EP1363916A4 - Emittierende multichromophorische systeme - Google Patents

Emittierende multichromophorische systeme

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Publication number
EP1363916A4
EP1363916A4 EP02763188A EP02763188A EP1363916A4 EP 1363916 A4 EP1363916 A4 EP 1363916A4 EP 02763188 A EP02763188 A EP 02763188A EP 02763188 A EP02763188 A EP 02763188A EP 1363916 A4 EP1363916 A4 EP 1363916A4
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Prior art keywords
diode
compound
light
layer
source
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French (fr)
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EP1363916A2 (de
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Michael J Therien
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University of Pennsylvania Penn
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University of Pennsylvania Penn
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene

Definitions

  • This invention relates to synthetic multichromophoric systems that preferably exhibit: (i) low energy emissive excited states in which the transition dipoles of the constituent pigment building blocks are correlated in defined phase relationships, (ii) excited state polarization over long timescales, (iii) emission quantum yields that have an unusual dependence upon supramolecular structure and emission wavelength, (iv) collective oscillator behavior in their respective electrochemically excited states, and (v) integrated emission oscillator strengths that are large with respect to that manifest by the benchmark monomeric chromophore.
  • E is the emission energy
  • n and ⁇ are respectively the medium's refractive index and dielectric strength
  • ( ⁇ ) is the emission transition dipole moment.
  • the magnitude of l is a signature of the number of coupled oscillators; hence, for an assembly of m pigments exhibiting superradiant emission, the classically predicted, maximal value of k. that could be observed corresponds to m times the radiative rate constant determined for the corresponding monomeric chromophore.
  • the monomeric chromophoric building blocks are conjugated to form dimers, trimers, oligomers or polymers.
  • the monomeric chromophoric building blocks can, for example, be porphyrins.
  • porphyrins are derivatives of porphine, a conjugated cyclic structure of four pyrrole rings linked through their 2- and 5-positions by methine bridges. Porphyrins can bear up to 12 substituents at meso (i.e. ⁇ ) and pyrrolic (i.e., ⁇ ) positions thereof.
  • Porphyrins can be covalently attached to other molecules.
  • the electronic features of the porphyrin ring system can be altered by the attachment of one or more substituents.
  • the term "porphyrin” includes derivatives wherein a metal atom is inserted into the ring system, as well as molecular systems in which ligands are attached to the metal.
  • the substituents, as well as the overall porphyrin structure, can be neutral, positively charged, or negatively charged.
  • Numerous porphyrins have been isolated from natural sources. Notable porphyrin- containing natural products include hemoglobin, the chlorophylls, and vitamin B12.
  • porphyrins have been synthesized in the laboratory, typically through condensation of suitably substituted pyrroles and aldehydes.
  • reactions of this type generally proceed in low yield, and cannot be used to produce many types of substituted porphyrins.
  • the present invention conjugated multichromophoric systems including a polymer comprising a plurality of linked porphyrinic monomer units having formula (I), (2), or (3):
  • R ⁇ ,-R ⁇ 4 and R ⁇ rR ⁇ s are, independently, H or chemical functional groups that can bear a negative charge prior to attachment to a porphyrin coumpound.
  • At least one of R ⁇ -R ⁇ or RBrRBs nas formula C ⁇ C(R£>).
  • at least one of R ⁇ -R ⁇ is haloalkyl having from 1 to about 20 carbon atoms.
  • at least one of R ⁇ ⁇ Bs 1S haloalkyl having 2 to about 20 carbon atoms or at least at are haloalkyl having from 1 to about 20 carbon atoms or haloaryl having from about 6 to about 20 carbon atoms.
  • at least one of R ⁇ 1 -R ⁇ 4 or R ⁇ rR ⁇ g includes an amino acid, peptide, nucleoside, or saccharide.
  • the present invention also provides processes and intermediates for preparing substituted porphyrins.
  • the processes comprise providing a porphyrin compound having formula (1), (2), or (3) wherein at least one of R A , -R ⁇ 4 or R ⁇ r R ⁇ g is a halogen and contacting the porphyrin compound with a complex having formula Y(L) 2 wherein Y is a metal and L is a ligand.
  • This contacting produces a second reaction product which, through reductive elimination, yields a third reaction product that contains a porphyrin substituted with R ⁇ .
  • the invention provides polymers comprising linked porphyrin units.
  • porphyrin units having formula (1), (2), or (3) share covalent bonds.
  • the remaining of can be H, halogen, alkyl or heteroalkyl having 1 to about 20 carbon atoms or aryl or heteroaryl having 4 to about 20 carbon atoms, C(RC) ⁇ C(R£))(RE), C ⁇ C(R j T)), or a chemical functional group that includes a peptide, nucleoside, and/or saccharide.
  • the linking group is cycloalkyl or aryl having about 6 to about 22 carbon atoms.
  • the invention also provides processes for preparing porphyrin-containing polymers.
  • the processes comprise providing at least two compounds that, independently, have formula (1), (2) or (3) wherein at least one of R ⁇ -R ⁇ or R ⁇ R ⁇ s in each of the compounds contains an olefinic carbon-carbon double bond or a chemical functional group reactive therewith.
  • at least one of A ⁇ R-A ⁇ or R ⁇ R ⁇ & in each of the compounds contains a carbon-carbon triple bond or a chemical functional group reactive therewith.
  • the compounds are then contacted for a time and under reaction conditions effective to form covalent bonds through the carbon-carbon double and/or triple bonds.
