, Tempe, AZ, USA), and/or 2000 ppfd White LEDs (6000K) (CREE, Durham, North Carolina, USA).
• White LED spectrum (6000K) is shown in FIG.3.

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