JP2007221168A - Emissive multichromophoric system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emissive multichromophoric system based on new highly conjugated porphyrin. <P>SOLUTION: A compounded multichromophoric system is provided, which shows excitation state of low energy fluorescence correlated with a phase relation, by which a transition dipole of a formation block of a pigment is designated. Polarized property of these singlet excitation state can be preserved with a long temporal measure (units in ns). In a preferred embodiment, ethylene- and butadiene-bridged multiporphyrin speices showing high anisotropic excitation state shows an exceptionally large light-emitting dipole intensity, and it is a new example for oligo pigment assembly having super radiation luminescence. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention preferably comprises (i) a low energy luminescent excited state in which the transition dipoles of the pigment building block as component are correlated in a defined phase relationship, and (ii) polarization of the excited state over a long time scale. , (Iii) luminescence quantum yield with anomalous dependence on supramolecular structure and emission wavelength, (iv) collective oscillator behavior in the respective electrochemically excited state, and (v) reference It relates to a synthetic multicolor chromophore system that exhibits an integrated luminescent oscillator strength greater than that exhibited by the monomeric chromophore.

  In the photophysical properties of a wide variety of conjugated oligomers and polymers, there has traditionally been considerable interest in the desire to enhance the superradiant emission and electroluminescence of manufacturable materials. (See, for example, Patent Document 1, which is incorporated herein by reference). Interestingly, these technically important electro-optical properties are derived from long-range electron excitations (one-dimensional excitons), both of which extend over many monomer units. Seems to be related in that Although electroluminescence of conjugated polymers has been an interesting issue for many years, the superradiant properties of these materials are that thin films of superradiant polymers are optically pumped with great strength. Stimulated by the observation that stimulated emission amplification (ASE) sometimes occurs, a detailed study has just begun.

Superradiance is interactive light emission that occurs when a set of illuminants (luminescent pigment blocks) is excited to a correlated state with a macroscopic dipole moment. One salient feature that is key to this optical nonlinear phenomenon is the emission of coherent radiation pulses with a peak intensity proportional to the square of the number of correlated emitters. Thus radiation rate constant k _r an array of super-radiant pigments shown in, Einstein equation relating spontaneous emission for each of the monomeric chromophoric building blocks (Equation 1)

Exceeds the value determined by the dependency highlighted in. In the above formula (1), E is the emission energy, n and e are the refractive index and dielectric constant of the medium, and <μ> is the transition dipole moment of emission. _{Note that} the magnitude of kr is a measure of the number of coupled oscillators. That maximum value of the observable k _r classically expected for a set of m pigment showing a super radiant emission, the radiation rate constant determined for chromophore monomer corresponding to m It corresponds to double.

  In one embodiment of the invention, the monomeric chromophore building blocks are conjugated to form a dimer, trimer, oligomer or polymer. The monomeric chromophore building block can be, for example, porphyrin. As can be appreciated by those skilled in the art, porphyrins are derivatives of porphins having a conjugated cyclic structure in which four pyrrole rings are linked through their methine bridges through their 2- and 5-positions. Porphyrins can have up to 12 substituents at their meso position (ie, α position) and pyrrole position (ie, β position) (see, for example, Patent Documents 2, 3 and 4. These patents are incorporated herein by reference. Porphyrins can be bound to other molecules by covalent bonds. The electronic characteristics of a porphyrin ring system can be altered by substituting one or more substituents. The term “porphyrin” includes derivatives in which a metal atom is inserted into the ring system, as well as molecular systems in which a ligand is bound to the metal. These substituents as well as the entire porphyrin structure can be neutral or can be positively or negatively charged.

Numerous porphyrins have been separated from natural raw materials. Famous porphyrin-containing natural products include hemoglobin, chlorophyll and vitamin B _12. Also, many porphyrins are typically synthesized in the laboratory by condensing an appropriate substituted pyrrole and an aldehyde. However, this type of reaction generally proceeds in a low yield and cannot be used to produce many types of substituted porphyrins.

US Pat. No. 5,798,306. U.S. Pat. No. 5,371,199. U.S. Pat. No. 5,783,306. US Pat. No. 5,986,090.

In one aspect of the invention, the conjugated multicolor chromophore system comprising a polymer comprises a number of linked porphyrin monomer units of the following formula (1), (2) or (3): ing.

In the above formula, M and M ′ are metal atoms, and R _{A1 to} R _A4 and R _{B1 to} R _B8 are independently H or a chemical functional group that can have a negative charge before binding to the porphyrin compound. It is a group. In some embodiments, at least one of R _{A1 to} R _A4 has the formula CH═CH ₂ , or at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 has the formula C (R _C ) = Although have _{C (R D) (R E} ), provided that _R C, at least one is not H of _{R D} and _{R E,} R C, _{R D} and _{R E} is independently H, F, Cl, Br, I, alkyl or heteroalkyl having 1 to about 20 carbon atoms, aryl or heteroaryl having about 4 to about 20 carbon atoms, alkenyl or heteroalkenyl having 1 to about 20 carbon atoms, alkynyl or heteroalkynyl having 1 to about 20 carbon atoms Trialkylsilyl or porphyrinate; M is a transition metal, lanthanide series, actinide series, rare earth metal or alkali metal. R _C , R _D and R _E can also include peptides, nucleosides and / or saccharides.

In other embodiments, at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 has the formula C≡C (R _D ). In yet another preferred embodiment, at least one of R _{A1 to} R _A4 is a haloalkyl having 1 to about 20 carbons. In still other preferred embodiments, at least one of R _{B1 to} R _B8 is a haloalkyl having 2 to about 20 carbons, or at least 5 of R _{B1 to} R _B8 are having 1 to about 20 carbons. It is haloalkyl or haloaryl having from about 6 to about 20 carbon atoms. In still other preferred embodiments, at least one of R _{B1 to} R _B8 is a haloaryl or haloheteroaryl having from about 4 to about 20 carbon atoms. In still other preferred embodiments, at least one of R _A1 -R _A4 or R _B1 -R _B8 can comprise an amino acid, peptide, nucleoside or saccharide.

The present invention also provides a method for producing a substituted porphyrin and an intermediate for producing the substituted porphyrin. In some embodiments, the method produces a porphyrin compound in which at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 is a halogen in formulas (1), (2) and (3) Contacting the compound with a complex having the formula Y (L) ₂ . Here, Y is a metal and L is a ligand. By this method, a first reaction product is obtained, which is represented by the general formulas T (R _L ) _z (R _O ), T (R _L ) _z (R _O ) _y (X _B ) _w , T (R ₀ ). Contact with the organometallic compound of (X _B ) or T (R _O ) _y . Where T is a metal; X _B is a halogen; R _L is a cyclopentadienyl or aryl having about 6 to about 20 carbon atoms; R 2 _O is an alkyl having 1 to about 10 carbon atoms, an alkenyl having about 2 to about 10 carbon atoms Or alkynyl, aryl having from about 6 to about 20 carbon atoms; z and w are greater than or equal to 0; y is at least 1. This contact produces a second reaction product from which a third reaction product containing porphyrin substituted with R 2 _O by reductive elimination is obtained.

In another aspect, the present invention provides a polymer comprising linked porphyrin units. In certain embodiments, porphyrin units having the formulas (1), (2) and (3) share a covalent bond. In another embodiment, at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 has a function as a linking group. In these embodiments, at least some of the linking groups are of the formula [C (R _C ) = C (R _D )) (R _E )] _x , [C≡C (R _D )] _x , [CH ₂ ( _RC ) -CH ( _RD ) ( _RE )] _x or [CH = CH ( _RD )] _x . Here, x is at least 1. Remaining R _{A1 to} R _A4 and R _B1
˜R _B8 is hydrogen, alkyl or heteroalkyl having 1 to about 20 halogen carbon atoms, or aryl or heteroaryl having 4 to about 20 carbon atoms, C (R _C ) ═C (R _D ) (R _E ), C≡ C (R _D ), or a chemical functional group, including peptides, nucleosides and / or saccharides. In other preferred embodiments, the linking group is a cycloalkyl or aryl having from about 6 to about 22 carbon atoms.

Moreover, according to this invention, the manufacturing method of a porphyrin containing polymer is provided. In certain embodiments, the method independently has the formula (1), (2) or (3), wherein at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 in each compound is olefinic. The method includes the step of producing at least two compounds containing a carbon-carbon double bond or a chemical functional group that reacts with the carbon-carbon double bond. In other embodiments, at least one of R _{A1 to} R _A4 or R _{B1 to} R _B8 in each compound includes a carbon-carbon triple bond or a chemical functional group that reacts therewith. The compound is then contacted under such effective conditions for a time effective to hang the covalent bond through a carbon-carbon double bond or carbon-carbon triple bond.

In another embodiment of the present invention, the building blocks of the luminescent pigment, such as independently formula (1), (
Conjugated dimers and trimers linking the porphyrin monomer units having 2) or (3) and exhibiting a low energy fluorescence excited state in which the transition dipoles of the pigment building blocks are correlated in a defined phase relationship Making oligomers, polymers or other highly conjugated synthetic multicolor chromophore systems. In other embodiments, ethyne- and butadiyne-bridged multiporphyrin species exhibiting a high degree of excited state anisotropy are analyzed by analyzing the intrinsic fluorescence decay rate and quantum yield data of the corresponding fluorescence. It can be seen that a new method for producing a superradiant oligo pigment aggregate can be obtained with a large emission dipole intensity. This photophysical behavior is not only due to the fact that the arrangement of these conjugated pigments behaves as collective oscillators, but also the large transition dipole moment and strong chromophore-chromophore of the porphyrin monomer unit. Derived from the fact that combined with an electronic coupling between them creates a large Frank-Condon barrier for intersystem crossing between the respective S ₁ and T ₁ states. These results show that substantial emission dipole intensities are actually realized for low energy fluorescent chromophores, and a high quantum yield design in the vicinity of infrared emitters with a simple consideration of the energy gap. Shows that it will not interfere.

In another aspect, according to the present invention, a conjugated compound comprising a partial structure linked by at least two covalent bonds is produced, and then emitted from each component partial structure with a wavelength of 650-2000 nm. There is provided a method comprising exposing the compound to an energy source under such effective conditions for a time effective to emit light having an intensity greater than the sum of the emitted light. The In a preferred embodiment, the emission of light from the material can be effected by optical or electrical pumping. For example, when these materials are optically pumped, the emission dipole intensity can be assessed by determining the quantum yield of the reaction and the corresponding emission decay rate using conventional methods. [For example, Lakowicz, J. et al. R. Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983); J. et al. Modern Molecular Photochemistry (The Benjamin / Cummings Publishing Co., Inc., Menlo Park, 1978); L. J. et al. Chem. Phys. 21, 836-850 (1953); Dicke, R .; H. Phys. Rev. 93, 99 (1954)],
For example, the fluorescence quantum yield (QY) can be determined by the method cited above (Lakuwicz, 1983) using the above relationship. Where ∫I _complex and ∫I _standard are the total integrated fluorescence intensity of the complex and luminescence standard, respectively, A _complex and A _standard are the absorbance specific to the corresponding wavelength, and QY _satnard is the tolerance for the standard chromophore. QY value of the fluorescence obtained. The quantity (n 0 _complex / n 0 _standard ) ² is a correction value for the refractive index of the solvent. A steady state emission spectrum can be obtained with a conventional luminescence spectrometer with a suitable emission detector. Typically, the sample concentration is adjusted so that the absorbance is between 0.005 and 0.04 at the excitation wavelength. The emission spectrum obtained for the chromophore (fluorophore, phosphorphore, or luminophore) is corrected so that the wavelength-dependent efficiency of the detection system can be explained. The efficiency of this wavelength-dependent detection system can be determined using the spectral output of the calibration light source obtained from National Bureau of Standard, USA. Secondary correction of the emission spectrum used to determine QY (eg, energy dependent intensity correction required for analysis grating monochromator variable bandpass / constant wavelength resolution data acquisition mode) Performed in the manner outlined in the literature [Lakowicz, 1983]. Quantum yield is typically determined using two standard criteria for each chromophore.

The emission dipole intensity is defined as <μ> _chromophore / <μ> _reference . Here, <μ> _reference corresponds to one emission dipole intensity of a partial structure bonded by a covalent bond that defines the conjugated compound. If the radiation rate constant k _r is determined by an appropriate time-resolved spectral method, the value of <μ> can be determined from the Einstein equation for stimulated emission. [Lakowicz, J .; R. Principles of Fluorescence Spectroscopy (Plenum Press, New York, 1983); J. et al. Modern Molecular Photochemistry (The Benjamin / Cummings
Publishing Co. , Inc. Dexter, D., Menlo Park, 1978); L. J. et al. Chem. Phys. 21, 836-850 (1953); Dicke, R .; H. Phys. Rev. 93, 99 (1954)].

  In some embodiments, the compound exhibits an integrated light emitting oscillator strength that is greater than the sum of the light emitting oscillator strengths exhibited by the component substructure. A typical partial structure includes a conjugated ring system. Preferably, at least one of these partial structures is a laser dye, a fluorophore, a luminophore, or a phosphorescent group. Particularly preferred substructures are porphyrin, porphycene, rubirin, rosarin, hexaphylline, sapphyrin, chlorophyll, chlorin, phthalocyanine, porphyrazine, bacteriochlorophyll, pheophytin, texaphyrin, and the corresponding metallized derivatives. Contains. Other types of typical partial structures have 16 or more carbon atoms and 4 heteroatoms such as N, O, S, Se, Te, B, P, As, Sb, Si, Ge, Sn, and Bi. A conjugated macrocyclic compound containing one or more.

  These substructures contain at least one carbon-carbon double bond, carbon-carbon triple bond or a combination thereof, or an imine, phenylene, thiophene, amide, ether, thioether, ester, ketone, sulfone, or carboimide group. It is out. Exemplary bond types are ethynyl, ethenyl, allenyl, butadiynyl, polyvinyl, polyynyl, thiophenyl, furanyl, pyrrolyl, p-diethynylallenyl bond; and diethynyl, di (polyynyl)), Divinyl, di (polyvinvir) (di (polyvinvir)), or any conjugated heterocyclic group containing a di (thiophenyl) substituent. Such materials thus include, for example, laser dyes, fluorophores, luminophores, and / or phosphorophores covalently linked by alkynyl or alkenyl bonds.

  The synthesized conjugated multicolor chromophore systems of the present invention can be used, for example, as dyes, catalysts, contrast-providing agents, anticancer agents, antiviral agents, electroluminescent materials, LEDs, lasers, photorefractive materials, and in chemical sensors and electro-optical devices. Can be used in That is, the present invention, in one embodiment thereof, is unable to substantially chemically react with the compound of the present invention and the compound, and cannot absorb light and emit light at a wavelength at which the compound absorbs light and emits light. A laser is provided in which a dye solution comprising an aqueous or non-aqueous solvent is disposed in a resonant cavity. The laser of the present invention further includes a pumping energy source that produces stimulated emission in the dye solution.

  Other lasers of the present invention include a solid, which then is a compound of the present invention and a host polymer that cannot react with the compound and cannot absorb and emit light at a wavelength at which the compound absorbs and emits light. Is included. Such lasers further include an energy source that couples with the solid to generate light in the solid or that couples with the host polymer to generate light therein. There is also provided an optical amplifier comprising a polymeric optical waveguide and a compound of the present invention.

The present invention also provides a polymer lattice comprising a body of electrically conductive organic polymer. Such a body has the shape of an open porous network and defines a porous network that has an expanded surface area and creates voids. An active electronic material comprising the compound of the present invention is disposed in at least a part of the void space created by the porous network structure. Conductive organic materials can also contain the compounds of the invention.

  The present invention also provides a polymer grid electrode comprising a body of an electrically conductive organic polymer electrically connected to an electrical terminal. This body has the form of an open porous network, defines a porous network that has an expanded surface area and creates voids, and at least a portion of the void space created by the porous network. An active electronic material comprising a compound of the present invention disposed therein is included.

  According to the invention, there is also provided a polymer lattice comprising a body of an electrically conductive organic polymer comprising a first electrode and a second electrode spaced apart from each other and comprising a compound of the invention. A solid state polymer lattice triode is provided. The body is preferably in the form of an open porous network, with a porous network having an extended surface area inserted between the first electrode and the second electrode to create a void. It prescribes.

  In another aspect, the present invention comprises a polymer lattice comprising first and second electrodes spaced apart from each other and comprising a body of an electrically conductive organic polymer. A light emitting polymer lattice triode is provided. The body in such a triode has the shape of an open, porous network that defines a network that has an extended surface area inserted between the first and second electrodes to create a void. is doing. An active light emitting semiconductor electronic material comprising the present invention is inserted between the first and second electrodes and serves to transport charge carriers between the first and second electrodes; The charge carriers are acted on by the polymer lattice so that when a voltage is applied between the first and second electrodes, the charge carriers are injected and emit light.

  The invention also includes a conductive first layer having a high work function; a second layer of semiconductor in contact with the first layer, the second layer comprising a compound of the invention. A photoresponsive diode system comprising a diode comprising a conductive third layer in contact with the second layer. The system of the present invention further includes a source that reverse biases across the diode, a source that strikes the diode with light, and a diode when the reverse bias is applied to the diode and light strikes the diode. A source for detecting the resulting current is included.

  The invention also includes a conductive first layer having a high work function; a second layer of semiconductor in contact with the first layer, the second layer comprising a compound of the invention. An optical response comprising a diode comprising an inorganic semiconductor doped to provide a conducting state, further comprising a conductive third layer in contact with the second layer; A diode system is provided. Such a system further includes a source that reversely biases across the diode, a source that impinges light on the diode, and a diode when the reverse bias is applied to the diode and light impinges on the diode. A source for detecting the resulting current is included.

  Further in accordance with the present invention is a conductive first layer having a high work function; a second layer of semiconductor comprising the compound of the present invention and in contact with the first layer; A dual function light emitting, light responsive input / output diode comprising a diode having a conductive third layer in contact with the two layers is provided. Such a system further includes a source that reversely biases across the diode, a source that impinges light on the diode, and a diode when the reverse bias is applied to the diode and light impinges on the diode. A source for detecting the resulting current is included.

  Further in accordance with the invention, a conductive first layer having a high work function; a semiconductor second layer in contact with the first layer comprising a compound of the invention; and the second layer A dual function light emitting, light responsive input / output diode is provided that includes a diode having a conductive third layer in contact therewith. Such a system further includes a source that reverse biases across the diode, a source that impinges light on the diode, and when the reverse bias is applied to the diode and a light input signal impinges on the diode. A source for detecting the current produced by the diode, a source for stopping reverse biasing, and a source for applying a positive bias output signal across the diode to properly emit the light output signal from the diode Is included.

  Also, according to the present invention, a current or voltage generated by a diode when a reverse bias is applied across the diode to cause the light input signal to collide with the diode and a reverse bias is applied to the diode and the light input signal collides with the diode. Is detected as an electrical input signal, reverse bias is stopped, a positive bias output signal is applied across the diode, and in response to the positive bias output signal, the diode appropriately outputs light. A dual function input / output method is provided that includes the step of emitting a signal.

  Further, according to the present invention, in a product having an integrated solid-phase electromagnetic radiation source, the electromagnetic radiation source is disposed at two intervals with the compound of the present invention sandwiched therebetween. A contact having a layered structure comprising a number of layers including a conductive layer, and further causing a current to flow between the conductive layers to emit non-coherent electromagnetic radiation of the first wavelength from the compound of the present invention. Product is provided. The layered structure includes an optical waveguide having first and second cladding areas having a core area therebetween, the optical waveguide having non-coherent electromagnetic radiation having the first wavelength. At least a portion of the optical waveguide, wherein the core region absorbs the non-coherent electromagnetic radiation of the first wavelength and responds to the absorbed non-coherent electromagnetic radiation from the first wavelength. Preferably, it also comprises a layer of a second organic material selected to emit coherent electromagnetic radiation having a long second wavelength.

  Moreover, according to this invention, the method of screening a compound is provided. In a preferred embodiment, such a method produces a conjugated compound comprising at least two covalently bonded substructures; a time effective to emit light at a wavelength of 650-2000 nm from the compound. Exposing the compound to an energy source under such effective conditions during the period of time, and the emitted light is (1) stronger than the sum of the light emitted individually by the covalently bonded substructure And (2) determining whether it has an intensity greater than the intensity of light emitted by any of the covalently bonded substructures.

  The present invention also provides a method of binding a compound of the present invention to a targeting agent that localizes the compound in selected body tissues. The compound can be excited to an emission state having a sufficient emission dipole intensity in a spectral region of 700 to 1100 nm by holding the light source for exploration from the outside and holding the tissue.

  Those skilled in the art will better understand the many objects and advantages of the present invention by referring to the accompanying drawings.

Detailed Description of the Invention Those skilled in the art will understand the various types of dimers, trimers, oligomers or polymers that can be made from the porphyrin-containing compounds of the present invention. For example, it is possible to form a slightly linear polymer chain in which a part of the polymer has the general formula (P _N ) _r .
Here, _PN is a porphyrin unit, and r is at least 2. In other embodiments, the general formula

A linear polymer chain is produced. Here, Q _L is a linking group, _PN is a porphyrin unit, and h, l, and s are independently selected to be at least 1. For example, some of these polymers have the formula

Can have. Where P _N1 and P _N2 are independently selected porphyrin units, Q _L1 and Q _L2 are independently selected linking groups, and l ′, l ″, s ′ and s ″ are at least 1. These substantially linear polymer chains are cross-linked, and a part of the polymer has the general formula

It can be made to have. Where Q _H is a linking group and h, u and v are independently selected to be at least 1. Some of these cross-linked polymers have the formula

Can have. Here, P _N3 is a porphyrin unit, Q _H1 and Q _H2 are independently selected linking groups, and h ′, h ″, u ′ and u ″ are at least 1. Thus one possible cross-linked polymer is

Have Here, r ′ is at least 1.

The dimers, trimers, oligomers or polymers of the present invention are generally made by contacting a substituted porphyrin with a second compound containing a functional group that reacts with a functional group contained within the porphyrin. Preferably, the porphyrin contains one olefinic carbon-carbon double bond, carbon-carbon triple bond, or some other reactive functional group. This contact must be made under conditions effective to produce covalent bonds between the individual functional groups that react. Preferably, the porphyrin-containing polymer is made, for example, by cross-coupling dibrominated porphyrin units via a metal. Porphyrin-containing polymers can be synthesized by using a known terminal alkyne coupling chemical reaction. (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 Eglington, et al. , Adv. Org. Chem. 1963, 4, 225. As can be appreciated, the second compound above can be a substituted porphyrin or any other moiety of the invention, such as an acrylate monomer. Therefore, a wide variety of copolymer structures can be synthesized using the porphyrin of the present invention. By careful selection of substituents, the porphyrins of the present invention can be incorporated into virtually any polymer matrix known in the art. These polymer matrices include, but are not limited to, polyacetylene, polyimide, polyacrylate, polyolefin, polyether, polyurethane, polyquinoline, polycarbonate, polyaniline, polypyrrole and polythiophene. For example, fluorescent porphyrins can be incorporated into such polymers as groups that cap the ends.

Conjugated synthetic multicolor chromophore systems of the present invention include, for example, dyes, catalysts, contrast-providing agents, anticancer agents, antiviral agents, liquid crystals, electroluminescent materials, LEDs, lasers, photorefractive materials as chemical sensors, electro-optical devices and solar Can be used for energy conversion device. They can also be incorporated into supramolecular structures. Polymers and supramolecular structures that fix porphyrin units in a relatively stable geometry must improve many known uses for porphyrins, and also for new and new uses such as solidification for sterilization of virus-containing solutions. Phase systems and novel applications as waveguides, molecular wires, optical triggers, and molecular lasers, optical amplifiers, dye lasers, polymer lattice triodes, light emitting and photoresponsive diode systems, LEDs, applications in photoelectric fields, and organic lasers It would even be possible to use the present invention in products including, ecological diagnostic methods and devices for detecting the emission of infrared radiation by reagents bound to human organs. Typical applications are described in the following patents. These patents are hereby incorporated by reference. U.S. Pat. No. 5,657,156 (van Veegel, et
al. U.S. Pat. No. 5,237,582 (Moses); U.S. Pat. No. 5,504,323 (Heeger, et al.); U.S. Pat. No. 5,563,424 (Yang, et al) U.S. Pat. No. 5,062,428 (Chance); U.S. Pat. No. 5,859,251 (Reinhardt, et al.); U.S. Pat. No. 5,770,737 (Reinhardt). U.S. Pat. No. 5,062,428 (Chance); U.S. Pat. No. 5,881,089 (Bergren, et al.); U.S. Pat. No. 4,895,682. (Ellis, et al.); U.S. Pat. No. 4,986,256 (Cohen); U.S. Pat. No. 4,668,670 (Ride). ut, et al.); U.S. Pat. No. 3,897,255 (Erickson); U.S. Pat. No. 3,899,334 (Erickson); U.S. Pat. No. 3,687,863 (Wacher). U.S. Pat. No. 4,647,478 (Formanek, et al.); And U.S. Pat. No. 4,957,615 (Ushizawa, et al.). Still other uses include, for example, British Patent No. 2,225,963 (Casson, et al.); International Publication No. 89/11277 (Dixon, et al.); International Publication No. 91/099631 ( Matthews, et al.); WO 98/50989 pamphlet (Forrest, et al.); WO 01/49475 pamphlet (Peumans, et al.); European Patent Application No. 85105490.8 ( Weishupt, et al.); European Patent Application 90202953.7 (Terrell, et al.); European Patent Application 89304234.1 (Matsushima, et al.); Lchn, Angew. Chem. Int. Ed. Engl, 1988, 27, 89; Wasielewski, Chem. Rev. 1992, 92, 435; Mansury, et al. Chem. Soc. , Chem. Comm. 1985, 155; Groves, et al. , J .; Am. Chem. Soc. , 1983, 105, 5791; and Giraud Godquin, et al. , Angew. Chem. Int. Ed. Engl, 1991, 30, 375. The porphyrin of the present invention can be replaced with the porphyrins described in the above documents.

  The fluorophore of the present invention is a light-emitting compound having the same spin multiplicity in the two states (typically excited state and ground state) included in the radiation transition. A luminophore consists essentially of two or more orbital arrangements in which one of the two states involved in the radiative transition (typically the excited state of the electrons) has different spin multiplicity. Is a luminescent compound derived from [See, for example, Lakowicz, J. et al. R. Principles of Fluorescence Spectroscopy (Plenum Press, New York, (1983); Turro, NJ Modern Molecular Photochemistry, Inventor P. M. 78. Invented by The Benjamin / Cummings. A group is a light-emitting compound in which the spin multiplicity of the two states (typically excited and ground states) involved in the radiative transition is different in each spin multiplicity. Any organic, inorganic, or coordination compound that has been confirmed to produce laser emission, typical laser dyes are Birge, RR; arte, FJ, Kodak Optical Products, Kodak Publication JJ-169B (Kodak Laboratory Chemicals; Rochester, NY (1990). Typical laser dyes include:

p-Terphenyl Sulfoeedamine B
p-Quaterphenyl Rhodamine 101
Carbostyril 124 Cresy Violet perchlorate popop DODC iodide Coumarin 120 Sulfolodamine 101
Coumarin 2 Oxazine 4-Perchlorate Coumarin 339 DCM
Coumarin 1 Oxazine 170 Perchlorate Coumarin 138 Nile Blue A Perchlorate Coumarin 106 Oxatin 1 Perchlorate Coumarin 102 Pyridine 1
Coumarin 314T Styryl 7
Coumarin 338 HIDC Iodide Coumarin 151 DTPC Iodide Coumarin 4 Cryptocyanine Coumarin 314 DOTC Iodide Coumarin 30 HITC Iodide Coumarin 500 HITC Perchlorate Coumarin 307 DTTC Iodide Coumarin 334 DTTC Perchlorate Coumarin 7 IR-144
Coumarin 343 HDTC Perchlorate Coumarin 337 IR-140
Coumarin 6 IR-132
Coumarin 152 IR-125
Coumarin 153 Boron dipyrromethene HPTS fluorescein rhodamine 110 2,7-dichlorofluorescein rhodamine 6G rhodamine 19 perchlorate rhodamine B

In preferred embodiments, the electronic structures of the substructures of the components in the compounds of the present invention are similar. Each one-electron redox potential is preferably different only within 250 mV. It is also preferred that the lowest energy electron transitions differ only within 2500 cm ⁻¹ .

  In accordance with the present invention, it has been found that various types of novel highly conjugated porphyrin based chromophore systems of the present invention have abnormal electro-optic properties and can function as collective oscillators. . The generation of collective oscillators and the accompanying light emission requires coupling of monomeric pigment transition dipoles. The preferred embodiment compounds of the present invention are of the multicolor chromophore system type that exhibits extremely strong pigment-to-pigment electronic coupling, these aggregates being carbon in the component porphyrin building block. It is characterized by having an ethyne and butadiyne partial structure directly linking the skeletons of (Fig. 1). These porphyrin sequences cross-linked with ethyne and butadiyne exhibit several surprising and surprising photoelectric properties, including their absorption shape, emission wavelength, redox properties, and spin distribution and orientation in the triplet state. Is widely regulated by the topological arrangement between porphyrin and porphyrin. The ability to widely change such a wide range of photophysical properties is the versatile synthesis that can vary the degree of coupling between excited and ground states between the pigments in these systems. Obtained by law. It should be noted that the pigment-pigment electron interaction in these supramolecular assemblies typically reduces the width of the electron transition regardless of the chromophore-chromophore linkage properties. Because it is large compared to the broadening vibration mode, the nature of the pigment's transition dipole interaction and the corresponding photophysical properties of the individual electronically excited singlet states can be closely controlled by the molecular structure. it can.

  In a preferred embodiment, the compounds of the present invention are synthetic multicolor chromophore systems that exhibit one or more of the following optical properties: (i) the transition dipole of the component pigment building block is Low energy luminescent excited states correlated in a defined phase relationship, (ii) excited state polarization over a long time scale, (iii) luminescent quanta with anomalous dependence on supramolecular structure and emission wavelength The yield, (iV) the characteristics of the collective oscillator behavior in each electronically excited state, and (v) an extreme with a magnitude exceeding the classically predicted maximum (equation (1)) Super radiation. The integrated intensity of the luminescent oscillator is greater than that shown by the standard monomeric chromophore.

In another embodiment of the present invention, the chromophore system produces a compound comprising at least two covalently bonded moieties, and the conjugated compound is allowed to undergo such a period of time effective for it to emit light. Created by a method of exposing to an energy source in effective conditions. The emitted light is preferably in the range of 650 to 2000 nm. The partial structure used is, for example, a porphyrin, which can be linked by at least one carbon-carbon double bond, carbon-carbon triple bond or a combination thereof. This linkage can be, for example, ethynyl, ethenyl, allenyl, or butadiynyl. In other embodiments of the invention, the moiety can be linked, for example, by a combination of these units or by at least one imine, phenylene or thiophene group.

Time-resolved fluorescence spectroscopy In the present invention, (porphinate) zinc (II) monomer (5-ethynyl-10,20-diphenylporphinate) zinc (II) (compound 1 ), incorporating standard ethyne ( 5,15-diethynyl-10,20-diphenylporphinate) zinc (II) (compound 2 ) and 2-ethynyl-5,10,15,20-tetraphenylporphinate) zinc (II) (compound 3 )) and conjugated (porphinato) SEQ compound singlet excited state (S ₁₎ of isotropic in and anisotropic kinetic behavior of lowest energy (compound 4-12) (Fig. 1) of zinc (II) Were characterized by time correlated single photon (TCSPC) spectroscopy.

  Fluorescence anisotropy (r (t)) measured at time t after optical excitation is expressed by the following equation from transient signals in parallel (I‖) and vertical (I⊥) directions.

Obtained using. The magnitude of initial anisotropy r (0) depends on the degeneracy and polarization of the respective absorption and emission states. The value r (0) (formula (3)) in the dilute solution is the product of the angular displacement (α) of the absorption and emission dipoles and the loss of anisotropy due to photoselectivity (2/5).

In the absence of the coherence effect, the initial anisotropy of fluorescence for a chromophore system based on a (porphinate) metal species will fall into four extreme cases: (i) Degenerate state of the excited state , The initial occupancy of the excited state is randomized between orthogonal energetically equivalent x- and y-polarized S ₁ states to give an r (0) value of 0.1. (Ii) If the degenerate state of the excited state is uncoupled and the absorption and emission dipoles are parallel (α = 0), r (0) will be equal to 0.4; (iii) excitation If the state is degenerate (the degeneracy is 1) and the absorption and emission dipoles are orthogonal (α = 90 °), a value of r (0) of −0.2 will be observed. ; (Iv) Find out if overlapping (multiple) states with different polarizations and degeneracy are pumped. When examined, a value of r (0) that is between the extreme values of -0.2 and 0.4 will be shown. For the present invention, it is important to note that the actual measurement of r (0) is extremely dependent on the time scale of the experiment. For example, if the current absorption and emission dipoles are parallel, but the empirically determined value of r (0) is less than 0.4, this is generally the time of the experiment. It shows that there exists a relaxation process that occurs on a time scale shorter than the resolution. Such a process can involve a nuclear dynamics process within the molecule (eg, rotational or vibrational motion) or an electronic (vibrational) relaxation pathway. Therefore, in the present invention, the degree of separation of energy between orthogonal excited states and the shape and size of the chromophore are reduced to zero (r (t) = 0) as the fluorescence anisotropy decays to zero. A scale will be determined and whether the experimental time domain is adequate to measure the initial anisotropy at the extreme values of 0.4 and -0.2.

The life and time-resolved fluorescence anisotropy data S ₁ excited state with respect to the present invention for the compound 1-12 are summarized in Figure 4. Typical isotropic (at magic angle) and anisotropic fluorescence decay shapes for these compounds are shown in FIG. In these experiments, the sample was excited on the low energy side of each lowest energy Q absorption band. The fluorescence decay was examined at a wavelength λ _max at the red end of the emission. A single exponential decay of isotropic fluorescence was observed (FIG. 4). Notably, all these species of the present invention have a similar (ns unit) fluorescence lifetime (τ _F ). In contrast, the kinetics of decay of fluorescence anisotropy varies widely in compound 1-12 of the present invention. The photophysical standard for porphyrins (5,10,15,20-tetraphenylporphinate) zinc (II) (TPPPZn) has a double-degenerate S ₁ excited state and has the lowest energy Q transition. (R (0) = 0.1; t = 20 ps) is shown as the initial anisotropy value after electronic excitation at the red edge. Initial anisotropy measurements (r (0) = 0.2; t = 20 ps) for compounds 1 , 2 and 3 of the present invention show that when expanding the porphyrin conjugation via the meso-ethynyl moiety, It shows that enough electronic perturbation is introduced to separate the transitions polarized in the direction and y-direction.

Compounds 4 to 12 of the present invention have a fluorescence anisotropy measured at 20 ps (picoseconds) after excitation in the range of 0.1 to 0.4, and doubly degenerate unpolarized state (r ( It shows that an excited state of the chromophore can be created over the range from 0) = 0.1) to a highly polarized state with a degeneracy of 1 (r (0) = 0.4). The nature of the topological arrangement between porphyrin and porphyrin is clearly important in establishing the magnitude of initial anisotropy. A chromophore crosslinked from β to β exhibits a r (0) value of about 0.1 (compounds 4 , 7 and 10 ), but only a meso to meso bridge (porphinate) zinc (II) The chromophore (compounds 6 , 9 , 11 and 12 ) shows a value of 0.4. In addition to the pigment-to-pigment electronic coupling depending on the topology, the degree of conformational mobility around the conjugated bridge is also the r (0 Often plays a role in determining the size of the compound (compounds 5 and 8 ).

Experimental data in the time degradation, the initial anisotropy typically indicates that the attenuation of a single exponential process for compounds 4-12 of the present invention. These results show that the fluorescence anisotropy at time t after excitation is determined by the time constant of rotation diffusion (τ _r ), the size of [r (t) = r ₀ e ^{(−t / τr)} ]. Show. These data are evidence that there is no process that causes a fast phase shift, and in compounds 4 to 12 , the phase relationship of the dipoles of the respective pigments is observed over the entire lifetime of the S ₁ excited state. It shows that the correlation is maintained. This can be seen most dramatically in meso to meso hethein- and butadiyne-crosslinked compounds 9 , 11 and 12 . These compounds have a single degenerate luminescent S ₁ state that is polarized only along their highly conjugated axes.

Ethyne In a preferred embodiment examples - and butadiyne - porphyrin array Compound 4-12 crosslinking, the size of life indicated by the configuration block 1-3 for each conjugated monomer (1.5 ≦ τ _F ≦ 2. The fact that it exhibits a fluorescence lifetime as large as 2 ns) (0.9 ≦ τ _F ≦ 1.7 ns) strongly indicates an unusually long time scale that can maintain the polarization of the excited state. Energy region of the compound 4 emission maximum of ~ 12 4,000cm ^-1 (621~836nm, Figure 1) over the anisotropy of the wavelength and the excited state of the fluorescent rather in these systems significantly reduce the tau _F Both show that it can be highly modified.

Stokes shift for compound 1-12 in superradiance emission Figure 5, B- and Q- transition dipole moment of the state, and the fluorescence quantum yield (QY) is listed. Emission QY monomeric porphyrin compound 1-3 incorporating ethyne noted that beyond the values measured for TPPZn and (5,15-diphenyl-porphylene diisocyanate) zinc (II) (DPPZn) reference compound I want to be. At the QY determined consistent with bis and tris [a (porphinato) zinc (II)] for the compounds 4-12 is larger than the measured value for monomeric 1-3. The bis - (Compound 4-9) and tris [(porphinato) zinc (II)] The absolute value of the phase geometry of the connection of QY for both species (Compound 10-12), and macrocyclic Note that it varies with the length of the cylindrical π-symmetry bridge connecting the aromatic moieties. When the analysis is based on the kinetic data shown in FIG. 4, the results summarized in FIG. 5 lead to some surprising conclusions.

When the excited state energy is changed in a series of compounds based on a single emission chromophore, the non-radiative decay rate constant ( _knr ) observed for a particular pigment is related to the ground and excited states It has been mentioned so far that a predictable dependence on the degree of overlap of each oscillation between the two must be followed. This quantum effect is usually called the law of energy gap. FIG. 3A highlights the extent of the energy interval between the initial and final states and its dependence on the magnitude of nuclear displacement (ΔQ) in equilibrium between these electronic states. . In the potential energy diagrams 1 and 2 of FIG. 3A, when the energy gap between S _{0 and} S ₁ decreases, the overlap of vibration wave functions increases, and as a result, the corresponding _knr increases. Since τ _F is equal to the reciprocal of the sum of the radiation rate constant (k _r ) and the non-radiation rate constant (τ _F = (k _r + k _nr ) ⁻¹ ), the lifetime of the excited state correspondingly corresponds to the emission of light. Decreases with decreasing energy. This simple prediction has now been demonstrated in several pigment systems.

If a significant deviation from the expected linear dependence of ln (k _nr ) on the emitted light energy is observed inside a series of related chromophores, this is typically the ground state in the equilibrium state. And the nuclear displacement in the excited state is not uniform within these pigments. In connection with this work, it is important to point out that gradually expanding the chromophore conjugation is an easy way to introduce such electronic structural perturbations. This is illustrated in the potential energy diagrams 1 and 3 of FIG. 3A. Note that as ΔQ decreases with constant S ₀ -S ₁ energy separation, the vibrational overlap decreases and the magnitude of _knr decreases. This has been detailed in classic studies of Meyer, substantially the value of k _nr decreases the π electrons Poripirujiru complex of ruthenium delocalized, compared to the prototype ruthenium tris (bipyridyl) It has been shown that the lifetime of light emission is increased. Such a research method is a realistic strategy for creating excited states of long-lived pigments with reduced emission energy compared to the parent chromophore.

However, it is important to point out that a high price is required to create a red-emitting chromophore with a long-lived excited state using a strategy based on the law of the energy gap. As the optical band gap is narrowed, the magnitude of the radiation rate constant k _r is because decreases in the interior of the chromophore isolated having a type substantially given one (Formula (1)), the emission quantum yield The magnitude of the rate (QY; QY = k _r / (k _r + k _nr ) ⁻¹ ) decreases dramatically. It is shown that when the emission energy is shifted moderately (about 2000 cm ⁻¹ ) by extending the chromophore conjugation, the observed QY of emission is greatly reduced by 10 times or more compared to the original pigment complex. It was done.

Taken in connection with the discussion of the law of the energy gap, Compound 4-12 of the present invention, it is long fluorescence lifetimes, and component (porphinato) significantly larger emission quantum than zinc (II) building block It is a surprising compound in that it exhibits both yields. Importantly, despite the fact that the maximum of the lambda _em for these species is at the energetically lower 700～4600Cm ^-1 compared to TPPZn is established group of standards, for compounds 4-12 The fluorescence QY is substantially increased compared to a simple (porphinate) zinc (II) complex (FIGS. 4-6). Since the transition probability of radiation is proportional to the cube of the emission energy, the compounds 4 to 12 of the present invention are substantially larger in fluorescence lifetime and emission quantum than the monomer (porphinate) zinc (II) reference compound. In order to show both yields simultaneously, these multicolor chromophore systems must behave as collective oscillators (<μ> _4-12 >><μ> _TPPPZn ) (Equation (1)).

The degree to which the aggregate of pigments performs superradiance is generally represented by a superradiance enhancement factor (light emission dipole intensity). Here, the value of <μ> _aggregate determined experimentally serves as a reference for <μ> measured with respect to a suitable monomer pigment standard. Thus, the superradiance enhancement factor is a directly observable quantity (observable), which is often taken as a classical measure of the length of excitation diffusion.

Emitting dipole strengths for compounds 1 ~ 12 (EDS) and radiation lifetime (tau _rad) listed in Fig. Bis in the present invention - and tris - (pigment) sequences all compounds 4-12 but indicates these data to indicate a dramatic superradiance reinforcer, consolidated from meso to β meso or meso The size of the EDS determined for the oligo [(porphinate) zinc (II)] system of the present invention with topological arrangement (compounds 5 , 6 , 8 , 9 , 11 and 12 ) is particularly impressive Is. These values greatly exceed the maximum expected values (ie, 2 and 3) predicted for an assembly composed of 2 or 3 monomeric pigment units, respectively (Equation (1)).

  EDS values of this magnitude for similar sized oligomers have not been found so far. Similarly, superradiant conjugated polymers made to date utilize monomer units with transition dipole moments much smaller than those exhibited by porphyryl substructures. Since there is no appropriate photophysical standard among superradiant conjugated organic materials, these data are for a strongly coupled chromophore assembly composed of similar pigment monomer units (bacteriochlorophyll and chlorophyll). It is useful to compare it with the data obtained for the characteristic superradiant biological light-harvesting proteins. Similar data obtained against biological criteria for comparison are shown in FIGS. The B820 subunit of Rhodospirillum rubrum and the Rhodobacter sphaeroides have been treated using bacteriochlorophyll a (Bchla) monomeric EDS as the chromophore standard and Rhodospirillum rubrum LH-2 protein. The appropriate data obtained for the non-light-harvesting complexes LH-1 and LH-2 were analyzed by Einstein's relationship (Equation (1)) and van Grondelle The radiation enhancement factors were shown to be 1.3, 2.8 and 3.8, respectively. These results show that the exciton diffusion length in the B820, LH-1 and LH-2 long wavelength absorbing pigment aggregates corresponds to the length defined by the respective number of Bchla units. I mean. Since the sequences of the strongly coupled chromophores of B820, LH-1 and LH-2 have 2, 16 and 32 pigments, respectively, the degree of excited state delocalization is significant in these LHCs, These experiments suggest that it is not an overall feature.

Clearly, the EDS determined for ethyne- and butadiyne-bridged (porphinate) zinc (II) sequence compounds with the characteristics of meso-to-meso or meso-to-β linkages are individually observed in these conjugated chromophore systems. Must be derived from factors that complement the collective in-phase oscillations of the pigment dipoles. These EDS can be reasonably explained considering the photophysical properties of the established triplet states of these species. In contrast to the singlet excited states of compounds 6 , 8 , 9 , 11 and 12 which show that the electron density is substantially delocalized,
According to studies by photoexcited EPR spectroscopy, it is concluded that the electron density distributions of the T ₁ -excited states in compounds 4 to 12 of the present invention are all highly localized. Importantly, these experiments show that the spatial spread of the T ₁ -excited state wave functions of these species is in each case a single (porphinate) zinc (II) unit and then laterally. This indicates that the size defined by the cylindrical π-symmetry substituent (ethyne or butadiyne) extending to the upper limit is not exceeded. The cause of localization of the wave function of T ₁ in compounds 4 to 12 can be derived from large lattice relaxation. Lattice relaxation is known in the oligo phenyleneethynylene reduce the spatial extent of the triplet electronic state compared to S _n state of being excited. Alternatively, the above causes may be due to the fundamental electronic state difference between the multifold created by singlet and triplet excited states that can be explained in connection with the approximation of point dipoles in a general exciton model. You can also lead from.

Since the exciton resonance is proportional to the square of the transition moment, the absorber (compounds 4 to 12 ) having a large oscillator strength has an unusually large Frank-Condon barrier with respect to the intersystem crossing between S _{1 and} T _1. Often has. Furthermore, as the delocalization of electrons in the S ₁ excited state in this series increases (λ _em increases), these Frank-Condon barriers would be expected to increase gradually as in FIG. 3B. This is because, regardless of the size of the pigment array, a similar highly localized T ₁ state appears for a given topological arrangement of porphyrin to porphyrin linkages. Because. τ _F = (k _r + k _nr ) ⁻¹ , and the magnitude of the non-radiative decay rate constant k _nr corresponds to the sum of all dynamic processes that cause the S ₁ excited state to disappear without light emission ( _{k nr = k IC + k ISC} , wherein an inter-system crossing rate constant between _{k ISC = S 1 -T 1,} k IC is overall speed for non-radiative internal conversion processes between _S 1 -S ₀ (Representing a constant), as k _ISC → 0, the fluorescence lifetime increases correspondingly (FIG. 3). As explained above, the energy gap law predicts that the value of k _IC increases for a given type of chromophore as the energy interval between S _{0 and} S ₁ decreases. In photophysical properties of S ₁ with respect to this compound 4-12 undoubtedly is plays a role to emission energy within at least a range of these species, an increase in the size of the k _IC is _Which is clearly greater than offset by a corresponding decrease in k _ISC with increasing λ _em . This effect, the magnitude of the fluorescence lifetime over the entire Compound 1-12 relatively remains constant value, key determinant for QY large fluorescent abnormally observed for red emitting chromophore in this series It is a factor. Thus, in addition to the strongly coupled pigment transition dipoles oscillating in phase, the delocalization of the S ₁ electronic state for these species increases while the k _ISC decreases. It plays a key role in establishing the extreme superradiance behavior as highlighted in FIG.

  Excited state deactivation pathways governing the photophysical properties of monomeric pigments do not necessarily control the excited state dynamics of the corresponding strongly coupled chromophore assembly. This study shows. Thus, the supramolecular multicolor pigment system of the present invention, which exists as a clear photophysical entity, can be constructed from simple chromophore building blocks. These ethyne- and butadiyne-crosslinked (porphinate) zinc (II) aggregates are essential properties of biological light-harvesting protein pigment aggregates, ie, substantial pigment-pigment coupling, excited state This shows the high polarization of and the photophysical properties of the coupled oscillator. When such conjugated aggregates are made to have a single degenerate excited state, the vibration modes at high and low frequencies of the chromophore and solvent are These singlet state polarized dipole-dipole correlated properties are preserved over a long time scale in ns, with little impact on the shift.

Analysis of fluorescence intrinsic decay rate and quantum yield data show that, in the present invention, ethyne- and butadiyne-bridged multiporphyrin species exhibiting a high degree of anisotropy in the excited state exhibit extreme superradiance enhancement factors. It is. Such photophysical properties are derived from the fact that these conjugated pigment array compounds behave as collective oscillators and exhibit large Franck-Condon barriers for intersystem crossing between their respective S ₁ and T ₁ states. These results are a significant limitation in creating isolated pigments that can actually achieve substantial emission dipole intensities for low energy fluorescent materials and exhibit high quantum yields and low energy fluorescence. The classical energy gap law also shows that it does not hinder the design of supramolecular systems exhibiting such photophysical properties.

  Finally, this study shows that monomer units with large absorption oscillator strengths can be combined into monomer-units that exhibit strong coupling, dipole-dipole alignment, and large values of excited state anisotropy. In combination with the merging mode, it suggests that a general strategy for producing electro-optic materials exhibiting extreme superradiance can be established. Low energy optical bandgap, singlet excited state with high anisotropy, and extreme superradiance can be designed in parallel, so the design concept expressed here is optical communication materials And the construction of pigments, the generation of singlets and triplets with many different cross sections from injected charge carriers, and applications in devices where large optical gains are considered important.

  Still other objects, advantages and novel features of the present invention will become apparent to those skilled in the art upon review of the following examples. These examples do not limit the invention. Still other synthetic methods for the compounds of the present invention are described in the following references. (1) Highly conjugated acetylenyl-bridged porphyrins: a new model for light-harvesting antenna systems: S. -Y. Lin, S .; G. DiMagno, and M.M. J. et al. Therien, Science (Washington, D.C.) 1994, 264, 1105-1111; (2) Extensive changes in the absorption and emission properties of the ethynyl- and butadiynyl-bridged bis- and tris (porphinate) zinc chromophore series Of the topology of porphyrin-porphyrin linkages in V. S. -Y. Lin and M.M. J. et al. Therien, Chem. Eur. J. et al. 1995, 1,645-651; (3) Singlet and triplet excited states of luminescent conjugated bis (porphyrin) compounds verified by optical and EPR spectroscopic methods: Shediac, M .; H. B. Gray, H.C. T. T. et al. Uyeda, R .; C. Johnson, J.M. T. T. et al. Happ, P.M. J. et al. Angiolo, and M.M. J. et al. Therien, J .; Am. Chem. Soc. 2000, 122, 7017-7033.

5,15-Diphenylporphyrin A 1000 ml flask equipped with a magnetic stirrer bar was dried in a bowl, to which 2,2-dipyrylmethane (458 mg, 3.1 mmol), benzaldehyde (315 μL, 3.1 mmol) and 600 mL Of freshly distilled (added CaH ₂ ) was charged with methylene chloride. The solution was degassed with a stream of dry nitrogen for 10 minutes. Trifluoroacetic acid (150 μL, 1.95 mmol) was added via syringe, the flask was shielded from light with aluminum foil, and the solution was stirred at room temperature for 2 hours. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 900 mg, 3.96 mmol) was added to quench the reaction, and the reaction mixture was stirred for an additional 30 minutes. Neutralize the reaction mixture with 3 mL of triethylamine and inject it directly onto a column of silica gel (20 × 2 cm) packed in hexane. This product is eluted in 700 mL of solvent. Evaporation of the solvent left purple crystals (518 mg, 1.12 mmol, 72.2%). This product is sufficiently pure for the next reaction. Visible (CHCl ₃ : 421 (5.55), 489 (3.63), 521 (4.20), 556 (4.04), 601 (3.71), 658 (3.73).

5,15-Dibromo-10,20-diphenylporphyrin 5,15-Diphenylporphyrin (518 mg, 1.12 mmol) was dissolved in 250 ml chloroform and cooled to 0 ° C. Pyridine (0.5 mL) is added to act as an acid scavenger. N-bromosuccinimide (400 mg, 2.2 mmol) was added directly to the flask, then TCL was performed on the mixture (50% CH ₂ Cl ₂ , eluent hexane). After 10 minutes, the reaction was complete and quenched with 20 mL of acetone. The solvent was evaporated and the product was washed several times with methanol and vacuumed to dryness to give 587 mg of a reddish purple solid (0.94 mmol, 85%). This compound was sufficiently pure to be used in the next reaction. Visible (CHCl ₃ : 421 (5.55), 489 (3.63), 521 (4.20), 556 (4.04), 601 (3.71), 658 (3.73).

5,15-dibromo-10,20-diphenyl porphyrinato zinc 5,15-diphenyl porphyrin (587 mg, 0.94 mmol) was suspended in DMF and 30mL containing ZnCl ₂ in 500 mg. The mixture was heated to reflux for 2 hours and poured into distilled water. The precipitated purple solid was filtered through a fine fritted disc, washed with water, methanol, and acetone and dried in vacuo to give 610 mg (0.89 mmol, 95%) of a red purple solid. . This compound was recrystallized from THF / heptane to give large purple crystals of the title compound (564 mg, 0.82 mmol, 88%). Visible (THF): 428 (5.50), 526 (3.53), 541 (3.66), 564 (4.17), 606 (3.95).

Meso-substituted porphyrin General method In each of the following examples, 5,15-dibromo-10,20-diphenylporphyrinato zinc (0.1 mmol) and Pd (PPh ₃ ) ₄ (0.0025 mmol) were sealed. Dissolved in 35 mL of distilled and degassed THF with 1 mmol of organometallic reagent described below in a storage tube and heated to 60 ° C. for 48 hours. The reaction was monitored by TCL on the removed sample. The reaction of the mixture was quenched with water, extracted with chloroform, dried over CaCl _2, evaporated and purified by column chromatography.

A. 5,15-Diphenyl-10,20-dimethylporphyrinatozinc The organometallic reagent was methylzinc chloride made from a solution containing methyllithium and anhydrous zinc chloride in THF.

The crude product is dissolved in THF / heptane, poured onto 10 g of silica gel and evaporated to dryness. The silica gel was loaded onto a column packed in 50% CH ₂ Cl ₂ / hexane. Elution with a single band (50% CH ₂ Cl ₂ / hexane) gave pure 5,15-diphenyl-10,20-dimethylporphyrinato zinc (48 mg, 88%). An analytical sample was recrystallized from THF / acetone with slow evaporated under N _2. ¹ H NMR (500 MHz, 3: 1 CDCl ₃ , D ₈ -THF) Epsilon 9.34 (d, 4H, J = 4.6); 8.71 (d, 4H, J = 4.6); 8.02 (dd, 4H, J1 = 7.5 , J2 = 1.4); 7.57 (m, 6H); 4.51 (s, 6H). ¹³ C NMR (125 MHz, 3: 1 CDCl ₃ , Da-THF) Epsilon 150.07 (0), 148.88 (0), 143.34 (0), 134.18 (1), 131.42 (1), 128.09 (1), 126.73 ( 1), 125.88 (1), 119.29 (0), 113.74 (0), 20.81 (3). Visible (THF)
424 (5.58), 522 (3.40), 559 (4.12); 605 (3.88).

B. 5,15-Diphenyl-10,20-divinylporphyrinatozinc The organometallic reagent was tri-n-butyltin.

  The crude was absorbed onto silica and loaded onto a column packed in hexane.

Elution was performed using a _{CH 2 Cl 2 (0~50%)} / hexanes. The main fraction was obtained from a small amount of purple material. The main elution zone was evaporated to give pure 5,15-diphenyl-10,20-divinylporphyrinato zinc (53 mg, 91%). Samples for analysis were recrystallized from chloroform. ¹ H NMR (500 MHz, CDCl ₃ epsilon 9.52 (d, 4H, J = 4.7); 9.24 (dd, 2H, J1 = 17.3, J2 = 9.1); 8.92 (d, 4H, J = 4.7); 8.19 (dd , 4H, J1 = 6.8, J2 = 2.0); 7.75 (m, 6H); 6.48 (dd, 2H, J1 = 11.0, J2 = 1.9);. 6.05 (dd, 2H, J1 = 17.3, J2 = 2.0) 13 C NMR (125 MHz, CDCl ₃ epsilon 163.40 (1), 149.90 (0), 149.21 (0), 142.83 (0), 137.97 (0), 134.40 (1), 132.10 (1), 130.39 (1), 127.50 (1), 126.73 (2)
126.57 (1), 121.05 (0).

C. 5,15-bis (2,5-dimethoxyphenyl) -10,20-diphenylporphyrinatozinc The organometallic reagent was made from 1,4-dimethoxybenzene and t-butyllithium in ether at −78 ° C. 2 , 5-dimethoxyphenyllithium. This organolithium reagent was added to a solution of ZnCl _{2 in} THF to obtain an organozinc chloride reagent. This reagent was used immediately.

At the completion of the reaction, two spots with high fluorescence intensity were visible by TLC. The crude product was chromatographed on silica using CHCl ₃ as the eluent. First elution band leaving the column was found to be 5,15-bis (2,5-dimethoxyphenyl) _{10,20-C 2h} isomer of diphenyl porphyrinato zinc. The elution zone was evaporated to leave 33 mg (42%) of pure product. Samples for analysis were recrystallized from chloroform. ¹ H NMR (500 MHz, CDCl ₃ epsilon 8.91 (s, 8H); 8.22 (d, 4H, J = 6.5); 7.75 (m, 6H); 7.59 (d, 2H, J = 2.2); 7.26 (broad s 3.86 (s, H); 3.54 (s, 6H) ¹³ C NMR (125 MHz, CDCl ₃ epsilon 154.10 (0), 152.30 (0), 150.13 (0), 143.00 (0), 134.10 ( 1), 132.62 (0), 132.00 (1), 131.44 (1), 127.35 (1), 126.44 (1), 121.34 (1), 120.69 (0), 110.59 (0), 114.76 (1), 112.31 ( 1), 56.70 (3), 55.95 (3), Visible -424 (5.64), 551 (4.34), 584 (3.43).

The C _2v isomer is eluted from the column after the C _2h isomer. Evaporation of the solvent left 30 mg (32%) of pure 5,15-bis (2,5-dimethoxyphenyl) -10,20-diphenylporphyrinato zinc. This compound dissolves in chloroform much more easily than the C _2h isomer. Stereochemical assignments were made from NMR data. ¹ H NMR (500
MHz, CDCl ₃ Epsilon 8.90 (s, 8H); 8.21 (d, 2H, J = 7.9); 8.19 (d, 2H, J = 6.5)
; 7.

D. 5,15-bis [(4-methyl) -4′-methyl-2,2′-dipyridyl)]-10,20-diphenylporphyrinato zinc The organometallic reagent is 4,4′-dimethyl-2,2 Tri-n-butyl [(4-methyl) -4'-methyl formed by lithiation of 1-dipyridyl with 1 equivalent of lithium diisopropylamide in THF at -78 ° C and warming the reaction mixture to room temperature -2,2'-dipyridyl)] tin. The organolithium reagent was treated with 1.1 equivalents of tributyltin chloride. The resulting organotin compound was used without further purification.

The crude reaction mixture was chromatographed on silica using a mixture of CH ₂ Cl ₂ , isopropanol and triethylamine. Porphyrin was obtained in one elution zone. The product obtained in this way (68% yield) was contaminated with a small amount (0.2 equivalents per equivalent of porphyrin) of triphenylphosphine. ¹ H NMR (500 MHz, CDCl 3) Epsilon 9.37 (d, 4H, J = 4.7); 8.87 (d, 4H, J = 4.7); 8.52 (s, 2H); 8.29 (d, 2H, J = 5.1); 8.20 (d, 2H, J = 5.2); 8.10 (m, 6H); 7.71 (m, 6H); 7.01 (d, 2H, J = 5.0); 6.88 (d, 2H, J = 4.2); 6.46 (s , 4H); 2.32 (s, 6H).

E. 5,15-bis (trimethylsilylethynyl) -10,20-diphenylporphyrinatozinc The organometallic reagent was trimethylsilylethynylzinc chloride made from trimethylsilylethynyllithium and anhydrous zinc chloride in THF.

After 48 hours, the reaction mixture became light green. This solid crude was absorbed onto silica gel, loaded onto a column packed in hexane and chromatographed using 20-30% CH ₂ Cl ₂ / hexane. This method resulted in a clean separation of the product from a small amount of deprotected product. The solvent was evaporated and the purple solid was washed twice with hexane and dried in vacuo. ¹ H NMR (500 MHz, CDCl ₃ epsilon 9.68 (d, 4H, J = 4.6); 8.89 (d, 4H, J = 4.6); 8.15 (dd, H, J1 = 7.9, J2 = 1.7); 7.75 (m 0.58 (s, 18H) ¹³ C NMR (125 MHz, CDCl ₃ epsilon 152.22, 150.26
, 142.10, 134.39, 132.77, 131.29, 27.69, 126.67, 115.08, 107.34, 102.00, 0.32.

Pyrrole Substituted Porphyrin General Methods 2-Bromo-5,10,15,20-tetraphenylporphyrinato zinc (0.1 mmol) and palladium dichloride 1,1′-bis (diphenylphosphino) ferrocene (Pd ( dppf) Cl ₂ , 7 mg) was combined with 1.0 mmol of the following organometallic reagent in 35 mL of dry, degassed THF. This solution was allowed to stand for 12 hours, the solvent was evaporated, and the compound was purified by flash chromatography.

A. 2-vinyl-5,10,15,20-tetraphenylporphyrinatozinc The organometallic reagent was tributylvinyltin.

The crude reaction mixture was chromatographed on silica, eluting with 50% CH ₂ Cl ₂ / hexane. ¹ H NMR (250 MHz, CDCl ₃ epsilon 8.97 (s, 1H); 8.90 (m, 4H); 8.87 (d, 1H, J = 4.7); 8.79 (d, 1H, J = 4.7); 8.20 (m, 6H); 8.06 (d, 2H, J = 6.6); 7.74 (m, 12H); 6.39 (dd, 1H, J1 = 17.0, J2 = 9.1); 5.83 (dd, 1H, J1 = 17.1, J2 = 2.0) 5.01 (dd, 1H, J1 = 10.7, J2 = 2.0) Visible (CHCl ₃ ) 426 (5.53), 517 (3.68); 555 (4.22), 595 (3.68).

B. 2- (2,5-dimethoxyphenyl) -5,10,15,20-tetraphenylporphyrinatozinc The organometallic reagent is 2,2-dichlorinated chloride made from the corresponding lithium reagent and anhydrous zinc chloride in THF / diethyl ether. It was 5-dimethoxyphenylzinc.

The crude reaction mixture was flash chromatographed using chloroform. The title compound was isolated in 78% yield. ¹ H NMR (500 MHz, CDCl ₃ epsilon = 8.94 (d, 1H
, J = 4.7); 8.93 (s, 2H); 8.92 (d, 1H, J = 4.8); 8.85 (s, 1H); 8.84 (d, 1H, J = 4.7); 8.70 (d, 1H, J = 4.7); 8.23 (m, 6H); 7.98 (d, 1H, J = 7.0); 7.70 (m, 10H); 7.25 (quintet, 2H, J = 7.4); 7.15 (t, 1H, J = 7.0); 6.92 (d, 2H, J = 3.1); 6.54 (dd, 1H, J1 = 9.0, J2 = 3.2); 6.40 (d, 1H, J = 9.1); 3.68 (s, 3H); 3.42 (s, 3H) . ¹³ C NMR
(125 MHz, CDCl ₃ epsilon = 152.59 (0), 151.33 (0), 150.46 (0), 150.31 (0), 150.27 (0), 150.15 (0), 150.12 (0), 150.03 (0), 148.30 ( 0), 147.16 (0), 143.32 (0), 142.97 (0)
, 142.86, 140.71 (0), 135.63 (1), 135.20 (1), 134.45 (1), 134.13 (1), 132.52 (1), 132.02 (1), 131.91 (1), 131.82 (1), 131.32 ( 1), 129.27 (0), 127.44 (1), 127.38 (1), 127.18 (1), 126.53 (1), 126.50 (1), 124.91 (1), 121.70 (1), 122.36 (0), 121.30 ( 0), 120.91 (0)
, 120.54 (0), 113.15 (1), 113.03 (1), 110.35 (1), 55.98 (3), 54.87 (3). Visible (CHCl3) 421.40 (5.60), 513.2 (3.45), 549.75 (4.28), 587.15 (3.45).

C. 2- (Trimethylsilethynyl) -5,10,15,20-tetraphenylporphyrinatozinc The organometallic reagent trimethylsilethynylzinc chloride was made from the corresponding lithium reagent and anhydrous zinc chloride in THF.

The crude reaction mixture was chromatographed on silica, eluting with 50% CH ₂ Cl ₂ / hexane. ¹ H NMR (250 MHz, CDCl ₃ epsilon 9.25 (s, 1H); 8.89 (m, 4H); 8.85 (d, 1H, J = 4.9); 8.76 (d, 1H, J = 4.9); 8.16 (m, 8.09 (d, 2H, J = 7.1); 7.67 (m, 12H); 0.21 (s, 9H) Visible (CHCl3) 431 (5.43), 523 (shoulder); (4.18), 598 (3.67) .

D. 2-n-butyl-5,10,15,20-tetraphenylporphyrinato zinc butyl zinc chloride was made from n-butyl lithium and anhydrous zinc chloride in THF.

The crude reaction mixture was chromatographed on silica, eluting with 50% CH ₂ Cl ₂ / hexane. ¹ H NMR (250 MHz, CDCl ₃ epsilon 8.97 (m, 4H); 8.91 (d, 1H, J = 4.7); 8.77 (d, 1H, J = 4.7); 8.74 (s, 1H); 8.22 (m, 8.13 (d, 2H, J = 7.3); 7.77 (m, 12H); 2.81 (t, 2H, J = 7.7); 1.83 (quint, 2H, J = 7.8); 1.30 (quint, 2H, J = 7.6); 0.91 (t, 3H, J = 8.2).

Vinyl-crosslinked porphyrins and their polymers cis-bis-1,2- [5- (10,15,20-triphenylporphyrinato) zinc] ethene 5-bromo- (10,15,20-triphenylporphyrinato) zinc (0.2 mmol) ) And Pd (PPh ₃ ) ₄ (0.02 mmol) are dissolved in 25 mL of dry, degassed THF. A solution of cis-bis (tri-n-butyltin) ethene (0.2 mmol) in 5 mL of THF is added and the solution is heated to reflux for 2 days. The reaction is stopped by adding water, extracted with methylene chloride, dried over calcium chloride and the solvent is evaporated. The crude solid was chromatographed on silica using an eluent of methylene chloride / hexane to separate the dimer in formula (3) where R _A1 , R _A3 and R _A4 are phenyl and M is Zn.

B. cis-Bis-1,2- [5- [10,15,20-tris (pentafluorophenyl)]-2,3,7,8,12,13,17,18-octakis- (trifluoromethyl) porphy Linate zinc] -1,2-difluoroethene 5-bromo-10,15,20-tris (pentafluorophenyl) porphyrinato zinc (0.2 mmol) and Pd (PPh ₃ ) ₄ (0.02 mmol) ) Is dissolved in 25 mL dry THF. A solution of cis-bis- (tri-n-butyltin) -1,2-difluoroethene (0.2 mmol) in 5 mL of THF is added and the solution is heated to reflux for 2 days. The reaction is stopped by adding water, extracted with methylene chloride, dried over calcium chloride and the solvent is evaporated. The crude solid was chromatographed on silica using methylene chloride / hexane eluent and cis-bis-1,2- [5- [10,15,20-tris (pentafluorophenyl) porphyrinato zinc]. -1,2-Difluoroethene was isolated.

This material was dissolved in chloroform and reacted with a large excess of N-bromosuccinimide as in Example 2 to perbrogate the positions of R _{B1 to} R _B8 on both porphyrins. The resulting material is filtered through a fine fritted disc, washed with water, methanol, and acetone, dried in vacuo, and then recrystallized from THF / heptane. In the dark as in Example 4, cis-bis-1,2- [5- [10,15,20-tris (pentafluorophenyl)]-2,3,7,8,12,13,17, 18-octabromoporphyrinato zinc] is reacted with Pd (dppf) and a large excess of CuCF ₃ . After a reaction period of about 48 hours, the product was chromatographed on silica using CH ₂ Cl ₂ / CCl ₄ eluent to give the title compound.

C. Cofacial-bis- [cis-ethenyl-meso-bridged] porphyrin [CEBP] (formula (5)) and polymerized-bis- [cis-ethenyl-meso-bridged] porphyrin [PABP] (formula (6))
5,15-Dibromo-10,20-diphenylporphyrinato zinc (0.2 mmol) and Pd (PPh ₃ ) ₄ (0.02 mmol) are dissolved in 25 mL of dry and degassed THF. A solution containing cis-bis- (tri-n-butyltin) ethene (0.2 mmol) in 5 mL of THF is added and the solution is heated to reflux for 2 days. The reaction is stopped by adding water, extracted with methylene chloride, dried over calcium chloride and the solvent is evaporated. The crude solid is chromatographed on silica using methylene chloride / hexane eluent to produce a cofacial-bis- [cis-ethenyl-meso-bridged] zinc porphyrin complex of formula (5) and polymerization of formula (6). A bis- [cis-ethenyl-meso bridged] porphyrin species was isolated. In these formulas, R _A1 and R _A3 are phenyl and M is Zn.

D. Fluorinated cofacial-bis- [cis-ethenyl-meso-bridged] porphyrin [FCEBP] and fluorinated polymerized-bis- [cis-ethenyl-meso-bridged] porphyrin [FPEBP]
5,15-Dibromo-10,20-bis- (pentafluorophenyl) porphyrinato zinc (0.2 mmol) and Pd (PPh ₃ ) ₄ (0.02 mmol) are dissolved in 25 mL of dry THF. A solution containing cis-bis- (tri-n-butyltin) -1,2-difluoroethene (0.02 mmol) in 5 mL of THF is added and the solution is heated to reflux for 2 days. The reaction is stopped by adding water, extracted with methylene chloride, dried over calcium chloride and the solvent is evaporated. The crude solid was chromatographed on silica using methylene chloride / hexane eluent, cofacial-bis- [cis-ethenyl-meso bridged] zinc porphyrin complex and polymerized bis- [cis-ethenyl-meso bridged]. Porphyrin species were isolated. Cofacial species and polymer species are dissolved separately in chloroform. The cofacial-porphyrin complex dissolved in chloroform is reacted with a large excess of N-bromosuccinimide as in Example 2 and perbromination is performed at positions R _{B1 to} R _B8 on both porphyrins. The resulting material was filtered through a fine fritted disc, washed with water, methanol and acetone, dried in vacuo and then recrystallized from THF / heptane to give the title compound. The separated material is reacted with Pd (dppf) and a large excess of CuCF ₃ in the dark as in Example 4. After a reaction time of about 48 hours, the product was chromatographed on silica using CH ₂ Cl ₂ / CCl ₄ eluent to give a perfluorinated CEPB of the homologous series of formula (5). Perfluorinated PEBP was synthesized in a similar manner to obtain a homologous series of chemical species of formula (6) in which highly fluorinated porphyrins are linked via fluorovinyl units.

E. Cofacial-bis- [1,8-anthracenyl-meso-bridged] porphyrin [CBAP] (formula (7)) and polymerized-bis- [1,8-anthracenyl-meso-bridged] porphyrin [PBAP] (formula (8))
5,15-Dibromoporphyrinato zinc (0.2 mmol) and Pd (PPh ₃ ) ₄ (0.02 mmol) are dissolved in 25 mL of dry and degassed THF. A solution containing 1,8-anthracenyl-bis- (tributyltin) (0.2 mmol) in 5 mL of THF is added and the solution is heated to reflux for 2 days. The reaction is stopped by adding water, extracted with methylene chloride, dried over calcium chloride and the solvent is evaporated. The crude solid was chromatographed on silica using methylene chloride / hexane eluent to obtain a cofacial-bis- [1,8-anthracenyl-meso-bridged] zinc porphyrin complex of formula (7) and of formula (8). Polymerized-bis- [1,8-anthracenyl-meso-bridged] zinc porphyrin species was isolated. In the above formula, R _A1 and R _A3 are phenyl, and M is Zn.

Acetylene-type porphyrin polymer Poly (5,15-bis (ethynyl) -10,20-diphenylporphyrinato zinc)
See generally Advances in Organic Chemistry, Raphael, et al. , Eds. , 1963, Interscience Publishers, Eglington, et al. The Coupling of Acetyletic Compounds, p. In a solution of cupric acetate (0.4 mmol) in 20 mL of a pyridine / methanol 1: 1 mixture according to the method described in 311, 5,15-bis (ethynyl) contained in pyridine (20 mL). -10,20-diphenylporphyrinato zinc (0.2 mmol) is added slowly.

B. Poly (5,15-bis (ethynylphenyl) -10,20-diphenylporphyrinato zinc)
5,15-diethynyl-10,20-diphenylporphyrinato zinc (0.2 mmol) and 1,4-dibromobenzene are combined in a mixture of 30 mL toluene and 10 mL diisopropylamine. CuI (0.4 mmol) and Pd (Ph ₃ ) ₄ (0.02 mmol) are added and the mixture is heated to 65 ° C. for 3 days. The crude solid is washed with methanol and acetone and dried in vacuo.

  Alternatively, the polymer is made from 1,4-diethynylbenzene and 5,15-dibromo-10,20-diphenylporphinate zinc in a similar manner.

Doped Porphyrin Polymer Skothim, ed. , Handbook of Conducting Polymers, Volume 1, pp. 405-437, Marcel Dekker, 1986, using catalytic amounts of MoCl ₅ , Me (CO) ₆ , WC 1 ₆ or W (CO) ₅ , 5,15-bis (ethynyl) Polymerize -10,20-diphenylporphyrinato zinc. The polymer was oxidizing agent, for example, doped with iodine or SbF _5.

Metallation of brominated porphyrins Sodium naphthalide contained in THF and generally according to Rieke's method (J. Org. Chem. 1984, 49, 5280 and J. Org. Chem. 1988, 53, 4482) and A fine powder of zinc metal was made from zinc chloride (0.18 mmol each). A solution of [5-bromo-10,20-diphenylporphinate] zinc (100 mg, 0.17 mmol) dissolved in 40 mL of THF was added to the zinc metal suspension by syringe and the mixture was stirred overnight at room temperature. did. During this time, all zinc metal was dissolved. Porphyrins with metallized rings are suitable for coupling with a wide variety of aryl and vinyl halides using palladium as a catalyst.

Cross-coupling with ring metallized porphyrin using palladium as a catalyst 5-[(10,20-diphenylporphinate) zinc] zinc (0. 2 mmol) and place in a dry 100 mL Schlenk tube. A solution containing 2-iodothiophene (0.4 mmol) in 5 mL of THF was added via syringe. Pd (dppf) (3 mg) is made by stirring a suspension of Pd (dppf) Cl ₂ in THF over Mg cuttings for 20 minutes and transferring it into the reaction mixture using a cannula. . The solution is stirred overnight, quenched with an aqueous solution of ammonium chloride, extracted with CH ₂ Cl ₂ and dried over CaCl ₂ . The solvent was evaporated to dryness and chromatographed using 1: 1 CH ₂ Cl ₂ as the eluent. The product [5- (2-thiophenyl) -10,20-diphenylporphinate] zinc elutes as one elution zone and is separated in 90% yield.

Polymerization with ring metallized porphyrin derivative [5,15-bis (zinc bromide) -10,20-diphenylporphinate)]-zinc (0. 2 mmol) and place in a dry 100 mL Schlenk tube. A solution containing [5,15-dibromo-10,20-diphenylporphinate)]-zinc (0.2 mmol) in 15 mL of THF is added by syringe. Pd (dppf) (3 mg) is made by stirring a suspension of Pd (dppf) Cl ₂ in THF over Mg cuttings for 20 minutes and transferring it into the reaction mixture using a cannula. . The mixture is heated to 60 ° C. for 3 days, cooled to room temperature, and filtered through a fine fritted glass disc. The filtered polymer is washed with hexane, then with methanol and dried in vacuum.

Carbonylation of [5-bromo-10,20-diphenylporphinate] -zinc 5-[(10,20-diphenylporphinate) zinc] -magnesium (0 .2 mmol) and place in a dry 100 mL Schlenk tube. The vessel is cooled to 0 ° C. and dry CO ₂ gas is passed through the solution. The solution is stirred at room temperature for 1 hour, quenched with 0.1 M HCl, extracted with CH ₂ Cl ₂ and dried over CaCl ₂ . The solvent is evaporated to dryness and chromatographed using THF: CH ₂ Cl ₂ as the eluent. The solvent was evaporated to separate [5-carboxy-10,20-diphenylporphinate] zinc in 85% yield.

Coupling with non-metallized porphyrin derivatives Use of Organozinc Chloride Reagent Trimethylsilylacetylene (3 mmol) is deprotonated with n-butyllithium (3 mmol) in THF at −78 ° C. and gradually warmed to room temperature. Excess ZnCl ₂ (650 mg) in 5 mL of THF is transferred into the solution by cannula. A suspension of Pd (dppf) Cl ₂ in THF is stirred over a Mg cut piece for 20 minutes to produce Pd (dppf) (3 mg) and transferred into this solution via a cannula. The entire reaction mixture is transferred to a dry 100 mL Schlenk tube containing 340 mg of 5,15-dibromo-10,20-diphenylporphyrin. The solution is heated to 40 ° C. and sealed overnight. After 18 hours, TLC of the reaction mixture showed a mixture of fluorescent substances. The mixture is quenched with aqueous ammonium chloride solution, extracted with CH ₂ Cl ₂ and dried over CaCl ₂ . The solvent was evaporated to dryness and chromatographed using 1: 1 CH ₂ Cl ₂ : hexane as eluent. Most of the material collects in two elution zones, [5- (2-trimethylsilylethynyl) -10,20-diphenylporphinate] zinc and [5,15-bis (2-trimethylsilylethynyl) -10,20-diphenyl. Porfinate] was found to be zinc. The two products were separated with an overall yield of 83%.

B. Use of organotrialkyltin reagent 5,15-Dibromo-10,20-diphenylporphyrin is placed in a dry 100 mL Schlenk tube and dissolved in 30 mL of THF. A solution of vinyltributyltin (3 mmol) in 5 mL of THF was added to the reaction mixture. A suspension of Pd (dppf) Cl ₂ in THF is stirred for 20 minutes on a Mg cut piece to make Pd (dppf) (3 mg), and the reaction mixture is transferred into the reaction mixture by cannula. . The solution is stirred overnight, quenched with aqueous ammonium chloride solution, extracted with CH ₂ Cl ₂ and dried over CaCl ₂ . The solvent was evaporated to dryness and chromatographed using 1: 1 CH ₂ Cl ₂ : hexane as eluent. The product 5,15-diphenyl-10,20-divinylporphyrin elutes in one elution zone and is separated in 90% yield.

Coupling with dilithiated porphyrin derivatives Arnold, J. et al. Chem. Soc. Commun. Make a solution containing N, N ″ -dithio-5,15-dibromo-10,20-diphenylporphyrin (0.2 mmol) in 15 mL of THF according to the general procedure described in 1990,976. A solution of vinyltributyltin (2 mmol) in THF is added to the reaction mixture A suspension of Pd (dppf) Cl ₂ in THF is stirred over a Mg cutting piece for 20 minutes to give Pd (dppf ) (3 mg) and transfer the reaction mixture by cannula into the reaction mixture, stir overnight, quench with anhydrous NiCl ₂ in THF, extract with CH ₂ Cl ₂ , . dried over CaCl ₂ and the solvent is evaporated to dryness, 1 as eluent: 1 _CH 2 Cl _2:. chromatographed with hexane of the product [5,15 Diphenyl-10,20-divinylporphinate] -nickel elutes in one elution zone and is separated in 90% yield.

Bis [5,5 ′,-10,20-diphenylporphinato) zinc (II)] ethyne Lithium bistrimethylsilylamide (1 mmol) is added in 20 mL of THF (5-ethynyl-10,20-diphenylporphinate). A (5-ethynyllithium-10,20-diphenylporphinate) zinc (II) reagent is made in addition to a solution containing zinc (II) (50 mg, 0.1 mmol). (5-Bromo-10,20-diphenylporphinate) zinc (II) (60 mg, 0.1 mmol) and 10 mg of Pd (PPh ₃ ) ₄ in 20 mL of THF were added to this solution by trocar. . After completion of this metal-mediated cross-coupling reaction, it was chromatographed on silica using 9: 1 hexane: THF as eluent. The first green elution band was separated and evaporated to give 77.2 mg of product (yield = 72% with respect to (5-ethynyl-10,20-diphenylporphinate) zinc (II)). 1H NMR (250 MHz, CDCl3): □ 10.43 (d, 4H, J = 4.6 Hz), 10.03 (s, 2H), 9.21 (d, 4H, J = 4.4 Hz), 9.06 (d, 4H, J = 4.5 Hz), 8.91 (d, 4H, J = 4.4Hz), 8.22 (m, 8H), 7.72 (m, 12H). Visible (CHCl3) 413.9 (4.96), 420.5 (4.97), 426.0 (4.96), 432.6 (4.92), 445.8 (4.89), 477.7 (5.1), 549.2 (4.15), 552.5 (4.14), 557.8 (4.15), 625.1 (4.09), 683.4 (4.37). FAB MS: 1070 (calculated value 1070).

5,15-bis [5′-10,20-diphenylporphinate) zinc (II)] ethynyl]-[10,20-diphenylporphinate) zinc (II)
A solution of (5-bromo-10,20-diphenylporphinate) zinc (II) (120 mg, 0.2 mmol) in 20 mL of THF was added to Pd (PPh ₃ ) ₄ (20 mg, 0.0173 mmol) and CuI. (10 mg) was added. (5,15-diethynyl-10,20-diphenylporphinate) zinc (II) (57 mg, 0.1 mmol) and 0.35 mL of diethylamine in 20 mL of THF were added to the solution by cannula. After completion of this metal-mediated cross-coupling reaction, the precipitated product was filtered off and then recrystallized from a pyridine-hexane mixture to give 66.5 mg of product. (Yield = 41% with respect to raw material (5,15-diethynyl-10,20-diphenylporphinate) zinc (II)) 1H NMR (500 MHz, CDCl3): □ 10.86 (d, 4H, J = 4.5 Hz) , 10.78 (d, 4H, J = 4.4Hz), 10.39 (s, 2H), 9.50 (d, 4H, J = 4.3Hz), 9.42 (d, 4H, J = 4.4Hz), 9.32 (d, 4H, J = 4.8Hz), 9.15 (d, 4H, J = 4.0Hz), 8.52 (m, 4H), 8.47 (m, 8H), 7.89 (m, 6H), 7.85 (m, 12H). Visible (10: 1 CHCl3: pyridine): 420.5 (4.84), 437.0 (4.72), 457.2 (4.66), 464.5 (4.66), 490.9 (4.85), 500.8 (4.95), 552.0 (3.99), 802.2 (4.63). FAB MS: 1616 (calculated value 1616).

The method described below includes a partial structure bonded with at least two covalent bonds, and the composite conjugated compound emits light in the wavelength region of 650 to 2000 nm and is more than any of the partial structures bonded with a covalent bond (or This is a method for producing a conjugated compound having a light emission dipole intensity (greater than the sum of light emission dipole intensities of the respective partial structures bonded by two covalent bonds).

  Known fluorophores, luminophores, or phosphorophores that emit light at a wavelength of 450 nm or longer when optically or electrically pumped, either on the head or tail of the lowest energy transition dipole Halogenation is performed on the conjugated skeleton at a position that defines or spatially close to it. It is possible to determine the direction of the lowest energy transition dipole on the reference coordinates of a molecule using experimental methods such as pump-probe transient anisotropy measurement. It will be obvious to industry experts.

  Next, the halogenated fluorophore, luminophore, or phosphorophore is subjected to a cross-coupling reaction using a metal as a catalyst to generate an ethyne bond at the atom to which the halogen partial structure is bonded.

  Next, for this ethinylated fluorophore, luminophore, or phosphorphore, along a vector that defines the direction in which each of the two transition dipoles is aligned or approximately aligned in a head-to-tail manner. Under conditions suitable to produce a bis (fluorophore, luminophore, or phosphorophore) compound in which the ethyne moiety connects the two luminescent moieties, the metal is used as a catalyst. A second cross-coupling reaction is performed with the fluorophore, luminophore or phosphorescent group.

  Known fluorophores, luminophores, or phosphorophores that emit light at a wavelength of 450 nm or longer when optically or electrically pumped, either on the head or tail of the lowest energy transition dipole It will be appreciated by those skilled in the art that it can be dihalogenated on its conjugated backbone at a position that defines These chemical species can be subjected to a metal-catalyzed cross-coupling reaction to generate an ethyne bond at the position of the two atoms to which the halogen partial structure is bonded.

  Experts in the industry will combine the individual covalently linked compounds that combine halogenated, dihalogenated, ethynylated or butadiynylated fluorophores, luminophores or phosphorophores to form conjugated compounds. A dimer in which ethyne or butadiyne groups link individual light-emitting units in such a way that the low energy transition dipoles of the substructure bound to are aligned in a head-to-tail manner or approximately so. It will be appreciated that trimer, tetramer and oligomeric species can be synthesized directly.

In the following examples, all operations were performed under nitrogen through an O ₂ scrubber tower (Schweitzerhall R3-11 catalyst) and a drying tower (Linde 3-A molecular sieve) unless otherwise stated. . Air sensitive solids were handled in a Braun 150-M glove box. Air sensitive solutions were handled using the standard Schlenk method. CH ₂ Cl ₂ and tetrahydrofuran (THF) was distilled from CaH ₂ and K / 4-benzoyl biphenyl under _{N 2,} respectively. N, N-dimethylformamide (DMF) and benzonitrile were dried over MgSO ₄ and _P 2 _{O 5,} respectively, were distilled under reduced pressure. Commercially available products were used as they were for all NMR solvents. ZnCl ₂ was dried by heating under vacuum and stored under N ₂ . Catalysts Pd (PPh ₃ ) ₄ and tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ dba ₃ ) and triphenylarsenic (AsPh ₃ ) were purchased from Strem Chemicals and used as they were. Meso-heptafluoropropyldipyrylmethane ((a) Wijesekera, TP Can, J. Chem. 1996, 74, 1868-1871, (b
) Nishino, N .; Wagner, R .; W. Lindsey, J .; S. J. et al. Org. Chem. 1996, 61, 7534-7544) and trimethylsilylpropynal (Kruithof, KJH .; Schmitz, RF; Klumpp, GW Tetrahedron 1983, 39, 3073-3081) according to published methods. Manufactured. The supporting electrolyte used in the electrochemical experiments, tetra-n-butylammonium hexafluorophosphate, was recrystallized twice from ethanol and dried at 70 ° C. under vacuum overnight before use.

The chemical shift of the ¹ H NMR spectrum is based on the tetramethylsilane (TMS) signal in the deuterated solvent (TMS, δ = 0.00 ppm), and the chemical shift of the ¹⁹ F NMR spectrum is based on fluorotrichloromethane. (CFCl ₃ , δ = 0.00 ppm). All J values were reported in Hertz units. Flash chromatography and size exclusion column chromatography were performed on a bench top using silica gel (EM Science, 230-400 mesh) and Bio-Rad Bio-Beads SX-1 as media, respectively. Mass spectra were obtained at Mass Spectrometry Center at the University of Pennsylvania, USA. MALDI-TOF mass spectral data were obtained in the laboratory of Dr. Virgil Percec (University of Pennsylvania, Department of Chemistry).
Obtained using a Voyager DE instrument. The sample was prepared as a μmolar solution of THF, and dithranol (manufactured by Aldrich) was used as a matrix.

Apparatus : Electronic spectra were recorded using an OLIS UV-NIR spectrophotometer system based on a Cary 14 spectrophotometer. The emission spectra were recorded on a SPEX Fluoroluminescence luminescence spectrophotometer using a T-pass shape and a PMT / InGaAs / Extended-InGaAs detector. These spectra were corrected using a calibration light source supplied by National Bureau of Standards, USA. The NMR spectra were recorded using either a Bruker 200 MHz AM-200, 250 MHz AC-250 or 500 MHz AMX-500 spectrometer. Cyclic voltammetry was measured with a model 273A potentiostat / galvanostat from EG & G Princeton Applied Research. The electrochemical cell used in these experiments uses a platinum disk working electrode, a platinum wire counter electrode and a saturated calomel reference cell (SCE). This reference electrode is separated from the whole solution by a connecting bridge filled with the corresponding solvent / supporting electrolyte solution. A ferrocene / ferrosium redox couple was used as an internal reference for voltage measurements.

All electronic structure calculations are performed using the GAUSSIAN 98 program (Frisch, et
al. Gaussian 98, Revision A .; 9; Gaussian, Inc: Pittsburgh, PA, 1998). Geometric optimization was performed using the semi-empirical PM3 method. In order to minimize the computational effort to the minimum, the phenyl substituent of the tris [(porphinate) zinc (II)] structure is solubilized and replaced with a hydrogen atom, while simultaneously replacing the C ₃ F ₇ group with C ₂ F ₅ Replaced by group. Models for conjugated DDD and DAD tris (porphinate) zinc (II)] compounds were optimized under the limitations of D _2h and C _2h symmetry, respectively.

9-methoxy-1,4,7-trioxanonyl tosylate (1) : p-Toluenesulfonic acid chloride (17.69 g, 9.28 × 10 ⁻² mol) is dissolved in 50 mL of dry pyridine, Cool to -5 ° C. Triethylene glycol monomethyl ether (13.50 mL, 8.44 × 10 ⁻² mol) is added dropwise to the solution and the reaction mixture is stirred at −5 ° C. for 4 hours under N ₂ . The reaction mixture is poured onto ice and extracted 3 times with CH ₂ Cl ₂ . The combined organic phases were washed with 6M HCl, saturated aqueous NaCl, and dried over Na ₂ SO ₄ . The solvent was evaporated to give a viscous oil. Yield = 26.09 g (97% with respect to 13.50 mL of triethylene glycol monomethyl ether). ¹ H NMR (250 MHz, CDCl ₃ : δ 7.80 (d, 2H, J = 8.2 Hz, Ph—H), 7.35 (d, 2H, J = 8.2 Hz, Ph—H), 4.16 (t, 2H, _{J = 4.8Hz, -O-CH 2} -C), 3.69 (t, 2H, J = 4.8Hz, -O-CH 2 -C), 3.61 (m, 6H, -O-CH 2 -C), 3.53
(M, 2H, -O-CH 2 -C), 3.38 (s, 3H, -OCH 3, 2.45 (s, 3H, -CH 3 .CI MS m / z: 319 [(M + H) + calc 319).

3,5-bis (9-methoxy-1,4,7-trioxanonyl) benzaldehyde (2) : 3,5-dihydroxybenzaldehyde (3.052 g, 2.21 × 10 ⁻² mol), K ₂ CO ₃ (9.00 g, 6.51 × 10 ⁻² mol) and 60 mL of dry DMF are added to a two-necked flask and the mixture is stirred under N ₂ . A solution of ( 1 ) (16.53 g, 5.19 × 10 ⁻² mol) in 40 mL dry DMF solution was added to the reaction mixture, which was then refluxed for 1 h, cooled and cooled to 100 mL H _2. Dilute with O and extract several times with CH ₂ Cl ₂ . The combined organic phases are washed with water, saturated aqueous NaCl solution and dried over Na ₂ SO ₄ . After evaporation of the solvent, the residue is chromatographed on silica gel using 50: 1 CH ₂ Cl ₂ : MeOH as eluent. Yield 6.779 g (71% with respect to 3.052 g of 3,5-dihydroxybenzaldehyde). ¹ H NMR (250 MHz, CDCl ₃ : δ9.88 (s, 1H, —CHO), 7.02 (d, 2H, J = 2.3 Hz, o-Ph—H), 6.76 (t, 1H, J = 2.3 Hz) , p-Ph-H), 4.16 (m, 4H, -O-CH 2 -C), 3.87 (m, 4H, -O-CH 2 -C), 3.75 (m, 4H, -O-CH 2 - C), 3.67 (m, 8H , -O-CH 2 -C), 3.56 (m, 4H, -O-CH 2 -C), 3.38 (s, 6H, -OCH 3 .CI MS m / z: 431 [(M + H) ⁺ calculated 431).

5,15-bis [3,5-bis (9-methoxy-1,4,7-trioxanonyl) phenyl] porphyrin (3) : 2,2′-dipyrylmethane (2.29 g, 1.57 × 10 ^{− 2} mol) and ( 2 ) (6.70 g, 1.56 × 10 ⁻² mol) are dissolved in 2.7 L of dry CH ₂ Cl ₂ . After N ₂ was passed through the solution for 20 minutes to purge air, trifluoroacetic acid (0.30 mL, 3.89 × 10 ⁻³ mol) was added via syringe. The reaction mixture was stirred at room temperature under N ₂ in the dark. DDQ (5.35 g, 2.36 × 10 ⁻² mol) is then added to the reaction mixture and the solution is stirred for an additional 2 hours. The solvent is evaporated and the residue is chromatographed on silica gel using 30: 1 CH ₂ Cl ₂ : MeOH as eluent. Yield = 2.820 g (33% with respect to 6.70 g of ( 2 )). ¹ H NMR
(250 MHz, CDCl ₃ : δ 10.31 (s, 2H, meso-H), 9.38 (d, 4H, J = 4.6Hz, δ-H), 9.15 (d, 4H, J = 4.7Hz, δ-H ), 7.46 (d, 4H, J = 2.2Hz, o-Ph-H), 6.97 (t, 2H, J = 2.2Hz, p-Ph-H), 4.34 (m, 8H, -O-CH _2- C), 3.96 (m, 8H , -O-CH 2 -C), 3.79 (m, 8H, -O-CH 2 -C), 3.71 (m, 8H, -O-CH 2 -C), 3.64 ( _{m, 8H, -O-CH 2} -C), 3.50 (m, 8H, -O-CH 2 -C), 3.32 (s, 12H, -OCH 3, -2.03 (s, 2H, NH). visible ( _{CH 2 Cl 2: λ max 407,504,537,573,629} nm.ESI MS m / z: 1133.5267 [ calculated 1133.5310 for _{^{(M + Na) + 60 H}} 78 N 4 O 16).

5,15-Dibromo-10,20-bis [3,5-bis (9-methoxy-1,4,7-trioxanonyl) phenyl] porphyrin (4) : Compound ( 3 ) (2.655 g, 2. 39 × 10 ⁻³ mol) is dissolved in 300 mL chloroform and cooled to −5 ° C. Pyridine (2.0 mL) and N-bromosuccinimide (0.893 g, 5.02 × 10 ⁻³ mol) were added directly to the reaction mixture and the reaction was followed by TLC (30: 1 CHCl ₃ : MeOH). . After 20 minutes, the reaction mixture was poured into water and the orange layer was separated, dried over Na ₂ SO ₄ and evaporated. The residue was chromatographed using 30: 1 CHCl ₃ : MeOH as eluent. Yield = 2.950 g (97% with respect to 2.655 g of raw porphyrin).
¹ H NMR (250 MHz, CDCl ₃ : δ 9.60 (d, 4H, J = 4.9 Hz, β-H), 8.92 (d, 4H, J = 4.9 Hz)
, Β-H), 7.35 (d, 4H, J = 2.3Hz, o-Ph-H), 6.95 (t, 2H, J = 2.2Hz, p-Ph-H), 4.31 (m, 8H, -O _{-CH 2 -C), 3.95 (m} , 8H, -O-CH 2 -C), 3.78 (m, 8H, -O-CH 2 -C), 3.70 (m, 8H
_{, -O-CH 2 -C),} 3.63 (m, 8H, -O-CH 2 -C), 3.50 (m, 8H, -O-CH 2 -C), 3.32 (s, 12H, -OCH 3) , -2.44 (s, 2H, NH). Visible (CH ₂ Cl ₂ : λ _max 424, 520, 556, 599, 658 nm. ESI MS m / z: 1289.3452 [(M + Na) ⁺ calculated value 1289.3520).

(5,15-dibromo-10,20-bis [3,5-bis (9-methoxy-1,4,7- (trioxanonyl) phenyl] porphinate) zinc (II) (5) : Compound ( 4 ) (2.856 g, 2.25 × 10 ⁻³ mol) in 200 mL chloroform and refluxed Zinc acetate dihydrate (1.23 g, 5.60 × 10 ^{−3 in} 50 mL methanol) The reaction mixture is refluxed for a further 2 hours, after cooling to ambient temperature, the solvent is evaporated and the residue is chromatographed on silica gel using 30: 1 CHCl ₃ : MeOH as eluent. Yield = 2.914 g (97% with respect to 2.856 g of raw porphyrin) ¹ H NMR (250 MHz, CDCl ₃ : δ9.68 (d, 4H, J = 4.7 Hz,
β-H), 8.98 (d, 4H, J = 4.7Hz, β-H), 7.45 (d, 4H, J = 2.3Hz, o-Ph-H), 6.92 (t, 2H, J = 2.2Hz, p-Ph-H), 4.32 (m, 8H, -O-CH 2 -C), 3.88 (m, 8H, -O-CH 2 -C), 3.65 (m, 8H, -O-CH 2 -C ), 3.48 (m, 8H, -O-CH 2 -C), 3.03 (m, 8H, -O-CH 2 -C), 2.76 (m, 8H, -O-CH 2 -C), 2.58 (s , 12H, -OCH _{3 visible. (CH 2 Cl 2: λ} max 426,559,601 nm.ESI MS m / z: 1351.2683 [(M + Na) + calcd 1351.2656).

(5,15-bis [trimethylsilyl] -10,20-bis [3,5-bis (9-methoxy-1,4,7- (trioxanonyl) phenyl] porphinate) zinc (II) (6) : Dry THF (20 mL) and (trimethylsilyl) acetylene (0.36 mL, 2.5 × 10 ⁻³ mol) were added to a 100 mL Schlenk tube, cooled to −78 ° C. and stirred. .4M solution, 1.80 mL, 2.52 × 10 ⁻³ mol) was added to this solution and stirred for 30 minutes before warming the solution to room temperature and ZnCl ₂ (0.734 g in 30 mL dry THF). 5.39 × 10 ⁻³ mol) was transferred into the reaction mixture and stirred for 10 min.This solution under N ₂ was contained in 30 mL dry THF ( 5 ). (0.224 g, 1.68 × 10 ⁻⁴ mol) and Pd (PPh ₃ ) ₄ (0.031 g, 2.7 × 10 ⁻⁵ mol) are cannula transferred to a Schlenk tube for 16 hours at 60 ° C. The reaction mixture was then quenched with water and extracted with CHCl ₃ , then the organic layer was washed with water, dried over CaCl ₂ and evaporated 30: 1 CH ₂ Cl ₂ : The crude product was chromatographed on silica gel using MeOH as eluent Yield = 0.206 g (90% with respect to 0.224 g of raw porphyrin) ¹ H NMR (250 MHz, CDCl ₃ : δ9. 62 (d, 4H, J = 4.6Hz, β-H), 8.93 (d, 4H, J = 4.7Hz, β-H), 7.41 (d, 4H, J = 2.2Hz, o-Ph-H), 6.89 (t, 2H, J = 2.2Hz, p-Ph-H), 4.29 (m, 8H
_{, -O-CH 2 -C),} 3.86 (m, 8H, -O-CH 2 -C), 3.65 (m, 8H, -O-CH 2 -C), 3.49 (m, 8H, -O-CH _{2 -C), 3.12 (m,} 8H, -O-CH 2 -C), 2.89 (m, 8H, -O-CH 2 -C), 2.71 (s, 12H, -OCH 3
, 0.61 (s, 18H, -Si -CH 3 visible _{(CH 2 Cl 2:. Λ} max (logε) 437 (5.56), 578 (4.05)
629 (4.39) nm. ESI MS m / z: 1387.5280 [(M + Na) ⁺ calculated value 1387.5236).

(5,15-diethynyl-10,20-bis [3,5-bis (9-methoxy-1,4,7- (trioxanonyl) phenyl] porphinate) zinc (II) (7) : 30 mL of CH2Cl2 Solution containing ( 6 ) (0.156 g, 1.14 × 10 ⁻⁴ mol) in tetrabutylammonium fluoride (1M solution in THF, 0.34 mL, 3.4 × 10 ⁻⁴ mol) under N ₂ The solution was extracted with water, dried over CaCl ₂ and evaporated, and the residue was chromatographed on silica gel using 25: 1 CHCl ₃ : MeOH as eluent. = 0.108 g (77% with respect to 0.156 g of the raw porphyrin) ¹ H NMR (250 MHz, CDCl ₃ : δ9.67 (d, 4H, J = 4.5 Hz, β-H), 8.97 (d, 4H, J = 4.5Hz, β-H), 7.44 (d, 4H, J = 2.2Hz, o-Ph-H), 6. 90 (t, 2H, J = 2.1Hz, p-Ph-H), 4.
29 (m, 8H, -O- CH 2 -C), 3.86 (m, 8H, -O-CH 2 -C), 3.65 (m, 8H, -O-CH 2 -C), 3.49 (m, 8H _{, -O-CH 2 -C),} 3.12 (m, 8H, -O-CH 2 -C), 2.89 (m, 8H, -O-CH 2 -C), 2.71 (s, 12H, -OCH 3, 0.61 (s, 18H, —Si—CH _3. Visible (CH ₂ Cl ₂ : λ _max 429, 558, 609 nm. ESI
MS m / z: 1243.4413 [(M + Na) ⁺ calculated value 1243.4445).

3,3-dimethyl-1-butyl tosylate (8): it was dissolved p- toluenesulfonyl chloride in pyridine (17.35g, 9.10 × ^{1 -2} mol) was dried 50 mL, cooled to 0 ℃ . 3,3-Dimethyl-1-butanol (11.0 mL, 9.10 × 10 ⁻² mol) was added dropwise and the mixture was stirred at 0 ° C. for 4 hours under N ₂ and then poured onto ice. Extracted twice with CH ₂ CH ₂ . The combined organic layers were washed twice with 6M HCl, saturated aqueous NaHCO ₃ , saturated aqueous NaCl, and dried over MgSO ₄ . The solvent was evaporated at room temperature to give a viscous oil. Yield = 23.063 g (99% with respect to 11.0 mL of 3,3-dimethyl-1-butanol). ¹ H NMR (250 MHz, CDCl ₃ : δ 7.80 (d, 2H, J = 8.3 Hz, Ph—H), 7.35 (d, 2H, J = 8.1 Hz, Ph—H), 4.09 (t, 2H, _{J = 7.4Hz, -O-CH 2} -C), 2.46 (s, 3H, -CH
_{3, 1.58 (t, 2H,} J = 7.4Hz, -OC-CH 2 -C), 0.87 (s, 9H, -C-CH 3 .CI MS m / z: 257 [(M + H) + calc 257).

3,5-bis (3,3-dimethyl-1-butyroxy) benzaldehyde (9) : 3,5-dihydroxybenzaldehyde (4.008 g, 2.90 × 10 ⁻² mol), K ₂ CO ₃ (8.016 g) 5.80 × 10 ⁻² mol) and 50 mL of dry DMF were stirred in a 100 mL round bottom flask under N ₂ . Compound ( 8 ) (14.869 g, 5.80 × 10 ⁻² mol) was added and the solution was stirred at 80 ° C. for 13 hours. The reaction mixture was then cooled, filtered and evaporated, after which water was added to the residue and the aqueous mixture was extracted 3 times with CHCl ₃ . The combined organic layers were washed with 2% HCl, aqueous NaHCO ₃ solution, aqueous NaCl solution and dried over MgSO ₄ . After removal of volatiles, the residue was chromatographed on silica gel with CHCl ₃ . Yield = 7.314 g (82% with respect to 4.008 g of 3,5-dihydroxybenzaldehyde). ¹ H NMR (250 MHz, CDCl ₃ : δ9.85 (s, 1H, —CHO), 6.98 (d, 2H, J = 2.3 Hz, o-Ph—H), 6.68 (t, 1H, J = 2.3 Hz) , p-Ph-H), 4.04 (t, 4H, J = 7.3Hz, -O-CH 2 -C), 1.74 (t, 4H, J = 7.3Hz, -OC-CH 2 -C), 1.00 ( s, 18H, -C-CH _3. CI MS m / z: 307 [(M + H) ⁺ calculated value 307).

5,15-bis [3 ′, 5′-di (3,3-dimethyl-1-butoxy) phenyl] porphyrin (10) : dipyrrylmethane (1.604 g, 1.10 × 10 ⁻² mol) and ( 9 ) (3.342 g, 1.09 × 10 ⁻² mol) was dissolved in 2.1 L of dry CH ₂ Cl ₂ . Expelling air from the solution by passing a 20 min _{N 2,} then trifluoroacetic acid (0.19mL, 2.47 × ^{10 -3} mol) was added via syringe. The reaction mixture was stirred for 22 hours under N ₂ at room temperature in the dark. DDQ (3.70 g, 1.63 × 10 ⁻² mol) was then added and the reaction mixture was stirred for an additional hour. The solvent was evaporated and the residue was chromatographed on silica gel using CH ₂ Cl ₂ as the eluent. Yield = 2.234 g (47% with respect to 3.342 g of ( 9 )). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.31 (s, 2H, meso-H), 9.39 (d, 4H, J = 4.7 Hz, β-H), 9.19 (d, 4H, J = 4.7 Hz, β-H), 7.43
(D, 4H, J = 2.3Hz, o-Ph-H), 6.91 (t, 2H, J = 2.2Hz, p-Ph-H), 4.21 (t, 8H, J = 7.4Hz, -O-CH _{2 -C), 1.86 (t,} 8H, J = 7.4Hz, -OC-CH 2 -C), 1.00 (s, 36H, -C-CH 3, -2.06
(S, 2H, NH). Visible (CH ₂ Cl ₂ : λ _max 408, 503, 535, 574, 628 nm. ESI MS m / z: 863.5494 [(M + H) ⁺ calculated value 863.5476).

5-Bromo-10,20-bis [3 ′, 5′-bis (3,3-dimethyl-1-butyroxy) phenyl] porphyrin (11) : Compound ( 10 ) (1.667 g, 1.93 × 10 ^{− 3} mol) was dissolved in 300 mL CHCl ₃ and cooled to −5 ° C. Pyridine (2 mL) and N-bromosuccinimide (0.345 g, 1.94 × 10 ⁻³ mol) were then added and the reaction was followed by TCL. After 15 minutes, the reaction mixture is poured into water, the organic layer is separated,
Dry over Na ₂ SO ₄ , filter and evaporate. The residue was chromatographed on silica gel using 3: 2 CHCl ₃ : hexane as eluent. 5,15-Dibromo-10,20-bis [3 ′, 5′-bis (3,3-dimethyl-1-butoxy) phenyl] porphyrin (0.390 g, 20%) and the target compound (1.058 g, Two products were recovered (58% relative to 1.667 g of porphyrin). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.16 (s, 1H, meso-H), 9.73 (d, 2H, J = 4.9 Hz, β-H), 9.28 (d, 2H, J = 4.6 Hz, β-H), 9.08 (d, 2H, J = 4.7Hz, β-H), 9.07 (d, 2H, J = 4.8Hz, β-H), 7.37 (d, 4H, J = 2.1Hz, o- Ph-H), 6.90 (t , 2H, J = 1.8Hz, p-Ph-H), 4.20 (t, 8H, J = 7.4Hz, -O-CH 2 -C), 1.85 (t, 8H, J _{= 7.4Hz, -OC-CH 2 -C} ), 1.00 (s, 36H, -C-CH 3, -2.20 (s, 2H
, NH). Visible (CH ₂ Cl ₂ : λ _max 417, 511, 544, 587, 644 nm. ESI MS m / z: 941.4597 [(M + H) ⁺ calculated value 941.4580).