  • emissive pigment building blocks such as porphyrin monomer units that, independently, have formula (1), (2), or (3), are linked to form a conjugated dimer, trimer, oligomer, polymer, or other highly conjugated synthetic multichromophoric systems that exhibits low energy fluorescent excited states in which the transition dipoles of the pigment building blocks are correlated in defined phase relationships.
  • Analyses of corresponding fluorescence intrinsic decay rate and quantum yield data show that, in another embodiment, ethyne- and butadiyne-bridged multiporphyrin species that manifest high excited-state anisotropies display exceptionally large emitting dipole strengths, establishing a new precedent for superradiant oligopigment assemblies.
  • the present invention provides methods comprising the steps of providing a conjugated compound comprising at least two covalently bound moieties and then exposing the compound to an energy source for a time and under conditions effective to cause it to emit light that has a wavelength of 650-2000 nm and is of an intensity that is greater than a sum of light individually emitted by the component moieties.
  • emission from said materials can be effected by optical or electrical pumping. For example, when these materials are optically pumped, evaluation of the emission dipole strength can be made from determination of the emission quantum yield and the corresponding emission decay rate using conventional methods [see for example: Lakowicz, J.
  • the fluorescence quantum yield (QY) can be determined by the reference method[Lakowicz, 1983], using the above relation where fl comp ⁇ ex and Jl slandard are the respective, total integrated fluorescence intensities of the complex and emission standard, A comp
  • the quantity ("o comp i ex ⁇ o standard ) 2 represents the solvent refractive index correction.
  • Steady state emission spectra can be obtained on a conventional luminescence spectrometer having the appropriate emission detectors. Sample concentrations are adjusted typically such that the absorbance is between 0.005 and 0.04 at the excitation wavelength.
  • Emission spectra obtained for the chromophore are corrected to account for the wavelength-dependent efficiency of the detection system which can be determined using the spectral output of a calibrated light source obtained from the National Bureau of Standards.
  • Secondary corrections to the emission spectra used to determine QYs are performed as outlined by Lakowicz[Lakowicz, 1983]. Quantum yields are determined typically using two standard benchmarks for each chromophore.
  • Emitting dipole strengths are defined as ⁇ > chromophore / ⁇ ⁇ > reference5 where ⁇ > refercnce corresponds to the emission dipole strength of one of the covalently bound moieties that defines the conjugated compound.
  • ⁇ > values can be determined from the Einstein equation for spontaneous emission, when the radiative rate constant k. has been determined from appropriate time-resolved spectroscopic techniques [Lakowicz, J. R. Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983); Turro, N. J. Modern Molecular Photochemistry (The Benjamin/Cummings Publishing Co., Inc., Menlo Park, 1978); Dexter, D. L. J. Chem. Phys. 21, 836-850 (1953); Dicke, R. H. Phys. Rev. 93, 99 (1954)].
  • the compound exhibits an integral emission oscillator strength that is greater than a sum of emission oscillator strengths exhibited by its component moieties.
  • Representative moieties are those that include a conjugated ring system.
  • At least one of the moieties is a laser dye, fluorophore, lumophore, or phosphore.
  • Particularly preferred moieties include porphyrins, porphycenes, rubyrins, rosarins, hexaphyrins, sapphyrins, chlorophyls, chlorins, phthalocyanines, porphyrazines, bacteriochlorophyls, pheophytins, texaphyrins, and their corresponding metalated derivatives.
  • Another class of representative moieties are conjugated macrocycles comprising 16 or more carbon atoms and four or more heteroatoms such as N, O, S, Se, Te, B, P, As, Sb, Si, Ge, Sn, and Bi.
  • the moieties preferably are bound by at least one carbon-carbon double bond, carbon- carbon triple bond, a combination thereof, or an imine, phenylene, thiophene, amide, ether, thioether, ester, ketone, sulfone, or carbodiimide group.
  • Representative bond types include ethynyl, ethenyl, allenyl, butadiynyl, polyvinyl, polyynyl, thiophenyl, furanyl, pyrrolyl, p- diethynylarenyl bonds and any conjugated hetrocycle that bears diethynyl, di(polyynynyl), divinyl, di(polyvinvyl), or di(thiophenyl) substituents.
  • Such materials thus include, laser dyes, fluorophores, lumophores, and/or phosphore that are covalently bound with, for example, alkynyl or alkenyl bonds.
  • the conjugated synthetic multichromophoric systems of the invention can be used, for example, as dyes, catalysts, contrast agents, antitumor agents, antiviral agents, electroluminescent materials, LEDs, lasers, photorefractive materials and in chemical sensors and electrooptical devices.
  • the present invention provides lasers in which a dye solution is disposed in a resonant cavity and comprises a compound of the invention and an aqueous or non-aqueous solvent that is substantially unable to chemically react with said compound and to absorb and emit light at a wavelength at which said compound absorbs and emits light.
  • Lasers according to the invention further include a pumping energy source that produces stimulated emission in the dye solution.
  • lasers according to the invention are those that include a solid body that, in turn, includes a compound of the invention and a host polymer that is unable to chemically react with the compound and unable to absorb and emit light at a wavelength at which the compound absorbs and emits light.
  • Such lasers further include an energy source that either is coupled with the solid body and generates light in the solid body, or is coupled with the host polymer and generates light therein.
  • an optical amplifier comprising a polymeric optical waveguide and a compound of the invention is provided.
  • the present invention also provides polymer grids comprising a body of electrically conducting organic polymer.
  • a body has an open and porous network morphology and defines an expanded surface, area void-defining porous network.
  • An active electronic material comprising a compound of the invention is located within at least a portion of the void spaces defined by the porous network.
  • the conducting organic polymer may also include a compound of the invention.
  • the present invention also provides polymer grid electrodes comprising a body of electrically conducting organic polymer that is electrically joined to an electrical connector.
  • the body should have an open and porous network morphology and define an expanded surface area, void-defining porous network, with an active electronic material comprising a compound of the invention located within at least a portion of the void spaces defined by the porous network.
  • the invention also provides solid state polymer grid triodes comprising a first electrode and a second electrode spaced apart from one another with a polymer grid comprising a body of electrically conducting organic polymer that includes a compound of the invention.
  • the body preferably has an open and porous network morphology and defines an expanded surface area void-defining porous network interposed between the first electrode and the second electrode.
  • the present invention provides light-emitting polymer grid triodes comprising a first electrode and a second electrode spaced apart from one another with a polymer grid comprising a body of electrically conducting organic polymer.
  • the body in such a triode has an open and porous network morphology and defines an expanded surface area, void-defining porous network interposed between the first and second electrodes.
  • An active luminescent semiconducting electronic material comprising a compound of the invention is interposed between the first and second electrodes, and serves to transport electronic charge carriers between the first and second electrodes, the carriers being affected by the polymer grid such that on applying a turn-on voltage between the first and second electrodes, charge carriers are injected and light is emitted.
  • the present invention also relates to light-responsive diode systems comprising a diode that, in turn, includes: a conducting first layer having high work function; a semiconducting second layer in contact with the first layer, the second layer made comprising a compound of the invention; and a conducting third layer in contact with the second layer.
  • Systems according to the invention further include a source for applying a reverse bias across the diode, a source for impinging light upon the diode, and a source for detecting an electrical current produced by the diode when the reverse bias is applied to the diode and light is impinged upon the diode.
  • the present invention also provides light-responsive diode systems that comprise a diode that itself includes: a conducting first layer having high work function; a semiconducting second layer in contact with the first layer, the second layer made comprising a compound of the invention; and a conducting third layer in contact with the second layer, the third layer comprising an inorganic semiconductor doped to give rise to a conductive state.
  • Such systems further include a source for applying a reverse bias across the diode, a source for impinging light upon the diode, and a source for detecting an electrical current produced by the diode when the reverse bias is applied to the diode and light is impinged upon the diode.
  • dual function light-emitting, light responsive input-output diode systems comprising a diode having a conducting first layer having high work function, a semiconducting second layer in contact with the first layer comprising a compound of the invention, and a conducting third layer in contact with the second layer.
  • Such systems further comprise a source for applying a reverse bias across the diode, a source for impinging light upon the diode, and a source for detecting an electrical current produced by the diode when the reverse bias is applied to the diode and light is impinged upon the diode.
  • the present invention also provides dual function light-emitting, light responsive input-output diode systems comprising a diode having a conducting first layer having high work function, a semiconducting second layer in contact with the first layer that comprises a compound of the invention, and a conducting third layer in contact with the second layer.
  • Such systems further include a source for applying a reverse bias across the diode, a source for impinging an input signal or light upon the diode, a source for detecting an electrical current produced by the diode when the reverse bias is applied to the input signal of light is impinged upon the diode, a source for halting the applying of reverse bias, and a source for applying a positive bias output signal across the diode, the positive bias output signal being adequate to cause the diode to emit an output signal of light.
  • the invention also provides dual function input-output processes comprising the steps of applying a reverse bias across the diode and impinging an input signal of light upon the diode, detecting as an electrical input signal an electrical current or voltage produced by the diode when the reverse bias is applied to the diode and the input signal of light is impinged upon the diode, halting the applying of reverse bias, and applying a positive bias output signal across the diode, the positive bias output signal being adequate to cause the diode to emit an output signal of light in response thereto.
  • articles comprising a unitary solid state source of electromagnetic radiation, in which the source has a layer structure that comprises a multiplicity of layers, including two spaced apart conductor layers with compound of the invention therebetween, and further comprising contacts for causing an electrical current to flow between the conductor layers, such that incoherent, electromagnetic radiation of a first wavelength is emitted from the compound of the invention.
  • the layer structure preferably comprises an optical waveguide comprising a first and a second cladding region with a core region therebetween, with the optical waveguide disposed such that at least some of said incoherent electromagnetic radiation of the first wavelength is received by the optical waveguide, and the core region comprises a layer of a second organic material selected to absorb the incoherent electromagnetic radiation of the first wavelength, and to emit coherent electromagnetic radiation of a second wavelength, longer than the first wavelength, in response to the absorbed incoherent electromagnetic radiation.
  • the present invention also provides methods for screening compounds.
  • such methods comprise the steps of providing a conjugated compound comprising at least two covalently bound moieties; exposing the compound to an energy source for a time and under conditions effective to cause it to emit light that has a wavelength of 650-2000 nm; and determining whether or not that emitted light is either (1) of an intensity that is greater than a sum of light emitted individually by the moieties or (2) larger than emitted by either of the covalently bound moieties.
  • a compound of the invention is attached to a targeting agent which provides localization of the compound in select body tissues.
  • a probe light source can be held external to the tissue to excite the compound into an emissive state that has significant emission dipole strength in the 700-1100 nm spectral domain.
  • FIG. 1 shows conjugated porphyrin arrays (compounds 4-12), as well as electronic absorption spectra thereof. Uncorrected emission spectra are shown as insets.
  • FIG. 2 shows anisotropic fluorescence dynamics of compounds 4-6.
  • FIG. 3 is a schematic of (A) Potential energy diagram illustrating the dependence of the magnitude of electronic state energy separation and the extent of equilibrium nuclear displacement ( ⁇ Q) upon vibrational wave function overlap. (B) Potential energy diagrams highlighting the effect of increasing S,-T, nuclear displacement upon the magnitude of intersystem crossing rate constants k ⁇ sc .
  • FIG. 4 shows photophysical properties of S l -excited states of (porphinato)zinc(II)
  • Complexes 1-12 including (5-ethynyl-10,20-diphenylporphinato)zinc(II) (Compound 1), (5,15-diethynyl-10,20-diphenylporphinato)zinc(II) (Compound 2), and (2-ethynyl-5, 10, 15,20- tetraphenylporphinato)zinc(II) (Compound 3): fluorescence lifetime and time-resolved anisotropy data.
  • a_ d (a) Samples for transient spectroscopic studies were kept rigorously dry using standard inert-atmosphere techniques; all data presented were recorded at 293 K in 10:1 CHCl 3 :pyridine.
  • FIG. 5 shows Fluorescence Quantum Yield, Stokes Shift, and Calculated Transition
  • Steady state fluorescence emission spectra were obtained on a Perkin-Elmer LS 50 Luminescence Spectrometer. The concentrations of all samples were adjusted such that their absorbance was between 0.01 and 0.04 at the excitation wavelength. All spectra were collected with the single excitation and emission monochromators set at 5 nm. Fluorescence spectra obtained for the (porphinato)zinc(II) complexes as well as the chromophores used as emission standards were corrected to account for the wavelength-dependent efficiency of the detection system which was determined using the spectral output of a calibrated light source obtained from the National Bureau of Standards.
  • Benchmark fluorescence emitters utilized were [dye (QY; solvent; ⁇ « ⁇ (nm))]: (i) TPPZn (0.033; benzene; (598, 647)); (ii) TPPZn (0.028; 10:1
  • the computed QY was always within ⁇ 10% of established literature value, confirming the appropriateness of the emission correction factors implemented throughout the 600- 850 nm spectral regime in these experiments.
  • the standard error in quantum yields determined by this method is typically taken as ⁇ 20% of the reported value.
  • the QY entries correspond to the average of values obtained from at least three independent measurements.
  • FIG. 6 shows Comparative Radiative Lifetimes and Emitting Dipole Strengths of Conjugated Chromophores 1-12 vs. Benchmark Biological Antennae Systems.
  • Emitting dipole strengths ⁇ > chromop hor e / ⁇ ⁇ > refe r e n ce - ⁇ > values were determined using eq. 5; emission energies used in this calculation correspond to the frequency that partitions the integrated emission oscillator strength into blue and red components having equivalent area.
  • emitting dipole strengths are referenced both to TPPZn and an appropriate benchmark ethyne-derivatized (porphinato)zinc(II) monomer.
  • compound 1 served as the reference
  • linear polymer chains can be formed wherein a portion of the polymer has general formula (P] ⁇ ) r where P J V is a porphyrin unit and r is at least 2.
  • linear polymer chains have general formula:
  • Q ⁇ is a linking group
  • Pjy is a porphyrin unit
  • h, 1, and s are independently selected to be at least 1.
  • a portion of such polymers can have formula:
  • P / Y J and Fj ⁇ 2 are independently selected porphyrin units, Q , and Q 2 are independently selected linking groups, and 1', 1", s', and s" are at least 1.
  • These essentially linear polymer chains can be cross-linked such that a portion of the polymer has general formula:
  • r' is at least 1.
  • the dimers, trimers, oligomers and polymers of the invention are generally formed by contacting a substituted porphyrin with a second compound containing functionality that is reactive with the functionality contained within the porphyrin.
  • the porphyrin contains an olefinic carbon-carbon double bond, a carbon-carbon triple bond or some other reactive functionality.
  • the contacting should be performed under conditions effective to form a covalent bond between the respective reactive functionalities.
  • porphyrin- containing polymers are formed by metal-mediated cross-coupling of, for example, dibrominated porphyrin units.
  • porphyrin-containing polymers can be synthesized using known terminal alkyne coupling chemistry, (see, e.g., Patai, et al., The Chemistry of Functional Groups, Supplement C, Part 1, pp. 529-534, Wiley, 1983; Cadiot, et al., Acetylenes, pp. 597-647, Marcel Dekker, 1964; and Eglinton, et al., Adv. Org. Chem., 1963, 4, 225)
  • the second compound noted above can be a substituted porphyrin of the invention or some other moiety such as an acrylate monomer.
  • copolymeric structures can be synthesized with the porphyrins of the invention.
  • porphyrins of the invention can be incorporated into virtually any polymeric matrix known in the art, including but not limited to polyacetylenes, polyimides, polyacrylates, polyolefins, pohyethers, polyurethanes, polyquinolines, polycarbonates, polyanilines, polypyrroles, and polythiophenes.
  • fluorescent porphyrins can be incorporated into such polymers as end-capping groups.
  • the conjugated synthetic multichromophoric systems of the invention can be used, for example, as dyes, catalysts, contrast agents, antitumor agents, antiviral agents, liquid crystals, electroluminescent materials, LEDs, lasers, photorefractive materials, in chemical sensors and in electrooptical and solar energy conversion devices. They also can be incorporated into supramolecular structures.
  • the polymers and supramolecular structures which anchor porphyrin units in a relatively stable geometry, should improve many of the known uses for porphyrins and even provide a number of new uses, such as in a solid phase system for sterilizing virus-containing solutions, as well as new uses as wave guides, molecular wires, optical triggers, and in molecular lasers, optical amplifiers, dye lasers, polymer grid triodes, light emitting and light responsive diode systems, LEDs, photovaltaics, as well as articles comprising an organic laser, and using the invention in methods and devices for in vivo diagnosis detecting IR emission by agents bound to body organs.
  • Representative uses are disclosed by, for example, the following patents, which are incorporated herein by reference: U.S. Pat.
  • a flurophore according to the invention is an emissive compound in which the spin multiplicity of the two states involved in the radiative transition (typically an electronically excited state and the ground state) have identical spin multiplicities.
  • a lumophore is an emissive compound in which one of the two states involved in the radiative transition (typically the electronically excited state) derives from substantial mixing of two or more orbital configurations having different spin multiplicities [see for example, Lakowicz, J. R. Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983); Turro, N. J. Modern Molecular Photochemistry (The Benjamin/Cummings Publishing Co., Inc., Menlo Park, 1978)].
  • a phosphore according to the invention is an emissive compound in which the spin multiplicity of the two states involved in the radiative transition (typically an electronically excited state and the ground state) differ in their respective spin multiplicities.
  • a laser dye according to the invention is any organic, inorganic, or coordination compound that has been established previously to lase. Representative laser dyes can be found in Birge, R. R.; Duarte, F. J. Kodak Optical Products, Kodak Publication JJ-169B (Kodak Laboratory Chemicals; Rochester, NY (1990). Representative laser dyes include: p-terphenyl Sulforhodamine B p-quaterphenyl Rhodamine 101 carbostyryl 124 Cresy Violet perchlorate popop DODC Iodide
  • Rhodamine 110 7-dichlorofluorescein Rhodamine 6G Rhodamin 19 Perchlorate Rhodamine B
  • the .electronic structure of the component moieties in compounds of the invention are similar.
  • the respective one-electron oxidation and reduction potentials thereof preferably differ by less than 250 mV.
  • the energies of the respective lowest energy electronic transitions preferably differ by less than 2500 cm "1 . It has been found in accordance with the present invention that a wide variety novel highly conjugated porphyrin-based chromophore systems of the invention have unusual electooptic properties, and can function as collective oscillators. The formation of a collective oscillator and cooperative emission requires coupling of the transition dipoles of monomeric pigments.
  • the compounds in the preferred embodiment of the invention are a class of multichromophoric systems that display extremely strong pigment-pigment electronic coupling; these assemblies feature ethyne and butadiyne moieties that directly link the carbon frameworks of their constituent porphyrin building blocks (FIG. 1).
  • These ethyne- and butadiyne-bridged porphyrin arrays exhibit a number of surprising and unexpected optoelectronic characteristics, and are remarkable in that their optical absorption profiles, emission wavelengths, redox properties, as well as spin distribution and orientation in their photoactivated triplet states, are regulated extensively by the mode of porphyrin-to-porphyrin linkage topology.
  • the compounds of the invention are synthetic multichromophoric systems that exhibit one or more of the following optical properties: (i) low energy emission excited states in which the transition dipoles of the constituent pigment building blocks are correlated in defined phase relationships, (ii) excited state polarization over long timescales, (iii) emission quantum yields that have an unusual dependence upon supramolecular structure and emission wavelength, (iv) the hallmarks of collective oscillator behavior in their respective electronically-excited states, and (v) extreme superradiance, the magnitude of which exceeds the maximal value predicted classically (eq 1). Integrated emission oscillator strengths that are large with respect to that manifest by the benchmark monomeric chromophore.
  • the multichromophoric systems are generated by the process of providing a conjugated compound comprising at least two covalently bound moieties and exposing the conjugated compound to an energy source for a time and under conditions effective to cause the compound to emit light.
  • the light emitted is preferably in the range of 650-2000 nm.
  • the moieties used are, for example, porphyrins, and they may be bound by at least one carbon-carbon double bond, carbon-carbon triple bond, or a combination thereof.
  • the bond can be, for example, ethynyl, ethenyl, allenyl, or butadiynyl.
  • the moities may, for example, be bound by a combination of those units, or at least one imine, phenylene, or thiophene group.
  • the isotropic and anisotropic dynamics of the lowest energy singlet excited (Si) states of benchmark ethyne-elaborated (porphinato)zinc(II) monomers (5- ethynyl-10,20-diphenylporphinato)zinc(II) (Compound 1), (5,15-diethynyl-10,20- diphenylporphinato)zinc(II) (Compound 2), and (2-ethyny 1-5,10,15,20- tetraphenylporphinato)zinc(II) (3) as well as those of conjugated (porphinato)zinc(II) arrays (Compounds 4-12) (FIG. 1) were characterized employing the time-correlated single-photon counting (TCSPC) spectroscopic technique.
  • TCSPC time-correlated single-photon counting
  • the fluorescence anisotropy (r(t)) measured at time t following optical excitation is obtained from the parallel (I upfront ) and perpendicular (I x ) transient signals using the following expression:
  • the magnitude of the initial anisotropy, /Q) depends on the respective degeneracies and polarizations of the absorptive and emissive states.
  • the value of in a dilute solution (eq 3) is a product of the angular displacement ( ⁇ ) of the absorption and emission dipoles and the loss of anisotropy due to photoselection (2/5).
  • the actual measured value of r (0) depends intimately upon the experimental timescale; for example, if the interrogated absorption and emission dipoles are parallel, but an experimentally determined value of r (0) less than 0.4 is manifest, it generally indicates the existence of relaxation processes that occur on time scales shorter than the time resolution of the experiment. Such processes can involve nuclear dynamics (e.g., rotational or librational motion) of the molecule, or electronic (vibronic) relaxation pathways.
  • Si -excited state lifetime and time-resolved fluorescence anisotropy data for the present invention are summarized in FIG. 4 for compounds 1-12; typical isotropic (magic angle) and anisotropic fluorescence decay profiles for these species are presented in FIG. 2.
  • samples were excited on the low energy side of their respective lowest energy Q absorption bands; fluorescence decays were probed at wavelengths to the red of the emission ⁇ m ax- Monoexponential decay of the isotropic fluorescence was observed (FIG. 4); notably, all of these species of the present invention possess similar (ns) fluorescence lifetimes ( ⁇ F ).
  • the anisotropic fluorescence dynamics vary extensively in compounds 1-12 of the present invention.
  • TPPZn 5, 10, 15,20-Tetraphenylporphinato)zinc(II)
  • TPPZn a porphyrinic photophysical benchmark
  • the nature of the porphyrin-to-porphyrin linkage topology is clearly important in establishing the magnitude of the initial anisotropy.
  • ⁇ -to- ⁇ bridged chromophores display rrj values of ⁇ 0.1 (compounds 4, 7, and 10), while only meso-t -meso bridged (porphinato)zinc(II) chromophores (compounds 6, 9, 11, and 12) exhibit values of 0.4.
  • the extent of conformational mobility about the conjugated bridge likely plays a role in determining the magnitude of r (0) in meso-to- ⁇ bridged pigments (compounds 5 and 8).
  • FIG. 5 chronicles the Stokes shifts, B- and Q-state transition dipole moments, and fluorescence quantum yields (QYs) for compounds 1-12. Note that emission QYs of ethyne- elaborated monomeric porphyrin compounds 1-3 exceed that measured for TPPZn and (5,15- diphenylporphinato)zinc(II) (DPPZn) benchmarks.
  • QYs determined for bis- and tris[(porphinato)zinc(II)] compounds 4-12 are larger than that measured for the monomers 1-3; note also that for both bis-(compounds 4-9) and tris[(porphinato)zinc(II)] (compounds 10-12) species, the absolute magnitudes of the QYs vary with linkage topology and the length of the cylindrically ⁇ -symmetric bridge that connects the aromatic macrocycles.
  • FIG. 3A highlights its dependence upon extent of initial and final state energy separation, and the magnitude of equilibrium nuclear displacement ( ⁇ Q) between these electronic states.
  • ⁇ Q equilibrium nuclear displacement
  • the radiative transition probability is proportional to the cube of the emission energy (eq 1)
  • compounds 4-12 of the present invention in order for compounds 4-12 of the present invention to feature simultaneously substantial fluorescence lifetimes and emission quantum yields relative to their monomeric (porphinato)zinc(II) benchmarks, these multichromophoric systems must be behaving as collective oscillators (( ⁇ ) 4 12 » ( ⁇ ) TPPZn ) (eq 1).
  • the extent to which a pigment aggregate is superradiant is generally expressed in terms of a superradiance enhancement factor (emitting dipole strength) in which the experimentally determined ⁇ ⁇ > aggregate value is reference against ⁇ > measured for an appropriate monomeric pigment benchmark.
  • the superradiance enhancement factor is thus a direct observable that is often taken as a classical measure of the exciton diffusion length.
  • Emitting dipole strengths (EDSs) and radiative lifetimes ( ⁇ rad ) for compounds 1-12 are listed in FIG. 6. While these data show that, in the present invention, bis-and tris(pigment) arrays 4-12 all manifest dramatic superradiance enhancement factors, the magnitudes of the EDSs determined for oligo [(porphinato)zinc(II)] systems of the present invention featuring
  • meso-to-meso or meso-to- ⁇ linkage topologies are particularly striking: they greatly exceed the expected maximal values (i.e., 2 and 3) predicted for ensembles composed of two and three respective monomeric pigment units (eq 1). EDS values of this magnitude for similarly sized conjugated oligomers are without precedent. Likewise, superradiant conjugated polymers fabricated to date have exploited monomer units with transition dipole moments considerably smaller than that manifest by porphyryl moieties.
  • EDSs determined ethyne- and butadiyne-bridged (porphinato)zinc(II) arrays that feature meso-to-meso or meso-to- ⁇ linkage motifs must arise from factors supplemental to the collective, in-phase oscillation of the individual pigment dipoles in these conjugated chromophore systems.
  • These EDSs can be rationalized considering the established triplet photophysics of these species.
  • photoexcited EPR spectroscopic studies establish conclusively that the T, -excited-state electron density distributions in compounds 4-12 of the present invention are all highly localized.
  • T, -state wavefiinction in no case exceeds the dimensions defined by a single (porphinato)zinc(II) unit and its pendant, cylindrically ⁇ -symmetric (ethyne or butadiyne) substituents.
  • the genesis of this T, wavefiinction localization in compounds 4-12 may derive from large lattice relaxations, which are known to diminish the spatial extent of triplet electronic states relative to excited S n states in oligophenylene ethynylenes, or from fundamental electronic differences between the singlet and triplet excitation manifolds that can be rationalized within the context of the point-dipole approximation of the general exciton model.
  • conjugated assemblies When such conjugated assemblies are engineered to possess singly degenerate excited states, high and low frequency vibrational modes of the chromophore and solvent do not significantly impact excited-state electronic dephasing, and the polarized, dipole-dipole correlated nature of these singlet excited states is maintained over long, ns timescales.
  • reaction was quenched by the addition of 2,3-dichloro-5,6-dicyano- 1 ,4-benzoquinone (DDQ, 900 mg, 3.96 mmol) and the reaction was stirred for an additional 30 minutes.
  • the reaction mixture was neutralized with 3 ml of triethylamine and poured directly onto a silica gel column (20 x 2 cm) packed in hexane.
  • the product was eluted in 700 ml of solvent. The solvent was evaporated, leaving pu ⁇ le crystals (518 mg., 1.12 mmol,
  • the precipitated pu ⁇ le solid was filtered through a fine fritted disk and washed with water, methanol, and acetone and dried in vacuo to yield 610 mg (0.89 mmol, 95%) of reddish pu ⁇ le solid.
  • the compound was recrystallized from THF/heptane to yield large pu ⁇ le crystals of the title compound (564 mg, 0.82 mmol, 88%). Vis(THF): 428 (5.50), 526 (3.53), 541 (3.66), 564 (4.17), 606 (3.95).
  • the organometallic reagent was methyl zinc chloride prepared from methyl lithium and anhydrous zinc chloride in THF.
  • the organometallic reagent was 2,5-dimethoxyphenyl lithium, prepared from 1 ,4- dimethoxybenzene and t-butyl lithium in ether at - 78° C.
  • the organolithium reagent was added to a solution of ZnCl 2 in THF to yield the organozinc chloride reagent. This reagent was used immediately.
  • the organometallic reagent was tri -n-butyl [(4-methyl)-4'-methyl-2,2'-dipyridyl)]tin, prepared by lithiating 4,4'-dimethyl-2,2'-dipyridyl with one equivalent of lithium diisopropylamide in THF at - 78° C. and warming the reaction mixture to room temperature.
  • the organolithium reagent was treated with 1.1 equivalent of tributyltin chloride. The resulting organotin reagent was used without further purification.
  • organometallic reagent was trimethylsilyl ethynyl zinc chloride prepared from trimethylsilylethynyl lithium and anhydrous zinc chloride in THF.
  • the organometallic reagent was 2,5-dimethoxyphenyl zinc chloride, prepared from the corresponding lithium reagent and anhydrous zinc chloride in THF/diethyl ether.
  • the organometallic reagent, trimethylsilylacetylide zinc chloride, was prepared from the corresponding lithium reagent and anhydrous zinc chloride in THF.
  • the crude reaction mixture was chromatographed on silica and eluted with 50%
  • Pd(PPh3)4 (0.02 mmol) are dissolved in 25 ml dry THF. A solution of cis-bis(tri-n-butyltin)- 1 ,2-difluoroethene (0.2 mmol) in 5 ml THF is added and the solution heated at reflux for 2 days. The reaction is quenched with water, extracted with methylene chloride, dried over calcium chloride, and the solvents evaporated.
  • the crude solid is chromatographed on silica using methylene chloride/hexanes eluent to isolate cis-bis-l,2-[5-[10,15,20- tris(pentafluorophenyl)po ⁇ hyrinato zinc]- 1 ,2-difluoroethene.
  • the crude solid is chromatographed on silica using methylene chloride/hexane eluant to isolate the Cofacial-bis-[cis-ethenyl meso-bridged]zinc po ⁇ hyrin complex of formula (5) and Polymeric-bis-[cisethenyl meso-bridged] porphyrin species of formula (6), wherein R ⁇ , and R / 4 3 are phenyl and M is Zn.
  • the crude solid is chromatographed on silica using methylene chloride/hexanes eluent to isolate the Cofacial-bis-[cisethenyl meso-bridged] zinc po ⁇ hyrin complex as well as the Polymeric-bis-[cis-ethenyl meso-bridged] po ⁇ hyrin species.
  • the cofacial and polymeric species are dissolved separately in chloroform.
  • the cofacial po ⁇ hyrin complex dissolved in chloroform and reacted with a large excess of N- bromosuccinimide as in Example 2 to perbrominate positions on both po ⁇ hyrins.
  • the crude solid is chromatographed on silica using methylene chloride/hexane eluant to isolate the Cofacial-bis-[l,8-anthracenyl-meso-bridged]zinc po ⁇ hyrin complex of formula (7) and the Polymeric-bis-[l ,8-anthracenyl-meso-bridged]zinc po ⁇ hyrin species of formula (8), where and R I and R ⁇ 3 are phenyl and M is Zn.
  • the polymer is prepared from 1 ,4-diethynylbenzene and 5,15-dibromo- 10,20-diphenylpo ⁇ hinato zinc via the identical procedure.
  • DOPED PORPHYRIN POLYMERS 5,15-Bis(ethynyl)-10,20-diphenylpo ⁇ hyrinato zinc is polymerized according to the general procedure provided by Skotheim, ed., Handbook of Conducting Polymers, Volume 1, pp. 405-437, Marcel Dekker, 1986 using a catalytic amount of MoCl 5 , Me(CO) 6 , WC1 6 , or W(CO) 5 .
  • the resultant polymer is then doped with an oxidant such as iodine or SbF 5 .
  • the entire reaction mixture was transferred to a dry 100 mL Schlenk tube containing 340 mg of 5,15-dibromo-10,20-diphenylpo ⁇ hyrin. The solution was heated to 40° C and left sealed overnight. TLC of the reaction mixture after 18 h shows a mixture of fluorescent products. The mixture was quenched with aqueous ammonium chloride, extracted with CH 2 C1 2 , and dried over CaCl 2 . The solvent was evaporated to dryness and chromatography was carried out with 1 : 1 CH 2 Cl 2 :hexane as eluant.
