Open-shell conjugated polymer conductors, composites, and compositions

A conjugated copolymer with unpaired electrons comprising:

• an electron rich, donor monomer;
• and
• an electron deficient pro-quinoidal acceptor monomer;
• wherein the conjugated copolymer has a narrow bandgap of 0 Ev-0.66 Ev, diradical or multiple diradical character, and unpaired electrons in orbitals of different energies;
• and
• optionally, the conjugated copolymer is end-capped;
• wherein the conjugated copolymer has an open-shell ground state with a singlet or triplet spin multiplicity;
• and
• wherein the copolymer has a copolymer structure exhibiting open-shell character consisting of alternating the donor-acceptor monomers and is selected from copolymers of the Formulae (I)-(VIII):
• wherein in Formulae (I)-(IV), πD is the donor monomer and Y is selected from the group consisting of S, Se, Te, Si, BR3, PR3, NH, NR2 and Si, and πD comprises a substituent R, wherein R is selected from the group consisting of unsubstituted C1-C36 hydrocarbyl, substituted C1-C36 hydrocarbyl, substituted C6-C20 aryl, substituted C3-C20 heteroaryl, unsubstituted C0-C36 hydrocarbylene C6-C20 aryl-C0-C36 hydrocarbyl, substituted C0-C36 hydrocarbylene C6-C20 aryl C0-C36 hydrocarbyl, —F, —Cl, —Br, —I, —CN, —SR2, —OR, —COOR, and —NR2R3, where R2 and R3 are independently selected from a C1-C24 hydrocarbyl group;
• wherein for Formulae (V)-(VIII), πD is the donor monomer and Y is selected from the group consisting of S, Se, Te, Si, BR3, PR3, NH, NR2 and Si, and πD comprises a substituents R′ and R″, wherein R′ and R″ are each independently selected from the group consisting of unsubstituted C1-C36 hydrocarbyl, substituted C1-C36 hydrocarbyl, substituted C6-C20 aryl, substituted C3-C20 heteroaryl, unsubstituted C0-C36 hydrocarbylene C6-C20 aryl-C0-C36 hydrocarbyl, substituted C0-C36 hydrocarbylene C6-C20 aryl C0-C36 hydrocarbyl, —F, —Cl, —Br, —I, —CN, —R2, —SR2, —OR2, —COOR2, and —NR2R3, where R2 and R3 are independently selected from a C1-C24 hydrocarbyl group;
• wherein for Formulae (I)-(VIII):
• represents a triplet state, and represents a singlet state,
• πS is a conjugated spacer,
• πA is a moiety that is electron deficient, highly planar, pro-quinoidal, induces a transition from an aromatic electronic state to the quinoidal state, narrows the band gap, lowers ΔEST, and enhances the multiple diradical character yi thus promoting open-shell character, and wherein πA is selected from substituted and unsubstituted moieties selected from the group consisting of thiadiazoloquinoxaline, quinoxaline, thienothiadiazole, thienopyridine, thienopyrazine, pyrazinoquinoxaline, benzothiadiazole, bis-benzothiadiazole, benzobisthiadiazole, thiazole, thiadiazolothienopyrazine, diketopyrrolopyrrole, and combinations thereof and tunability of yi can be achieved through the introduction of πS, and, for Formulae (VII)-(VIII), the multiple diradical character yi promotes open-shell character while stabilizing the triplet state relative to the singlet state;
• m of πD is either 1 or 2, n of the copolymer is an integer>1, and the resulting copolymer of formulae (I), (II), (V), and (VI) exhibits a singlet open-shell electronic ground state defined by an S0 electronic state lying below T1, and the resulting copolymer of formulae (III), (IV), (VII), and (VIII) exhibits a triplet open-shell electronic ground state defined by a To electronic state lying below S1,
• wherein the optional end-capped copolymer structure has a formula:
• wherein πn is the copolymer, and
• πe is any substituted and unsubstituted moiety selected from the group consisting of thiophene, bithiophene, dithienothiophene, selenophene, biselenophene, diselenoselenophene, cyclopentadithiophene, cyclopentadiselenophene, and any combination thereof, as well as unsubstituted C1-C36 hydrocarbyl, substituted C1-C36 hydrocarbyl, unsubstituted C6-C20 aryl, substituted C6-C20 aryl, unsubstituted C3-C20 heteroaryl, substituted C3-C20 heteroaryl, unsubstituted C0-C36 hydrocarbylene, substituted C0-C36 hydrocarbylene, —F, —Cl, —Br, —I, —CN, —R2, —SR2, —OH, —OR2, —COOH, —COOR2, —NH2, —NHR2, and —NR2R3, where R2 and R3 of πe are independently selected from a C1-C24 hydrocarbyl group, and wherein substituted derivatives of πe comprise hydrocarbyl, aryl, heteroaryl, or hydrocarbylene substituents functionalized with one or multiple R groups selected from the group consisting of a substituted C1-C24 hydrocarbyl group, and any combination thereof.