Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays
AssigneeNorth Carolina State University
InventorsRobert S. Loewe, Kin-ya Tomizaki, Jonathan S. Lindsey
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Abstract
The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: X1Xm+1)m (I) wherein m is at least 1; X1 is a charge separation group, and X2 through Xm+1 are chromophores. At least one of X2 through Xm+1 has at least one perylene group coupled thereto.
Claims81
A light harvesting array, comprising:
- (a) a first substrate comprising a first electrode;
- and
- (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I:
- X1Xm+1)m (I)
- wherein:
- m is at least 1;
- X1 is a charge separation group having an excited-state of energy equal to or lower than that of X2;
- X2 through Xm+1 are chomophores;
- and
- at least one of X2 through Xm+1 has at least one perylene group coupled thereto, and wherein said perylene group is a perylene (bis)imide group.
An electrical device according to 42, claim wherein said circuit comprises a resistive load.
A composition useful for the manufacture of a light harvesting array, comprising:
- (a) a non-polar organic solvent;
- and
- (b) from 2 microMolar to 100 milliMolar of light harvesting rods solubilized in said organic solvent, said light harvesting rods comprising a polymer of Formula I:
- X1Xm+1)m (I)
- wherein:
- m is at least 1;
- X1 is a charge separation group having an excited-state of energy equal to or lower than that of X2;
- X2 through Xm+1 are chromophores;
- and
- at least one of X2 through Xm+1 has at least one perylene group coupled thereto;
- wherein said perylene group is a compound of formula IV:
- wherein:
- R9 is a link to one of said chromophores;
- R1 and R6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin;
- Y2 through Y6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;
- and
- wherein either (i) Y4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y3 is halo, ethynyl, dialkylboronate, or trialkyltin.
A method of making a composition useful for the manufacture of light harvesting arrays, said composition comprising a non-polar organic solvent and from 2 microMolar to 100 milliMolar of light harvesting rods solubilized in said organic solvent, said light harvesting rods comprising a polymer of Formula I:
- X1Xm+1)m (I)
- wherein:
- m is at least 1;
- X1 is a charge separation group having an excited-state of energy equal to or lower than that of X2;
- X2 through Xm+1 are chromophores;
- and
- at least one of X2 through Xm+1 has at least one perylene group coupled thereto;
- wherein said perylene group is a compound of formula IV:
- wherein:
- R9 is a link to one of said chromophores;
- R1 and R6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin;
- and
- Y2 through Y6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;
- wherein either (i) Y4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y3 is halo, ethynyl, dialkylboronate, or trialkyltin;
- said method comprising the steps of:
- (a) providing a mixture of X1 through Xm+1 as monomers in said organic solvent with an amine and a catalyst;
- (b) polymerizing said monomers in said mixture to produce a polymer of Formula I;
- and then
- (c) separating amine and catalyst from said mixture to provide said composition having said polymer of Formula I solubilized therein.
A compound according to Formula II:
- wherein:
- Ar is an aromatic group;
- Porph is a porphyrinic macrocycle;
- Peryl1 is a first perylene group;
- and
- Peryl2 is a second perylene group.
A compound according to Formula III:
- wherein:
- Ar1 is a first aromatic group;
- Ar2 is a second aromatic group;
- Porph is a porphyrinic macrocycle;
- Peryl1 is a perylene group;
- Peryl2 is a second perylene group;
- m is from 1 to 3;
- and
- n is from 1 to 3.
A compound of formula IV:
- wherein:
- R1, R6, and R9 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate and trialkyltin;
- and
- Y2 through Y6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;
- wherein either (i) Y4 is halo, ethynyl, dialkylboronate, or trialkyltin, or (ii) Y3 is halo, ethynyl, dialkylboronate, or trialkyltin.
A compound of formula V:
- wherein:
- R1 and R6 are independently selected from the group consisting of H, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halo, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin;
- and
- R9 is selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, ethynylalkyl, ethynylaryl, dialkylboronate, and trialkyltin.
A compound of formula VI:
- wherein
- Ar is an aromatic group;
- and
- Y1 and Y2 are independently selected perylene mono-imide groups;
- and
- X is selected from the group consisting of formyl, halo, or 5-dipyrromethane.
Dependencies are inferred from the claim text.