  • Pd(dppf) (3 mg) is prepared by stirring a suspension of Pd(dppf)Cl 2 in THF over Mg turnings for 20 min. and is transferred into the reaction mixture by canula. The solution is stirred overnight, quenched with aqueous ammonium chloride, extracted with CH 2 C1 2 , and dried over CaCl 2 . The solvent is evaporated to dryness and chromatography is carried out with 1 :1 CH 2 Cl 2 :hexane as eluant. The product, 5,15-diphenyl-10,20- divinylprophyrin, elutes in one band and is isolated in 90% yield.
  • a solution of N,N"-dilithio-5,15-dibromo-10,20-diphenylp ⁇ hyrin (0.2 mmol) in 15 mL of THF is prepared generally according to the method of Arnold, J. Chem. Soc. Commun. 1990, 976.
  • a solution of vinyltributyltin (2 mmol) in 5 mL THF is added to the reaction mixture.
  • Pd(dppf) (3 mg) is prepared by stirring a suspension of Pd(dppf)Cl 2 in THF over Mg turnings for 20 min. and is transferred into the reaction mixture by canula. The solution is stirred overnight, and quenched with a solution of anhydrous NiCl 2 in THF.
  • EXAMPLE 15 Bis[(5,5',-10,20-diphenylpo ⁇ hinato)zinc(II)]ethyne.
  • Lithium bistrimethylsilylamide (1 mmol) was added to a solution of (5-ethynyl- 10,20- diphenylpo ⁇ hinato)zinc(II) (50 mg, 0.1 mmol) in 20 ml THF to yield the (5-ethynyllithium- 10,20-diphenylpo ⁇ hinato)zinc(II) reagent.
  • Pd(PPh3)4 (20 mg, 0.0173 mmol) and Cul (10 mg) were added to a solution of (5- bromo-10,20-diphenylpo ⁇ hinato)zinc(II) (120 mg, 0.2 mmol) in 20 ml THF.
  • (5,15- diethynyl-10,20-diphenylpo ⁇ hinato)zinc(II) (57 mg, 0.1 mmol) and 0.35 ml of diethylamine in 20 ml THF were added to this solution by canula.
  • the following is a general procedure for the preparation of a conjugated compound composed of at least two covalently bound moieties in which the composite conjugated compound emits in the 650-2000 nm wavelength domain and possesses an emission dipole strength that is large with respect to the either of the covalently bound moieties (or alternatively, the sum of the emission dipole strength of each of the two covalently bound moieties).
  • experimental techniques such as pump-probe transient anisotropy measurements, can be utilized to determine the orientation of the lowest energy transition dipole on the molecular reference frame.
  • This halogenated fluorophore, lumophore, or phosphore is now subjected to a metal catalyzed cross-coupling reaction which results in the formation of an ethyne bond at the atomic position that bore the above said halogen moiety.
  • This ethynylated fluorophore, lumophore, or phosphore is now subjected to a second metal-catalyzed cross-coupling reaction with the above said halogenated fluorophore, lumophore, or phosphore under conditions appropriate to produce an ethyne-bridged bis(fluorophore, lumophore, or phosphore) compound, in which the ethyne moiety connects the two component emissive moieties along a vector that is defined by, or approximates, the head-to-tail alignment of their two respective transition dipoles.
  • a known fluorophore, lumophore, or phosphore which is known to emit light at a wavelength greater than or equal to 450 nm when optically or electrically pumped, can be dihalogenated on its conjugated framework at the positions that define the head and tail of the lowest energy transition dipole.
  • This species can be subjected to a metal-catalyzed cross-coupling reaction which results in the formation of ethyne bonds at the two atomic position that bore the above said halogen moieties.
  • halogenated, dihalogenated, ethynylated, and diethynylated fluorophores, phosphores, or lumophores will enable the straightforward synthesis of dimeric, trimeric, tetrameric, and oligomeric species in which ethyne or butadiyne groups link the respective emissive units in a manner which provides head-to-tail alignment, or approximate head-to-tail alignment, of the low energy transition dipoles of the individual covalently bound moieties that comprise the conjugated compound.
  • EXAMPLE 18 In the following examples, all manipulations were carried out under nitrogen previously passed through an O2 scrubbing tower (Schweitzerhall R3-11 catalyst) and a drying tower (Linde 3-A molecular sieves) unless otherwise stated. Air sensitive solids were handled in a Braun 150-M glove box. Standard Schlenk techniques were employed to manipulate air-sensitive solutions. CH2CI2 and tetrahydrofuran (THF) were distilled from
  • Cyclic voltammetric measurements were carried out on an EG&G Princeton Applied Research model 273A Potentiostat/Galvanostat.
  • the electrochemical cell used for these experiments utilized a platinum disk working electrode, a platinum wire counter electrode, and a saturated calomel reference electrode (SCE).
  • the reference electrode was separated from the bulk solution by a junction bridge filled with the corresponding solvent/supporting electrolyte solution.
  • the ferrocene/ferrocenium redox couple was utilized as an internal potentiometric standard.
  • reaction mixture in 50 ml of dry THF was transferred to the reaction mixture by canula. After stirring for 10 rnin, the reaction mixture was transferred to a 250 mL Schlenk tube containing 12 (0.404 g, 4.02 x 10 "4 mol) and Pd(PPh 3 ) 4 (0.069 g, 5.97 x 10" 5 mol) and 40 ml of dry THF.
  • reaction mixture was stirred under 2 at 55 DC for 65 h, after which time it was
  • Tetrabutylammonium fluoride (1 M in THF, 1.12 ml, 1.12 x 10" 3 mol) was added to a
  • reaction mixture was stirred under N2 at 35 DC for 7 h, and
  • reaction mixture was stirred under N2 at 40 DC for 18 h, and
  • the invention can be practiced using other moieties, including ethene, polyines, phenylene, thiophene, anene, or allene.

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