Carbenium based organic redox flow batteries

A redox flow battery comprising:

• a catholyte comprising a radical dication of a compound of Formula I;
• and
• an anolyte comprising a neutral radical of a compound of Formula I;
• wherein the compound of Formula (I) is represented by the following structure:
• wherein:
• X is from −4 to +4;
• each of R1a, R1b, R1c, R1d, R2a, R2b, R2c, R2d, R3a, R3b, R3c, and R3d is independently H, halide, CF3, NH2, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, NO2, CN, CO2R, or Ar1;
• or R2a and R3d together form —X1—;
• or R1a and R2d together form —X2—;
• or R1d and R1a together form —X3—;
• or R1a and R1b together with atoms to which they are attached to form a phenyl;
• or R2c and R2d together with atoms to which they are attached to form a phenyl;
• each of X1, X2 and X3 is independently O, NR4a, PR4a, CR4aR4b, or SiR4aR4b;
• each of R4a and R4b is independently H, halide, CF3, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, Ar3, -L-Ar3, -L-Z, or -L2-Z2;
• each of Y is independently H, halide, OR5a, NR5aR5b, PR5aR5b, NO2, CN, CF3, CO2R, N3, or Ar2;
• each of R5a, and R5b is independently H, CF3, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, Ar4, -L1-Ar4, or -L1-Z1;
• each of L and L1 is independently C1-C12 alkylene, C1-C12 heteroalkylene, or arylene;
• each of L2 is independently C1-C12 alkylene;
• Z and Z1 are each independently a moiety comprising conjugated heterocyclic carbenium;
• Z2 is each independently —(OCH2CH2O)nCH3;
• n is each independently 1 to 20;
• each of R is independently C1-C12 alkyl or aryl;
• Ar1, Ar2, Ar3 and Ar4 are each independently unsubstituted or substituted phenyl or unsubstituted or substituted heteroaryl;
• each of Ar1, Ar2, Ar3 and Ar4 is independently substituted with 0 to 5 substituents;
• the substituents are each independently selected from the group consisting of halide, CF3, NH2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, NO2, CN, or aryl.

A redox flow battery comprising:

• a catholyte comprising a conjugated heterocyclic cationic compound in a first oxidation state;
• and
• an anolyte comprising a conjugated heterocyclic cationic compound in a second oxidation state;
• wherein the first oxidation state is a higher oxidation state than the second oxidation state,
• wherein the conjugated heterocyclic cationic compound in the catholyte and anolyte are each independently a compound of Formula I, wherein the compound of Formula (I) is represented by the following structure:
• wherein:
• X is from −4 to +4;
• each of R1a, R1b, R1c, R1d, R2a, R2b, R2c, R2d, R3a, R3b, R3c, and R3d is independently H, halide, CF3, NH2, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, NO2, CN, CO2R, or Ar1;
• or R2a and R3d together form —X1—;
• or R1a and R2d together form —X2—;
• or R1d and R1a together form —X3—;
• or R1a and R1b together with atoms to which they are attached to form a phenyl;
• or R2c and R2d together with atoms to which they are attached to form a phenyl;
• each of X1, X2 and X3 is independently O, NR4a, PR4a, CR4aR4b, or SiR4aR4b;
• each of R4a and R4b is independently H, halide, CF3, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, AP, -L-Ar3, -L-Z;
• or -L2-Z2;
• each of Y is independently H, halide, OR5a, NR5aR5b, PR5aR5b, NO2, CN, CF3, CO2R, N3, or Ar2;
• each of R5a, and R5b is independently H, CF3, C1-C12 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, Ar4, -L1-Ar4, or -L1-Z1;
• each of L and L 1 is independently C1-C12 alkylene, C1-C12 heteroalkylene, or arylene;
• each of L2 is independently C1-C12 alkylene;
• Z and Z1 are each independently a moiety comprising conjugated heterocyclic carbenium;
• Z2 is each independently —(OCH2CH2O)nCH3;
• n is each independently 1 to 20;
• each of R is independently C1-C12 alkyl or aryl;
• Ar1, Ar2, Ar3, and Ar4 are each independently unsubstituted or substituted phenyl or unsubstituted or substituted heteroaryl;
• each of Ar1, Ar2, Ar3, and Ar4 is independently substituted with 0 to 5 substituents;
• the substituents are each independently selected from the group consisting of halide, CF3, NH2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkyl amino, NO2, CN, or aryl.