Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications
A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,β fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.
1. A compound comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings, said compound having a formula selected from the group consisting of:
M is any element selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Ti, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U;
wherein R 1 , R 3 -R 5 , R 7 -R 8 and R 51 -R 82 are independently selected from the group consisting of hydrogen, alkyl, fluoroalkyl, hydroxyl, halo, mercapto group, amino, cyano, alkenyl, alkynyl, and aryl,
wherein R 2 and R 6 are independently selected from the group consisting of hydrogen, alkyl, fluoroalkyl, hydroxyl, alkoxy, halo, mercapto group, amino, cyano, alkenyl, alkynyl, 3,5-di-tert-butylphenyl, and aryl, and
wherein adjacent substituents R 51 -R 82 optionally form fused rings, wherein the fused rings are aromatic, unsaturated, or combinations of both aromatic and unsaturated rings, including four, five, six, seven, eight, or nine-membered rings, wherein the fused rings can include one or more heteroatoms independently selected from the group consisting of O, S, Se, Te, N, P, As, Si, Ge, and B.
2. The compound of claim 1 , having a formula selected from the group consisting of:
3. The compound of claim 1 , wherein R 1 , R 3 -R 5 , R 7 -R 8 , and R 51 -R 82 are independently selected from the group consisting of hydrogen, C 1 -C 15 alkyl, fluoroalkyl, hydroxyl, halo, mercapto group, amino, cyano, C 2 -C 15 alkenyl, C 2 -C 15 alkynyl, and aryl,
wherein R 2 and R 6 are independently selected from the group consisting of hydrogen, C 1 -C 15 alkyl, fluoroalkyl, hydroxyl, alkoxy, halo, mercapto group, amino, cyano, C 2 -C 15 alkenyl, C 2 -C 15 alkynyl, 3,5-di-tert-butylphenyl, and aryl.
4. The compound of claim 1 , wherein R 1 , R 3 -R 5 , R 7 -R 8 , and R 51 -R 82 are independently selected from the group consisting of hydrogen, C 1 -C 15 alkyl, C 2 -C 15 alkenyl, C 2 -C 15 alkynyl, and aryl,
wherein R 2 and R 6 are independently selected from the group consisting of hydrogen, C 1 -C 15 alkyl, C 2 -C 15 alkenyl, C 2 -C 15 alkynyl, 3,5-di-tert-butylphenyl, and aryl.
5. The compound of claim 1 , wherein the one or more non-activated polycyclic aromatic rings are selected from the group consisting of:
wherein the wave-line represents the fusion position of the polycyclic aromatic rings to the porphyrin; and
wherein the dot represents the point where the polycyclic aromatic rings are connected to the mesa position of the porphyrin.
6. The compound of claim 1 , wherein, when present, each one of R 51 -R 82 is hydrogen.
7. The compound of claim 1 , wherein the compound is
8. The compound of claim 1 , wherein the porphyrin and at least one of the polycyclic aromatic rings are fused in meso,β mode.
9. The compound of claim 1 , wherein the porphyrin and at least one of the polycyclic aromatic rings are fused in β,meso, β mode.