Methods of forming an object in a volume of a photohardenable composition, photohardenable compositions, and photoinitiators

A photohardenable composition comprising a photohardenable resin component and a photoswitchable photoinitiator, wherein the photoswitchable photoinitiator is activated by exposure to light having a first wavelength and light having a second wavelength to induce a crosslinking or polymerization reaction in the photohardenable resin component at an intersection of the lights of the two wavelengths, wherein the first and second wavelengths are different, and wherein the photoswitchable photoinitiator comprises a P-type photochromic molecule comprising a P-type diarylcycloalkene molecule represented by general formula (I):

• wherein:
• A represents a substituted or unsubstituted cycloalkene ring structure,
• X represents a heteroaryl group represented by following formula (Xa), (Xb), (Xc), or (Xd):
• wherein:
• E is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R6 substituent group (NR6),
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R7 substituent group (SR7), an oxygen atom with an R8 substituent group (OR8), or a cyano (CN) group,
• G is a member of the ring and represents a carbon atom with an R9 substituent group (CR9) or a nitrogen atom (N);
• L is a member of the ring and represents a carbon atom with an R1 substituent group (C R1) or a nitrogen atom (N), and
• R1 and R6-R9 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• or
• wherein:
• E is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R6 substituent group (NR6),
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R7 substituent group (SR7), an oxygen atom with an R8 substituent group (OR8), or a cyano (CN) group,
• G is a member of the ring and represents a carbon atom with an R substituent group (CR9) or a nitrogen atom (N);
• L is a member of the ring and represents a carbon atom with an R1 substituent group (C R1) or a nitrogen atom (N), and
• R1 and R6-R9 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• or
• wherein:
• E is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R6 substituent group (NR6),
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R7 substituent group (SR7), an oxygen atom with an R8 substituent group (OR8), or a cyano (CN) group, and
• R2-R8 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• or
• E is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R6 substituent group (NR6),
• Z represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R7 substituent group (SR7), an oxygen atom with an R8 substituent group (OR8), or a cyano (CN) group, and
• R2-R8 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• Y represents a heteroaryl group represented by formula (Ya), (Yb), (Yc) or (Yd):
• wherein:
• E′ is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R15 substituent group (NR15),
• Z′ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R16 substituent group (SR16), an oxygen atom with an R17 substituent group (OR17), or a cyano (CN) group,
• G′ is a member of the ring and represents a carbon atom with an R18 substituent group (CR18) or a nitrogen atom (N);
• L′ is a member of the ring and represents a carbon atom with an R10 substituent group (C R10) or a nitrogen atom (N), and
• R10 and R15-R18 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• wherein:
• E′ is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R15 substituent group (NR15),
• Z′ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R16 substituent group (SR16), an oxygen atom with an R17 substituent group (OR17), or a cyano (CN) group,
• G′ is a member of the ring and represents a carbon atom with an R18 substituent group, (CR18) or a nitrogen atom (N);
• L′ is a member of the ring and represents a carbon atom with an R10 substituent group (C R10) or a nitrogen atom (N), and
• R10 and R15-R18 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or
• unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• wherein:
• E′ is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R15 substituent group (NR15),
• Z′ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R16 substituent group (SR16), an oxygen atom with an R17 substituent group (OR17), or a cyano (CN) group, and
• R11-R17 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• or
• wherein:
• E′ is a member of the ring and represents an oxygen atom (O), a sulfur atom(S), a sulfur dioxide group (SO2), a selenium atom, or a nitrogen atom with an R15 substituent group (NR15),
• Z′ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkynyl group, a sulfur atom with an R16 substituent group (SR16), an oxygen atom with an R17 substituent group (OR17), or a cyano (CN) group, and
• R11-R17 are substituents, are the same or different, and independently represent, for example, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted ester group, a substituted or unsubstituted carbonate group, a substituted or unsubstituted ketone group, a substituted or unsubstituted aldehyde group, a substituted or unsubstituted imine group, a substituted or unsubstituted carboxyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted urethane group, a substituted or unsubstituted urea group, a substituted or unsubstituted tetrazine group, a substituted or unsubstituted amino group, iodo, bromo, chloro, fluoro, a cyano group (—CN), a nitro group (—NO2), a hydroxyl group (—OH), a thiol (—SH), a thioether group (R—X-R′ wherein R or R′ can independently represent an aryl or alkyl group), or a substituted or unsubstituted alcohol group;
• wherein X and/or Y includes at least one R substituent comprising a substituted or unsubstituted polycyclic group including at least two fused rings of atoms, wherein at least one of the fused rings of atoms includes one or more substituents, wherein at least one of the substituents comprises a double bonded oxygen attached to a carbon atom ring member included in one of the fused rings,
• wherein the polycyclic group is represented by general formula (PG-E):
• or a derivative thereof.