Polymerizable near-IR dyes

A polymer having a structure according to formula (II):

• or a tautomer, salt, hydrate, or solvate thereof,
• the polymer comprising a polymerizable near-IR dye and a monomer;
• wherein:
• Z1 is absent, O, NRZ1, or S;
• RZ1 is H, optionally substituted C1-C10 alkyl, or optionally substituted C2-C10 heteroalkyl;
• X1 is absent, optionally substituted C6-C10 arylene, or optionally substituted C1-C10 heteroarylene;
• Z2 is absent, NRX1, O, S, NRX2C(O), OC(O), SC(O), C(O)O, C(O)NRX3, C(S)O, or C(O)S;
• Z3 is absent or H;
• RX1, RX2, and RX3 are each independently H, optionally substituted C1-C10 alkyl, or optionally substituted C1-C10 heteroalkyl;
• L1 is absent, optionally substituted C1-C30 alkylene, or optionally substituted C1-C30 heteroalkylene;
• Q1 is NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• RZ3 is H, optionally substituted C1-C10 alkyl, optionally substituted C3-C10 cycloalkyl, optionally substituted C1-C10 heteroalkyl, or optionally substituted C1-C10 cycloheteroalkyl;
• RQ1 is H, Me, Et, or n-Pr;
• each of Y1 and Y4, independently, is absent or optionally substituted C1-C4 alkylene or optionally substituted C2-C4 heteroalkylene;
• each of Y2 and Y3, independently, is absent or, together with the carbon atoms to which each is attached, form optionally substituted C6-C10 aryl or optionally substituted C2-C10 heteroaryl;
• Y5 is absent or N or CR7;
• R7 is H, optionally substituted C1-C10 alkyl, optionally substituted C3-C10 cycloalkyl, optionally substituted C1-C10 heteroalkyl, or optionally substituted C1-C10 cycloheteroalkyl;
• each of W1 and W2, independently, is NR2, S, O, Se, or CR3R4;
• R2, R3, and R4 are independently H, optionally substituted C1-C30 alkyl, optionally substituted C1-C30 heteroalkyl, or -L2-Q2;
• L2 is optionally substituted C1-C30 alkylene or optionally substituted C1-C30 heteroalkylene;
• Q2 is H, C(RQ1)CH2, C6H4CHCH2, NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• each of R5 and R6, independently, is -L3-Q3, optionally substituted C1-C30 alkyl, or optionally substituted C6-C10 aryl;
• L3 is optionally substituted C1-C30 alkylene or optionally substituted C1-C30 heteroalkylene;
• Q3 is H, C(RQ1)CH2, C6H4CHCH2, NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• and
• each k is independently 0 or 1;
• wherein, the group Q1 is linked to a group J, and
• J is at least one monomer comprising HEMA (hydroxyethyl methacrylate), DMA (N,N-Dimethylacrylamide), HPA (Hydroxypropyl acrylate), methyl methacrylate, acrylamide, PEGMA (polyethyleneglycol methacrylate), methacrylic acid, hydroxyethyl acrylate, N-vinyl pyrrolidone, methacryloylaminopropyl trimethylammonium chloride, diallyl dimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, or sodium sulfopropyl methacrylate.

A polymer comprising a polymerizable near-IR dye and a monomer, said polymer having a repeating unit according to formula (III):

• wherein:
• each D1 and D2 is independently a residue of a polymerizable near-IR dye, wherein said polymerizable near-IR dye has a structure according to formula (I):
• or a tautomer, salt, hydrate, or solvate thereof,
• wherein:
• Z1 is absent, O, NRZ1, or S;
• RZ1 is H, optionally substituted C1-C10 alkyl, or optionally substituted C2-C10 heteroalkyl;
• X1 is absent, optionally substituted C6-C10 arylene, or optionally substituted C1-C10 heteroarylene;
• Z2 is absent, NRX1, O, S, NRX2C(O), OC(O), SC(O), C(O)O, C(O)NRX3, C(S)O, or C(O)S;
• Z3 is absent or H;
• RX1, RX2, and RX3 are each independently H, optionally substituted C1-C10 alkyl, or optionally substituted C1-C10 heteroalkyl;
• L1 is absent, optionally substituted C1-C30 alkylene, or optionally substituted C1-C30 heteroalkylene;
• Q1 is NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• RZ3 is H, optionally substituted C1-C10 alkyl, optionally substituted C3-C10 cycloalkyl, optionally substituted C1-C10 heteroalkyl, or optionally substituted C1-C10 cycloheteroalkyl;
• RQ1 is H, Me, Et, or n-Pr;
• each of Y1 and Y4, independently, is absent or optionally substituted C1-C4 alkylene or optionally substituted C2-C4 heteroalkylene;
• each of Y2 and Y3, independently, is absent or, together with the carbon atoms to which each is attached, form optionally substituted C6-C10 aryl or optionally substituted C2-C10 heteroaryl;
• Y5 is absent or N or CR7;
• R7 is H, optionally substituted C1-C10 alkyl, optionally substituted C3-C10 cycloalkyl, optionally substituted C1-C10 heteroalkyl, or optionally substituted C1-C10 cycloheteroalkyl;
• each of W1 and W2, independently, is NR2, S, O, Se, or CR3R4;
• R2, R3, and R4 are independently H, optionally substituted C1-C30 alkyl, optionally substituted C1-C30 heteroalkyl, or -L2-Q2;
• L2 is optionally substituted C1-C30 alkylene or optionally substituted C1-C30 heteroalkylene;
• Q2 is H, C(RQ1)CH2, C6H4CHCH2, NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• each of R5 and R6, independently, is -L3-Q3, optionally substituted C1-C30 alkyl, or optionally substituted C6-C10 aryl;
• L3 is optionally substituted C1-C30 alkylene or optionally substituted C1-C30 heteroalkylene;
• Q3 is H, C(RQ1)CH2, C6H4CHCH2, NRZ3C(O)C(RQ1)CH2, OC(O)C(RQ1)CH2, or SC(O)C(RQ1)CH2;
• and
• each k is independently 0 or 1;
• with the proviso that
• each J1 and J2 is a residue of HEMA (hydroxyethyl methacrylate), DMA (N,N-Dimethylacrylamide), HPA (Hydroxypropyl acrylate), methyl methacrylate, acrylamide, PEGMA (polyethyleneglycol methacrylate), methacrylic acid, hydroxyethyl acrylate, N-vinyl pyrrolidone, methacryloylaminopropyl trimethylammonium chloride, diallyl dimethyl ammonium chloride, vinyl benzyl trimethyl ammonium chloride, or sodium sulfopropyl methacrylate,
• wherein:
• D1 and D2 can be the same or different;
• J1 and J2 can be the same or different;
• m is an integer from 1 to 100;
• n is an integer from 0 to 100;
• a is an integer from 0 to 100;
• and
• z is an integer from 0 to 100.