( 5-Bromo-10,20-bis [3 ′, 5′-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II) (12) : Compound ( 11 ) (1.315 g , 1.40 × 10 ⁻³ mol) was dissolved in 150 mL of CHCl ₃ . Zinc acetate dihydrate (0.770 g, 3.51 × 10 ⁻³ mol) contained in 25 mL of methanol was slowly added and the reaction mixture was refluxed for 2 hours. After cooling and removing volatiles, the residue was chromatographed on silica gel using 15: 1 hexane: THF as eluent. Yield = 1.348 g (96% with respect to 1.315 g of raw porphyrin). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.23 (s, 1H, meso-H), 9.81 (d, 2H, J = 4.8 Hz, β-H), 9.37 (d, 2H, J = 4.6 Hz, β-H), 9.18 (d, 2H, J = 4.6Hz, β-H), 9.17 (d, 2H, J = 4.7Hz, β-H)
, 7.38 (d, 4H, J = 2.2Hz, o-Ph-H), 6.90 (t, 2H, J = 2.2Hz, p-Ph-H), 4.19 (t, 8H, J = 7.4Hz, -O _{. -CH 2 -C), 1.85 (} t, 8H, J = 7.4Hz, -OC-CH 2 -C), 1.00 (s, 36H, -C-CH 3 visible _{(CH 2 Cl 2: λ max} 418, 547, 580 nm, ESI MS m / z: 1002.3601 (M ⁺ calculated value 1002.3638).

(5-trimethylsilylethynyl-10,20-bis [3 ′, 5′-bis (3,3-dimethyl-1-butoxy) phenylporphinate) zinc (II) (13) : THF (20 mL) and (trimethylsilyl) Add acetylene (0.56 mL, 3.96 × 10 ⁻³ mol) to a 100 mL Schlenk tube, stir and cool to −78 ° C. Methyl lithium (1.4M solution in diethyl ether, 2.90 mL, 4.06 × 10 ⁻³ mol) was added and the solution was stirred for 30 minutes. After warming to room temperature, ZnCl ₂ (1.095 g, 8.03 × 10 ⁻³ mol) in 50 mL of dry THF was transferred to the reaction mixture via a cannula. After stirring for 10 minutes, ( 12 ) (0.404 g, 4.02 × 10 ⁻⁴ mol) and Pd (PPh ₃ ) ₄ (0.069 g, 5.97 × 10 ⁻⁵ mol) and 40 mL of dry THF were added. Transfer the reaction mixture to a 250 mL Schlenk tube containing. The mixture is stirred under N _{2 at} 60 ° C. for 16 hours before being quenched with water, extracted with CH ₂ Cl ₂ , washed with water, dried over CaCl ₂ and evaporated. The crude was chromatographed on silica gel using 10: 1 hexane: THF as eluent. Yield = 0.404 g (98% with respect to 0.404 g of raw porphyrin). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.18 (s, 1H, meso-H), 9.78 (d, 2H, J = 4.5 Hz, β-H), 9.33 (d, 2H, J = 4.5 Hz, H), 9.14 (d, 2H, J = 4.7Hz, β-H), 9.13 (d, 2H, J = 4.5Hz, β-H), 7.37 (d, 4H, J = 2.2Hz, o-Ph- H), 6.88 (t, 2H , J = 2.2Hz, p-Ph-H), 4.19 (t, 8H, J = 7.4Hz, -O-CH 2 -C), 1.84 (t, 8H, J = 7.4 _{. Hz, -OC-CH 2 -C} ), 1.00 (s, 36H, -C-CH 3, 0.62 (s, 9H, -Si-CH 3 visible _{(CH 2 Cl 2: λ max} (logε) 427 (5.51 ), 554 (4.15), 594 (3.70) nm ESI MS
m / z: 1021.5013 [(M + H) ⁺ calculated value 1021.5005).

(5-ethynyl-10,20-bis [3 ′, 5′-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II) (14) : in 40 mL of CH ₂ Cl ₂ ( 13 ) (0.375 g, 3.67 × 10 ⁻⁴ mol) in a solution containing tetrabutylammonium fluoride (1M solution in THF, 0.73 mL, 7.3 × 10 ⁻⁴ mol) under N _2. Was added. The reaction mixture was stirred for 10 minutes, quenched with water, extracted with _CH 2 Cl _2, dried over CaCl _2. After evaporation of the solvent, the residue was chromatographed on silica gel using 10: 1 hexane: THF as eluent. Yield = 0.340 g (97% with respect to 0.375 g of raw porphyrin). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.22 (s, 1H, meso-H), 9.79 (d, 2H, J = 4.7 Hz, β-H), 9.35 (d, 2H, J = 4.5 Hz, β-H), 9.17 (d, 2H, J = 4.7Hz, β-H), 9.15 (d, 2H, J = 4.6Hz, β-H), 7.37 (d, 4H, J = 2.2Hz, o- Ph-H), 6.88 (t , 2H, J = 2.6Hz, p-Ph-H), 4.18 (t, 8H, J = 7.4Hz, -O-CH 2 -C), 4.15 (s, 1H, - . CC-H), 1.84 ( t, 8H, J = 7.4Hz, -OC-CH 2 -C), 1.00 (s, 36H, -C-CH 3 visible _{(CH 2 Cl 2: λ max} 422,552, 590 nm, ESI MS m / z: 949.4595 [(M + H) ⁺ calculated value
949,4611).

Bis [ (5,5 ′, 10,20-bis [3,5-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II)] ethyne (DD) : Compound ( 12 ) ( 0.0696 g, 6.92 × 10 ⁻⁵ mol) and ( 14 ) (0.066 g, 6.94 × 10 ⁻⁵ mol), 20 mL dry THF, and 2.0 mL triethylamine are added to a 50 mL Schlenk tube. It was. Pd ₂ (dba) ₃ (0.019 g, 2.07 × 10 ⁻⁵ mol) and AsPh ₃ (0.051 g, 1.67 × 10 ⁻⁴ mol) were transferred to a Schlenk tube in a dry box and frozen under reduced pressure. Degassing was performed by repeating the thaw cycle three times in sequence. After the reaction mixture was stirred at 45 ° C. for 10.5 hours, the solvent was evaporated and the residue was chromatographed on silica gel using 10: 1 hexane: THF as eluent. Yield = 0.115 g (89% with respect to 0.0696 g of (12)). ¹ H NMR (250 MHz, CDCl ₃ : δ 10.48 (d, 4H, J = 4.7 Hz, β-H), 10.19 (s, 2H, meso-H), 9.37 (d, 4H, J = 4.4 Hz, β-H), 9.35 (d, 4H, J = 4.5Hz, β-H), 9.19 (d, 4H, J = 4.5Hz, β-H), 7.46 (d, 8H, J = 2.2Hz, o- Ph-H), 6.91 (t , 4H, J = 2.2Hz, p-Ph-H), 4.22 (t, 16H, J = 7.4Hz, -O-CH 2 -C), 1.86 (t, 16H, J _{= 7.4Hz, -OC-CH 2 -C} ), 1.01 (s, 72H, -C-CH 3 visible _{(CH 2 Cl 2:. λ} max (logε) 399 (5.06), 404 (5.06), 426 (5.03 ), 439 (4.96), 476 (5.42), 539 (4.19), 558 (4.23), 669 (4.62) nm MALDI-TOF MS m / z: 1871.65 (M ⁺ calculated value 1870.8906).

[(5, -10,20-bis [3,5-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II)]-[(5 ′, 15′-bromo-10 ′ , 20′-bis [3,5-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II)] ethyne (DD-Br) and 5,15-bis [[5 ′, − 10 ', 20'-bis [3,5-bis (3,3-dimethyl-1-butyoxy) phenyl] porphinate) zinc (II)] ethynyl] -10,20-bis [3,5-di (9 - methoxy-1,4,7-trioxanonyl) phenyl] porphinato) zinc (II) (DDD): compound (5) (0.692g, 5.19 × 10 -4 mol) and Pd _(PPh 3) ₄ (0.046g, 3.98 × ^{10 -5} mol), And CuI placed in a Schlenk tube (0.023g, 1.21 × ^{10 -4} mol) 100 mL. A solution containing ( 14 ) (0.307 g, 3.23 × 10 ⁻⁴ mol) and diethylamine (0.60 mL, 5.80 × 10 ⁻³ mol) in 30 mL of THF after adding 40 mL of dry THF. Was added using a trocar. The reaction mixture was stirred at 55 ° C. for 65 hours under N ₂ and then quenched with water. The organic layer was extracted with CHCl ₃ , washed with water, dried over CaCl ₂ and evaporated. The residue was chromatographed on silica gel using 1: 1 hexane: THF as eluent. Two products were recovered: 0.318 g DD-Br (45% with respect to 0.307 g ( 14 )) and 0.193 g DDD (24%). DD-Br: ¹ H NMR (250 MHz, CDCl ₃ : δ 10.49 (d, 2H, J = 4.6 Hz, β-H), 10.39 (d, 2H, J = 4.7H, β-H), 10.20 ( s, 1H, meso-H), 9.67 (d, 2H, J = 4.8Hz, β-H), 9.36 (d, 2H, J = 4.4Hz, β-H), 9.35 (d, 2H, J = 4.4 Hz, β-H), 9.17 (d, 2H, J = 4.5Hz, β-H), 9.17 (d, 2H, J = 4.6Hz
, Β-H), 8.99 (d, 2H, J = 4.7Hz, β-H), 7.51 (d, 4H, J = 2.1Hz, o-Ph-H), 7.45 (d, 4H, J = 2.2Hz , O-Ph-H), 6.91 (t, 2H, J = 2.0Hz, p-Ph-H), 6.88 (t, 2H, J = 2.7Hz, p-Ph-H), 4.30 (m, 8H, _{-O-CH 2 -C), 4.20} (t, 8H, J = 7.4Hz, -O-CH 2 -C), 3.83 (m, 8H, -O-CH 2 -C), 3.61 (m, 8H, _{-O-CH 2 -C), 3.44} (m, 8H, -O-CH 2 -C), 3.07 (m, 8H, -O-CH 2 -C), 2.82 (m, 8H, -O-CH 2 -C), 2.65 (s, 12H , -OCH 3, 1.84 (t, 8H, J = 7.3Hz, -OC-CH 2 -C), 0.99 (s, 36H, -C-CH 3. visible (CH ₂ Cl ₂ : λ _max 410, 429, 441, 479, 546, 686 nm MALDI-TOF MS m / z: 2198.1 (M ⁺ calculated value 2196.80) DDD: ¹ H NMR (250 MHz, CDCl ₃ : δ 10.53 (D, 4H, J = 4.6Hz, β-H), 10.41 (d, 4H, J = 4.5H, β-H), 10.18 (s
, 2H, meso-H), 9.37 (d, 4H, J = 4.7Hz, β-H), 9.35 (d, 4H, J = 5.6Hz, β-H), 9.20
(D, 4H, J = 4.6Hz, β-H), 9.16 (d, 4H, J = 4.5Hz, β-H), 7.57 (d, 4H, J = 2.0Hz, o-Ph-H), 7.44 (D, 8H, J = 2.1Hz, o-Ph-H), 6.84 (t, 6H, J = 2.1Hz, p-Ph-H), 4.23 (m
_{, 8H, -O-CH 2 -C} ), 4.17 (t, 16H, J = 7.4Hz, -O-CH 2 -C), 3.74 (m, 8H, -O-CH 2 -C), 3.50 (m _{, 8H, -O-CH 2 -C} ), 3.33 (m, 8H, -O-CH 2 -C), 2.99 (m, 8H, -O-CH 2 -C), 2.78 (m, 8H, -O _{-CH 2 -C), 2.61 (s} , 12H, -O-CH 3, 1.81 (t, 16H, J = 7.4Hz, -OC-CH 2 -C), 0.97 (s, 72H, -C-CH 3 Visible (CH ₂ Cl ₂ : λ _max (log ε) 410 (5.33), 490 (5.54), 542 (4.34), 563 (4.39), 742 (4.99) nm MALDI-TOF MS m / z: 3066.6 (M ⁺ Calculated value 3065.33).

5,15-bis [[15 ",-(5 ',-10'20'-bis [3,5-bis [(3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II)]- [(5 ",-10", 20 "-bis [3,5-di (9-methoxy-1,4,7-trioxanonyl) phenyl] porfinato) zinc (II)] ethyne] ethynyl] -10 , 20-bis [3,5-di (9-methoxy-1,4,7-trioxanonyl) phenyl] porphinate) zinc (II) (DDDDDD) : DD-Br (0.259 g, 1.18 × 10 ⁻⁴ mol), ( 7 ) (0.082 g, 6.71 × 10 ⁻⁵ mol), and diethylamine (0.20 mL, 1.93 × 10 ⁻³ mol) are added to a 100 mL Schlenk tube and 40 mL of Dissolved in dry THF. Pd (PPh ₃ ) ₄ (0.012 g, 1.04 × 10 ⁻⁵ mol) and CuI (0.006 g, 3.2 × 10 ⁻⁵ mol) were added in the dry box followed by a freeze-thaw cycle. Degassed 3 times. Stir at 50 ° C. for 84 hours under N ₂ . The reaction is then quenched with water, extracted with CHCl ₃ and dried over CaCl ₂ . After evaporation of the volatiles, the residue was chromatographed on silica gel using 30: 1 CHCl ₃ : MeOH as eluent. The product mixture was subjected to preparative size exclusion chromatograph (BioRad Bio-Beads SX-1, packed in THF, gravity flow) and then on silica gel using 20: 1 CHCl ₃ : MeOH as eluent. The product pentamer was chromatographed. Yield = 0.163 g (51% with respect to 0.259 g DD-Br). ¹ H NMR (500 MHz, CDCl ₃ : δ 10.51 (d, 4H, J = 4.6 Hz, β-H), 10.47 (m, 8H, β-H), 10.40 (d, 4H, J = 4.5 Hz, β-H), 10.15 (s, 2H, meso-H), 9.34 (d, 4H, J = 4.6Hz, β-H), 9.31 (d, 4H, J = 4.6Hz, β-H), 9.26 ( d, 4H, J = 4.5Hz, β-H), 9.22 (d, 4H, J = 4.1Hz, β-H), 9.17 (d, 4H, J = 4.5Hz, β-H), 9.12 (d, 4H, J = 4.5Hz, β-H), 7.51 (br s, 8H, o-Ph-H), 7.47 (br s, 4H, o-Ph-H), 7.40 (br s, 8H, o-Ph) -H), 6.76 (br s, 4H, p-Ph-H), 6.66 (br s, 4H, p-Ph-H), 6.50 (br s, 2H, p-Ph-H), 4.12 (t, 16H, J = 6.7Hz, -O- CH 2 -C), 4.04 (br s, 16H, -O-CH 2 -C), 3.91 (br s, 8H
_{, -O-CH 2 -C),} 3.52 (br s, 16H, -O-CH 2 -C), 3.41 (br s, 8H, -O-CH 2 -C), 3.31 (br s, 16H, - _{O-CH 2 -C), 3.22} (br s, 8H, -O-CH 2 -C), 3.15 (br s, 16H, -O-CH 2 -C), 3.08 (br s, 8H, -O- _{CH 2 -C), 2.90 (br} s, 16H, -O-CH 2 -C), 2.86 (br s, 8H, -O-CH 2 -C), 2.72 (br s, 24H, -O-CH 2 -C), 2.58 (s, 36H , -OCH 3, 1.76 (t, 16H, J = 7.2Hz, -OC-CH 2 -C), 0.93 (s, 72H, -C-CH 3. visible (CH ₂ Cl ₂ : λ _max (logε) 412 (5.45), 490 (5.68), 809 (5.27) nm MALDI-TOF MS m / z: 5454.6 (M ⁺ calculated value 5454.21).

5,15-bis (trimethylsilyl) -10,20-bis (heptafluoropropyl) porphyrin (15) : meso-heptafluoropropyldipyrylmethane (2.131 g)
, 6.78 × 10 ⁻³ mol) and trimethylsilylpropynal (0.856 g, 6.78 × 10 ⁻³ mol) were dissolved in 500 mL of dry CH ₂ Cl ₂ . The solution was degassed with N ₂ for 20 minutes and cooled to −5 ° C. BF ₃ .Et ₂ O (0.17 mL, 1.34 × 10 ⁻³ mol) was added via syringe and the reaction mixture was stirred for 2 hours. The solution was then warmed to room temperature, stirred for an additional 11 hours, and DDQ (2.30 g, 1.01 × 10 ⁻² mol) was added. After stirring for 1 hour, the solvent was evaporated and the residue was chromatographed on silica gel using 3: 1 hexane: CHCl ₃ as eluent. Yield = 0.314 g (11% with respect to 2.131 g of meso-heptafluoropropyldipyrylmethane). ¹ H NMR (250 MHz, CDCl ₃ : δ9.82 (d, 4H, J = 5.1 Hz, β-H), 9.46 (br s, 4H, β-H), 0.65 (s, 18H, -Si-CH ₃ , -2.08 (s, 4H, NH) ¹⁹ F NMR (188 MHz, CDCl ₃ : δ-79.6 (t, 6F), -83.9 (m, 4F), -120.8 (s, 4F) Visible (CH ₂ Cl ₂ : λ _max 435, 533, 567, 618, 678 nm, ESI MS m / z: 839.1719 [(M + H) ⁺ calculated value 839.1707).

