Photochromic Indeno Fused Phenanthrenopyran Compounds

A photochromic compound represented by the following Formula (I),

• wherein n is 1 to 3, and m is 1 to 4,
• R2 is selected from the group consisting of, hydrogen;
• halogen;
• linear or branched C1-C20 alkyl;
• linear or branched C1-C20 perhaloalkyl;
• —ORa;
• —SRa, where each Ra is independently selected from the group consisting of hydrogen, linear or branched C1-C20 alkyl, and linear or branched C1-C20 perhaloalkyl;
• —C(O)ORb, where Rb is hydrogen or linear or branched C1-C10 alkyl;
• substituted or unsubstituted aryl, each aryl substituent being independently selected from the group consisting of hydroxyl, halogen, carbonyl, linear or branched C1-C20 alkoxycarbonyl, cyano, linear or branched C1-C20 haloalkyl, linear or branched C1-C20 alkyl, linear or branched C1-C20 alkoxy, and linear or branched C1-C20 perhaloalkyl;
• and a group Y1;
• R6 and R7 are each independently selected from the group consisting of, hydrogen;
• halogen;
• a lengthening group L1;
• —ORc, and —SRc, where each Rc is independently selected from the group consisting of hydrogen, a lengthening group L2, linear or branched C1-C20 alkyl, —C(O)—Rd, and —S(O)(O)—Re, where Rd and Re are each independently selected from the group consisting of linear or branched C1-C10 alkyl, linear or branched C1-C10 perhaloalkyl, phenyl, linear or branched C1-C10 alkyl substituted phenyl, and linear or branched C1-C10 perhaloalkyl substituted phenyl, provided that at least one of R6 and R7 is other than hydrogen;
• R1 independently for each n, and R3 independently for each m are each independently selected from the group consisting of, hydrogen;
• cyano;
• a reactive substituent;
• a lengthening group L3;
• halogen selected from the group consisting of fluoro, chloro, and bromo;
• linear or branched C1-C20 alkyl;
• linear or branched C1-C20 perhaloalkyl;
• C3-C10 cycloalkyl;
• a group Y2;
• substituted or unsubstituted phenyl, the phenyl substituents being selected from the group consisting of at least one of hydroxyl, halogen, carbonyl, linear or branched C1-C20 alkoxycarbonyl, cyano, linear or branched C1-C20 haloalkyl, linear or branched C1-C20 alkyl, linear or branched C1-C20 alkoxy, linear or branched C1-C20 perhaloalkyl, and combinations thereof;
• —O—R10′, —S—R10′, —C(O)—R10′, —C(O)—OR10′, —OC(O)—R10′, —OC(O)O—R10′, —C(O)N(R1′)R10′, —N(R10′)C(O)N(R10′)(R10′), or —Si(OR10′)w(R10′)t, wherein each R10′ independently is hydrogen, linear or branched C1-C20 alkyl, phenyl(C1-C20)alkyl, mono(C1-C20)alkyl substituted phenyl(C1-C20)alkyl, mono(C1-C20)alkoxy substituted phenyl(C1-C20)alkyl, (C1-C20)alkoxy(C2-C20)alkyl, C3-C10 cycloalkyl, or mono(C1-C20)alkyl substituted C3-C10 cycloalkyl, and w and t are each independently 0 to 3, provided that w+t is 3;
• and
• —N(R11′)R12′, wherein R11′ and R12′ are each independently hydrogen, linear or branched C1-C20 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, linear or branched C1-C20 alkylaryl, C3-C10 cycloalkyl, C4-C20 bicycloalkyl, C5-C20 tricycloalkyl or linear or branched C1-C20 alkoxyalkyl, wherein the aryl group is phenyl or naphthyl, or R11′ and R12′ come together with the nitrogen atom to form a ring;
• R4 and R5 are each independently selected from the group consisting of,
• (i) hydrogen, hydroxyl, linear or branched C1-C20 alkyl, linear or branched C1-C20 haloalkyl, C3-C10 cycloalkyl, allyl, benzyl, or substituted benzyl, the benzyl substituents being chosen from halogen, linear or branched C1-C20 alkyl or linear or branched C1-C20 alkoxy;
• (ii) an unsubstituted, mono- di-or tri-substituted group chosen from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl, the group substituents in each case being independently chosen from halogen, linear or branched C1-C20 alkyl or linear or branched C1-C20 alkoxy;
• and
• (iii) a group Y3;
• or
• (iv) R4 and R5 together form a spiro substituent selected from the group consisting of a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 10 carbon atoms, a substituted or unsubstituted spiro-heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 10 carbon atoms including the spirocarbon atom, the spiro-carbocyclic ring and spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene rings, the substituents being hydrogen or linear or branched C1-C20 alkyl;
• and
• B and B′ are each independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, alkenyl, and alkynyl, or B and B′ taken together form a ring structure,
• wherein each lengthening group L1, L2, and L3 is independently represented by the following Formula (II),
• [S1]c-[Q1-[S2]d]d′-[Q2-[S3]e]e′-[Q3-[S4]f]f′—S5—P Formula (II)
• wherein:
• (a) Q1, Q2, and Q3 for each occurrence, are independently a divalent group selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted heterocycloalky, and substituted heterocycloalkyl;
• wherein the aryl substituents, heteroaryl substituents, cycloalkyl substituents, and heterocycloalkyl substituents are each independently selected from the group consisting of P, liquid crystal mesogens, halogen, poly(C1-C18 alkoxy), C1-C18 alkoxycarbonyl, C1-C18 alkylcarbonyl, C1-C18 alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C1-C18)alkoxy, perfluoro(C1-C18)alkoxycarbonyl, perfluoro(C1-C18)alkylcarbonyl, perfluoro(C1-C18)alkylamino, di-(perfluoro(C1-C18)alkyl)amino, perfluoro(C1-C18)alkylthio, C1-C18 alkylthio, C1-C18 acetyl, C3-C10 cycloalkyl, C3-C10 cycloalkoxy, straight-chain C1-C18 alkyl, and branched C1-C18 alkyl;
• wherein the straight-chain C1-C18 alkyl and branched C1-C18 alkyl are mono-substituted with a group selected from the group consisting of cyano, halogen, and C1-C18 alkoxy;
• or
• wherein the straight-chain C1-C18 alkyl and branched C1-C18 alkyl are poly-substituted with at least two groups independently selected from the group consisting of halogen, -M(T)(v-1) and -M(OT)(v-1), wherein M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and v is the valence of M;
• (b) c, d, e, and f are each independently chosen from an integer of 1 to 20;
• and each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit selected from the group consisting of:
• (i) alkylene, substituted alkylene, haloalkylene, substituted haloalkylene, —Si(CH2)g—, and —(Si[(CH3)2]O)h—, wherein g for each occurrence is independently chosen from an integer from 1 to 20;
• h for each occurrence is independently chosen from an integer from 1 to 16;
• and the substitutes for the alkylene and haloalkylene are independently selected from the group consisting of C1-C18 alkyl, C3-C10 cycloalkyl and aryl;
• (ii) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)2—C(Z′)2—, —N(Z)—C(Z)2—, and a single bond, wherein Z for each occurrence is independently selected from the group consisting of hydrogen, C1-C18 alkyl, C3-C10 cycloalkyl and aryl, and Z′ for each occurrence is independently selected from the group consisting of C1-C18 alkyl, C3-C10 cycloalkyl and aryl;
• and
• (iii) —O—, —C(═O)—, —C≡C—, —N═N—, —S—, —S(═O)—, —(O═)S(═O)—, —(O═)S(═O)O—, —O(O═)S(═O)O— and straight-chain or branched C1-C24 alkylene residue, the C1-C24 alkylene residue being unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen,
• provided that when two spacer units comprising heteroatoms are linked together the spacer units are linked so that heteroatoms are not directly linked to each other, and the bond between S5 and P is free of two heteroatoms linked to each other;
• (c) P for each occurrence is independently selected from the group consisting of hydroxy, amino, C2-C18 alkenyl, C2-C18 alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato, acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino, aminocarbonyl, C1-C18 alkyl aminocarbonyl, aminocarbonyl(C1-C18)alkyl, C1-C18 alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy(C1-C18)alkyl, C1-C18 alkyl, C1-C18 alkoxy, amino(C1-C18)alkyl, C1-C18 alkylamino, di-(C1-C18)alkylamino, C1-C18 alkyl(C1-C18)alkoxy, C1-C18 alkoxy(C1-C18)alkoxy, nitro, poly(C1-C18)alkyl ether, (C1-C18)alkyl(C1-C18)alkoxy(C1-C18)alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy(C1-C18)alkyl, methacryloyl, methacryloyloxy(C1-C18)alkyl, 2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato(C1-C18)alkyl, itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative, main-chain and side-chain liquid crystal polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, maleimide derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, and substituted or unsubstituted chiral or non-chiral monovalent or divalent groups chosen from steroid radicals, terpenoid radicals, alkaloid radicals and mixtures thereof, wherein the substituents are independently chosen from C1-C18 alkyl, C1-C18 alkoxy, amino, C3-C10 cycloalkyl, C1-C18 alkyl(C1-C18)alkoxy, fluoro(C1-C18)alkyl, cyano, cyano(C1-C18)alkyl, cyano(C1-C18)alkoxy or mixtures thereof, or P is a structure having from 2 to 4 reactive groups, or P is an unsubstituted or substituted ring opening metathesis polymerization precursor, or P is a substituted or unsubstituted photochromic compound;
• and
• (d) d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f is at least 1;
• and
• wherein each group Y1, Y2, and Y3 independently comprises at least one residue of a ring-opened cyclic monomer, wherein each ring-opened cyclic monomer is independently selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer.