Abstract: This invention provides a new procedure for attaching molecules to semiconductor surfaces, in particular silicon. The molecules, which include, but are not limited to porphyrins and ferrocenes, have been previously shown to be attractive candidates for molecular-based information storage. The new attachment procedure is simple, can be completed in short times, requires minimal amounts of material, is compatible with diverse molecular functional groups, and in some instances affords unprecedented attachment motifs. These features greatly enhance the integration of the molecular materials into the processing steps that are needed to create hybrid molecular/semiconductor information storage devices.

Abstract: A molecular memory cell includes first and second electrodes. First and second charge storage molecules have respective first and second oxidation potentials and are disposed between the first and second electrodes. A molecular linkage couples the first and second charge storage molecules to the first electrode and provides respective first and second electron transfer rates for the first and second charge storage molecules. The first and second different oxidation potentials are different and/or the first and second electron transfer rates are different. In particular, the second oxidation potential may be greater than the first oxidation potential and the first electron transfer rate may be greater than the second electron transfer rate, such that the first charge storage molecule may be used as fast, volatile primary memory and the second charge storage molecule can be used as slower, less volatile secondary memory.

Abstract: The present invention provides a method of making a metal complex. The method comprises the steps of: (a) acylating a dipyrromethane or a 1-monoacyldipyrromethane to form a mixed reaction product comprising a 1,9-diacyidipyrromethane; (b) combining the reaction product with a compound of the formula R2MX2 in the presence of a base, where R is alkyl or aryl, M is Sn, Si, Ge, or Pb (preferably Sn), and X is halo, OAc, acac, or OTf, to form a product comprising a metal complex of the formula DMR2 in the mixed reaction product, wherein D is a 1,9-diacyldipyrromethane; and then (c) separating the metal complex from the mixed reaction product. The method may be utilized for the convenient synthesis and separation of 1,9-diacyldipyrromethanes. Metal complex intermediates useful in such methods are also described.

Abstract: This invention provides approaches to improve the signal to noise ratio (S/N) in electrochemical measurements (e.g. amperometry, voltammetry, etc.). In particular, a method is described wherein the faradaic current is temporally dissociated from the charging current associated with reading the charge of a redox-active species (e.g. a self-assembled monolayer (SAM)). This method, designated herein as open circuit potential amperometry (OCPA), quantitatively reads the charge of the redox species bound to (electrically coupled to) an electrode surface, while discriminating against both charging current(s) and amperometric signal(s) that arise, e.g. from diffusion-based species in solution.

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: X1?Xm+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.

Abstract: The present invention provides methods of making porphyrins and related compounds such as chlorins by condensing suitable starting materials (e.g., a dipyrromethane-dicarbinol plus dipyrromethane) in a polar solvent in the presence of a Lewis acid. The reactions are preferably carried out in a manner that minimizes rearrangement of the reaction product.

Abstract: The present invention provides dipyrrin substituted porphyrinic macrocycles, intermediates useful for making the same, and methods of making the same. Such compounds may be used for purposes including the making of molecular memory devices, solar cells and light harvesting arrays.

Abstract: A method of forming a crosslinked, non-discotic backbone polymer coating on a substrate, comprises the steps of: (a) coupling a layer of porphyrinic macrocycles to the substrate; (b) cross-linking the layer of porphyrinic macrocycles to form a layer of cross-linked porphyrinic macrocycles; and then (c) coupling a subsequent layer of porphyrinic macrocycles to the layer of cross-linked porphyrinic macrocycles of step (b) to form a none-discotic backbone polymer of porphyrinic macrocycles between the cross linked layer of step (b) and the subsequent layer of porphyrinic macrocycles to form a crosslinked, non-discotic backbone polymer coating thereon. Light harvesting arrays and solar cells that can be produced by such methods are also described.

Abstract: A photolithographic method of making an information storage device having different storage characteristics at a plurality of discrete memory locations thereon, comprises the steps of: (a) providing a substrate having a surface portion, said surface portion having a linking group coupled thereto or charge storage group coupled thereto, said linking group or charge storage group having a photocleavable protecting group thereon; (b) exposing at least one first discrete segment of said surface portion to radiant energy sufficient to cleave said protecting group from said linking group or charge storage group and generate a deprotected group, so that said group is deprotected in at least one first discrete memory location and preferably said group remains protected in at least one second discrete memory location. Additional groups are then coupled to the deprotected group as desired. Products produced by such methods are also described.

Abstract: The present invention provides high density, non-volatile memory devices incorporating polymers comprised of sandwich coordination compounds. Such polymers can have multiple different and distinguishable oxidation states (e.g., ten different and distinguishable oxidation states), and thus provide molecules, information storage media and apparatus that store multiple bits of information. In addition, the polymers can be immobilized or bound to a substrate to produce other useful articles, such as electrochromic displays, molecular capacitors, and batteries.

Abstract: A method of making an oxochlorin comprises the steps of oxidizing a chlorin to produce a mixture of hydronchlorin and oxochlorin, and then oxidizing the hydroxychlorin in said mixture, preferably with DDQ, to produce a mixture consisting essentially of oxochlorin. The step of oxidizing a chlorin is carried out by exposing the chlorin to alumina, typically in the presence of an oxidizing agent such as air or alumina. The oxidizing steps may be carried out in an organic solvent such as toluene. The chlorin is preferably a C-methylated chlorin, and is preferably metalated.

Abstract: A method of making an oxochlorin comprises the steps of oxidizing a chlorin to produce a mixture of hydroxychlorin and oxochlorin, and then oxidizing the hydroxychlorin in said mixture, preferably with DDQ, to produce a mixture consisting essentially of oxochlorin. The step of oxidizing a chlorin is carried out by exposing the chlorin to alumina, typically in the presence of an oxidizing agent such as air or alumina. The oxidizing steps may be carried out in an organic solvent such as toluene. The chlorin is preferably a C-methylated chlorin, and is preferably metalated.

Abstract: A molecular memory cell includes first and second electrodes. First and second charge storage molecules have respective first and second oxidation potentials and are disposed between the first and second electrodes. A molecular linkage couples the first and second charge storage molecules to the first electrode and provides respective first and second electron transfer rates for the first and second charge storage molecules. The first and second different oxidation potentials are different and/or the first and second electron transfer rates are different. In particular, the second oxidation potential may be greater than the first oxidation potential and the first electron transfer rate may be greater than the second electron transfer rate, such that the first charge storage molecule may be used as fast, volatile primary memory and the second charge storage molecule can be used as slower, less volatile secondary memory.

Abstract: This invention provides novel high density memory devices that are electrically addressable permitting effective reading and writing, that provide a high memory density (e.g., 1015 bits/cm3), that provide a high degree of fault tolerance, and that are amenable to efficient chemical synthesis and chip fabrication. The devices are intrinsically latchable, defect tolerant, and support destructive or non-destructive read cycles. In a preferred embodiment, the device comprises a fixed electrode electrically coupled to a storage medium having a multiplicity of different and distinguishable oxidation states wherein data is stored in said oxidation states by the addition or withdrawal of one or more electrons from said storage medium via the electrically coupled electrode. The storage medium typically comprises a storage molecule that is a triple-decker sandwich heterodimer. Such dimers can provide 8 or more oxidation states and permit the storage of at least 3 bits per molecule.

Abstract: A method and/or system and/or apparatus for a molecular-based FET device (an m-FET) uses charge storing molecules between a gate and channel of an FET-type transistor. Further embodiments describe fabrication methods for using combinations of standard practices in lithography and synthetic chemistry and novel elements.

Abstract: A half-sandwich coordination complex, useful for the synthesis of triple-decker sandwich coordination compounds, is produced by reacting a precursor complex of the formula XM(R1)2 wherein X is a halogen, M is a metal, and R1 is an amide, with a free base porphyrinic macrocycle to produce said half-sandwich complex. The half-sandwich coordination complex can be used to make a triple-decker sandwich coordination compound by reacting a half-sandwich coordination complex as described above with a double-decker sandwich coordination compound.

Abstract: This invention provides novel high density memory devices that are electrically addressable permitting effective reading and writing, that provide a high memory density (e.g., 1015 bits/cm3), that provide a high degree of fault tolerance, and that are amenable to efficient chemical synthesis and chip fabrication. The devices are intrinsically latchable, defect tolerant, and support destructive or non-destructive read cycles. In a preferred embodiment, the device comprises a fixed electrode electrically coupled to a storage medium having a multiplicity of different and distinguishable oxidation states wherein data is stored in said oxidation states by the addition or withdrawal of one or more electrons from said storage medium via the electrically coupled electrode. The storage medium typically comprises a storage molecule that is a triple-decker sandwich heterodimer. Such dimers can provide 8 or more oxidation states and permit the storage of at least 3 bits per molecule.

Abstract: The present invention provides a convergent method for the synthesis of light harvesting rods. The rods are oligomers of the formula A1(Ab+1)b, wherein b is at least 1, A1 through Ab+1 are covalently coupled rod segments, and each rod segment A1 through A1+b comprises a compound of the formula X1(Xm+1)m wherein m is at least 1 and X1 through Xm+1 are covalently coupled porphyrinic macrocycles. Light harvesting arrays and solar cells containing such light harvesting rods are also described, along with intermediates useful in such methods and rods produced by such methods.

Abstract: A solar cell incorporates a light harvesting array that comprises: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to the first electrode, each of the light harvesting rods comprising a polymer of Formula I: X 1 ⁢ — ( X m + 1 ) m ( I ) wherein m is at least 1, and may be from two, three or four to 20 or more; X1 is a charge separation group (and preferably a porphyrinic macrocycle, which may be one ligand of a double-decker sandwich compound) having an excited-state of energy equal to or lower than that of X2; and X2 through Xm+1 are chromophores (

Abstract: The present invention provides a convergent method for the synthesis of light harvesting rods. The rods are oligomers of the formula A1(Ab+1)b, wherein b is at least 1, A1 through Ab+1 are covalently coupled rod segments, and each rod segment A1 through A1+b comprises a compound of the formula X1(Xm+1)m wherein m is at least 1 and X1 through Xm+1 are covalently coupled porphyrinic macrocycles. Light harvesting arrays and solar cells containing such light harvesting rods are also described, along with intermediates useful in such methods and rods produced by such methods.