5,15-bis (trimethylsilylethynyl) -10,20-bis (heptafluoropropyl) porphinate] zinc (II) (16) : Compound ( 15 ) (0.496 g, 5.91 × 10 ⁻⁴ mol) Dissolve in 100 mL CHCl ₃ and reflux. Zinc acetate dihydrate (0.260 g, 1.18 × 10 ⁻³ mol) contained in 15 mL of methanol is slowly added. The solution was refluxed for 2.5 hours, then cooled and evaporated. The residue was chromatographed on silica gel using 15: 1 hexane: THF as eluent. Yield = 0.506 g (95% with respect to 0.496 g of raw porphyrin). ^{1 H NMR (250 MHz, CDCl} 3: δ9.77 (d, 4H, J = 5.0Hz, β-H), 9.53 (br s, 4H, β-H), 0.65 (s, 18H, -Si-CH _3. ¹⁹ F NMR (188 MHz, CDCl ₃ : δ-79.4 (s, 4F), -79.7 (m, 6F), -120.0 (s, 4F)
. Visible (THF): λ _max (logε) 442 (5.71), 570 (4.05), 591 (4.15), 635 (3.39) nm. ESI MS m / z: 900.0769 (M ⁺ calculated 900.0764).

5,15 diethynyl 10,20-bis (heptafluoropropyl) porphinato] zinc (II) (17): Dry in THF (16) of 50mL (0.455g, 5.04 × 10 ^-4 mol) To the solution containing was added tetrabutylammonium fluoride (1M solution in THF, 1.12 × 10 ⁻³ mol) under N ₂ . The reaction mixture was stirred for 10 minutes, quenched with water, extracted with CHCl ₃ , washed with water, dried over CaCl ₂ and evaporated. The residue was chromatographed on silica gel using 15: 1 hexane: THF as eluent. Yield = 0.377 g (99% with respect to 0.455 g of raw porphyrin). ¹ H NMR (250 MHz, 1 drop of pyridine-d ₅ in CDCl ₃ : δ9.81 (d, 4H, J = 4.9 Hz
, Β-H), 9.58 (br s, 4H, β-H), 4.20 (s, 2H, -CC-H). ¹⁹ F NMR (188 MHz, CDCl ₃
Medium drop of pyridine-d ₅ : δ-78.8 (s, 4F), -79.7 (s, 6F), -119.8 (s, 4F). Visible (THF): λ _max 435, 564, 582 nm. ESI MS m / z: 790.9659 [(M + Cl) ⁺ calculated value 790.9662).

[ (5, -10,20-bis [3,5-bis (3,3-dimethyl-1-butyroxy) phenyl] porphinate) zinc (II)]-[(5'15'-ethynyl-10 ', 20'-bis [10,20-bis (heptafluoropropyl) porphinate) zinc (II)] ethyne (DA-ethyne) and 5,15-bis [5 ', 10', 20'-bis [3,5 -Di (3,3-dimethyl-1-butyroxy) phenyl] porphinate] zinc (II)] ethynyl] -10,20-bis (heptafluoropropyl) porphinate] zinc (II) (DAD) : Compound ( 12 ) (0.120g, 1.19 × ^{10 -4} mol) and (17) (0.108g, 1.43 × 10 -4 mol), S of THF with (30 mL) and triethylamine (3.0 mL) 100 mL It was added to the hlenk tube. Pd ₂ (dba) ₃ (16.3 mg, 1.78 × 10 ⁻⁵ mol) and AsPh ₃ (43.7 mg, 1.43 × 10 ⁻⁴ mol) were added in the dry box, followed by freezing and thawing. The solution was degassed by three cycles. The reaction mixture was stirred and evaporated at 35 ° C. under N ₂ for 7 hours. The residue was chromatographed on silica gel using 10: 1 hexane: THF as eluent. The recovered bis- and tris [porphinate] zinc (II) product was applied to a preparative size exclusion chromatograph (BioRad Bio-Beads SX-1, gravity flow packed in THF) before eluent. Further chromatography on silica gel with 8: 1 hexane: THF. Two products were obtained: 0.100 g DA-ethyne (50% for 0.120 g ( 12 )) and 0.031 g DAD (20%). DA-ethyne: ¹ H NMR (250 MHz, 1 drop of pyridine-d ₅ in CDCl ₃ : δ 10.56 (d, 2H, J = 4.9 Hz, β-H), 10.42 (d, 2H, J = 4.6 Hz) , Β-H), 10.15 (s, 1H, meso-H), 9.82
(D, 2H, J = 4.9Hz, β-H), 9.73 (br s, 2H, β-H), 9.60 (br s, 2H, β-H), 9.35 (d
, 2H, J = 4.6Hz, β-H), 9.31 (d, 2H, J = 4.5Hz, β-H), 9.13 (d, 2H, J = 4.5Hz, β-H), 7.48 (d, 4H , J = 2.2Hz, o-Ph -H), 6.94 (t, 2H, J = 2.2Hz, p-Ph-H), 4.26 (t, 8H, J = 7.4Hz, -O-CH 2 -C) , 4.22 (s, 1H, —CC—H), 1.89 (t, 8H, J = 7.4 Hz, —OC—CH ₂ —C), 1.03 (s, 36H, —C—CH _3. ¹⁹ F NMR (188 1 drop of pyridine-d _{5 in} MHz, CDCl ₃ : δ-78.9 (s, 4F), -79.6 (t, 6F), -119.8 (s, 4F) Visible (THF): λ _max (logε) 429 ( 5.06), 450 (4.92), 471 (4.96), 484 (4.95), 550 (4.25), 593 (4.14), 688 (4.55) nm MALDI-TOF MS m / z: 1686.64 (M ⁺ calculated value 1678.44) DAD: ¹ H NMR (250 MHz, 1 drop of pyridine-d ₅ in CDCl ₃ : δ 10.56 (d, 4H, J = 5.0 Hz, β-H), 10.45 (d, 4H, J = 4.7 Hz, β-H), 10.15 (s, 2H, meso-H), 9.76 (br s, 4H, β-H), 9.36 (d, 4H, J = 4.5Hz, β-H), 9.32 (d, 4H, J
= 4.4Hz, β-H), 9.14 (d, 4H, J = 4.4Hz, β-H), 7.49 (d, 8H, J = 2.2Hz, o-Ph-H), 6.94 (t, 4H, J = 2.1Hz, p-Ph-H ), 4.27 (t, 16H, J = 7.4Hz, -O-CH 2 -C), 1.90 (t, 16H, J = 7.4Hz, -OC-CH 2 -C) , 1.04 (s, 72H, -C-CH _3. ¹⁹ F NMR (188 MHz, 1 drop of pyridine-d ₅ in CDCl ₃ : δ-78.9 (s, 4F), -79.6 (s, 6F), -119.7 (S, 4F) Visible (THF): λ _max (logε) 432 (5.29), 506 (5.18), 566 (4.49), 593 (4.42), 735 (4.93) nm MALDI-TOF MS: m / z 2602 (calculated value 2600.87).

5,15-bis [[15 ",-(5 ',-10', 20'-bis [3,5-bis (3,3-dimethyl-1-butoxy) phenyl] porphinate) zinc (II)] -[(5 ",-(10", 20 "-bis (heptafluoropropyl) porphinate) zinc (II)] ethyne] ethynyl] -10,20-bis [3,5-di (9-methoxy-1 , 4,7-trioxanonyl) phenyl] porphinate) zinc (II) (DADAD) : DA-ethyne (0.085 g, 5.05 × 10 ⁻⁵ mol), ( 5 ) (0.0344 g, 2. 58 × 10 ⁻⁵ mol), dry THF (20 mL) and triethylamine (2.0 mL) were added to a 50 mL Schlenk tube. Pd ₂ (dba) ₃ (3.6 mg, 3.93 × 10 ⁻⁶ mol) and AsPh ₃ (9.7 mg, 3.17 × 10 ⁻⁵ mol) were added in the dry box and then to this solution. On the other hand, it was degassed by three freeze-thaw decompression cycles. The resulting mixture is stirred at 40 ° C. under N ₂ for 18 hours and evaporated. The residue was chromatographed on silica gel using 1: 1 hexane: THF as eluent. The recovered high molecular weight porphyrin product was separated by preparative size exclusion chromatograph (BioRad Bio-Beads SX-1, gravity flow packed in THF), and the elution band of the separated product was reduced to 25 1 CH ₂ Cl ₂ : MeOH as eluent and chromatographed once more on silica gel. Yield 0.027 g, (24% with respect to 0.085 g DA-ethyne). ¹ H NMR (250 MHz, 1 drop of pyridine-d ₅ in CDCl ₃ : δ 10.58 (d, 8H, J = 4.8 Hz, β-H), 10.46 (d, 4H, J = 4.3 Hz, β-H ), 10.40 (d, 4H, J = 4.8Hz, β-H), 10.16 (s
, 2H, meso-H), 9.80 (br s, 8H, β-H), 9.37 (d, 4H, J = 4.3Hz, β-H), 9.33 (d, 4H
, J = 4.4 Hz, β-H), 9.29 (d, 4H, J = 4.4 Hz, β-H), 9.15 (d, 4H, J = 4.6 Hz, β-H), 7.62 (d, 4H, J = 2.2Hz, o-Ph-H), 7.50 (d, 8H, J = 2.2Hz, o-Ph-H), 7.06 (t, 2H, J = 2.2Hz, p-Ph-H), 6.95 (t , 4H, J = 2.2Hz, p -Ph-H), 4.46 (m, 8H, -O-CH 2 -C), 4.28 (t
, 16H, J = 7.3Hz, -O -CH 2 -C), 4.05 (m, 8H, -O-CH 2 -C), 3.87 (m, 8H, -O-CH 2 -C), 3.77 (m _{, 8H, -O-CH 2 -C} ), 3.70 (m, 8H, -O-CH 2 -C), 3.55 (m, 8H, -O-CH 2 -C), 3.34 (s, 12H, -OCH ₃ , 1.91 (t, 16H, J = 7.3 Hz, —OC—CH ₂ —C), 1.05 (s, 72H, —C—CH _3. ¹⁹ F NMR (188 MHz, 1 drop of pyridine-d in CDCl _{3 5} : □ -79.0 (s, 8F), -79.6 (t, 12F), -11
9.7 (s, 8F). Visible (THF): λ _max (logε) 430 (5.35), 507 (5.41), 595 (4.54), 798 (5.25) nm. MALDI-TOF MS m / z: 4525.51 (M ⁺ calculated 4525.29).

  Those skilled in the art will appreciate that many variations and modifications can be made to the preferred embodiment of the present invention, and that such modifications and variations can be made without departing from the spirit of the invention. Will. For example, the method of the present invention can use porphyrin-related compounds such as chlorin, forvin, bacteriochlorin, porphyrinogen, saffirin, texaphyrin, and phthalocyanine instead of porphyrin. In addition to the ethyne and butadiyne partial structures, the present invention can use other moieties such as ethene, polyin, phenylene, thiophene, anene, or allene.

  Accordingly, the appended claims are intended to cover such equivalent modifications as fall within the true spirit and scope of this invention.

Conjugated porphyrin sequence compound (compounds 4 to 12 ) and its absorption spectrum. Uncorrected emission spectra are shown as nested. The solvent (Compound 4 ~ 10) = CHCl _3: solvent (Compound 11-12) = 10: 1 CHCl _3: pyridine. Dynamic properties of the fluorescence having the anisotropy of the compound 4-6. (A) Comparison of time-dependent decay for fluorescence polarized in directions parallel and perpendicular to the polarization direction of the excitation light. (B) Time dependence of fluorescence anisotropy. Excitation (λ _ex ) and emission (λ _em ) wavelengths, as well as fluorescence lifetime and anisotropic polarization time constants, are shown in Table 1. (A) A schematic diagram showing the dependence of the energy interval of the electronic state on the overlap of vibration wave functions and the dependence of the nuclear displacement (ΔQ) at equilibrium. (B) Potential energy diagram emphasizing the effect of increased nuclear displacement at S ₁ -T _{1 on intersystem} crossing rate constant k _ISC . (5-ethynyl-10,20-diphenylporphinate) zinc (II) (compound 1 ), (5,15-diethynyl-10,20-diphenylporphinate) zinc (II) (compound 2 ) and Photophysical properties of S ₁ -excited states of (porphinate) zinc (II) complexes 1 to 12 containing (2-ethynyl-5,10,15,20-tetraphenylporphinate) zinc (II) (compound 3 ) : Fluorescence lifetime and time-resolved anisotropy data ^ad .

(A) Samples for transient spectroscopic studies were kept strictly dry using standard inert atmosphere techniques. All data submitted was recorded at 293K in 10: 1 CHCl ₃ : pyridine.

(B) The lifetime of fluorescence was determined using the time-correlated single photon counting (TCSPC) apparatus (University of Pennsylvania, Regional Laser and Biotechnology Laboratory) already described above. Device response function = 20 ps fwhm. Data was analyzed using the Lifetime (RLBL) program. Compound 1-12 showed a single exponential decay of fluorescence isotropic. Average chi ² values calculated from the fit to the curve of these data (fitting) for 1-12 was 1.06 ± 0.08.

(C) Time-resolved anisotropic attenuation data were measured by alternately selecting parallel and vertical components of light emission using a rotary deflection filter. All other experimental methods are the same as for lifetime measurements. Correlation time of rotation was determined by Wahl, Holtom (Holtom, GR Proc. SP1E-Int Soc. Opt, Eng. 1204, 2-12 (1990); Wahl, P. Biophys. Chem. 10, 91-104 (1979). )), And λ _ex and λ _em represent the wavelengths for excitation and emission exploration, respectively. All anisotropic decay processes could be fitted as simple single exponential decays

(D) τ _F = fluorescence lifetime; τ ₀ = initial fluorescence anisotropy determined 20 ps after excitation; τ
_r = rotational diffusion time constant.

(E) τ ₀ determined at 20 ps after excitation.

  (F) It was determined by van Grondel (Monshower, R., Abrahamsson, M., van Mourik, F. & van Grondelle, R. J. Phys. Chem. B101, 7241-7248 (1997)).

(G) r ₀ determined at 8 ps after excitation for Bchla and at time 0 for B820, LH-2 and LH-1.

Conjugated [(porphinato) zinc] fluorescence quantum yield of the complex 1 ~ 12, Stokes shift, and the calculated transition dipole moment.

  (A) The fluorescence quantum yield (QY) of these chemical species was determined by the reference method using the following relationship.

Here, ∫I _complex and ∫I _standard are the total integrated fluorescence intensity of the complex and the luminescent standard, respectively. A _complex and A _standard are absorbances specific to the corresponding wavelength, and QY _standard is the acceptable fluorescence QY value of the standard chromophore. The quantity (n 0 _complex / n 0 _standard ) ² represents the correction of the refractive index of the solvent. Steady state fluorescence emission spectra were obtained with a Perkin-Elmer LS 50 Luminescence Spectrometer. The concentration of all samples was adjusted so that the absorbance was 0.01 to 0.04 at the wavelength of the excitation light. All spectra were collected using a single excitation and emission monochromator set at 5 nm. Fluorescence spectra obtained for the (porphinate) zinc (II) complex as well as the chromophore used as the luminescence standard were determined using a calibrated light source spectral output obtained from National Bureau of Standards, USA. Corrections were made to account for the wavelength dependent efficiency of. Secondary correction of the emission spectrum used to determine QY (eg, energy dependent intensity correction required for analysis grating monochromator variable bandpass / constant wavelength resolution data acquisition mode) is made by Lakowicz. Performed as outlined. Quantum yield was determined using two standards for each of the conjugated bis- and tris [(porphinate) zinc (II)] complexes. (Tetraphenylporphinate) zinc (II) (TPPPZn) (QY = 0.033, benzene) serves as the standard porphyrin fluorescent emitter, while sufficient overlap with that of the complex whose emission band shape is unknown. The standard laser dye shown serves as a secondary standard. The standard fluorescent emitters used were [dye (QY; solvent; λ _em (nm)]: (i) TPPZn (0.033; benzene); (598, 647)); (ii) TPPZn (0.028; 10: 1 CHCl ₃ : pyridine; (613,661)); (iii) DODCI (0.44; EtOH; (605)); (iv) HITCI (0.28; MeOH (59); (660)); (V) IR-125 (0.13; DMSO; (826)); (vi) DTDCI (0.78; DMSO; (684)). When TPPZn was used as the standard fluorescent emitter, both unknown and standard samples were excited at either 400 or 428 nm. DODCI, HITCI, when using IR-125 and DTDCI dyes as luminescent standard compound, lambda _ex corresponds to the interior of the wavelength of the multiple spaces of Q- states of Compound 1-12. As a verification for internal consistency, the QY for each emission standard was experimentally evaluated by a reference method using other laser dyes as standard fluorescent emitters. In all such experiments, the calculated QY is consistent with established literature values within ± 10%, and the emission correction factor used over the entire 600-850 nm region in these experiments is appropriate. It was confirmed that there was. The standard error of the quantum yield determined in this way is typically taken as ± 20% of the reported value. The listed QY values correspond to the average of measurements taken at least three times independently.

  (B) Transition dipole moment is a relational expression

Is calculated by plotting in an integral manner. Here, n ₀ is the refractive index of the solvent, and μ is Debye's transition dipole moment. For these calculations, the transition dipole moment in the B absorption band region corresponds to the integration performed over the 360 to 520 nm spectral region, while the reported Q absorption band value is 520 to 520 nm. Derived from similar integration over a wavelength of 900 nm.

  (C) R.I. Monshower, M, Abrahamsson, F.M. van Mourik, R.A. van Grondelle, J.M. Phys. Chem. B101, 7241-7248 (1997).

Relative radiation lifetime and emission dipole intensity of conjugated chromophores 1-12 relative to a standard biological antenna system.

(A) Radiation lifetime was calculated using the relationship τ _rad = τ _F / QY. The QY (fluorescence quantum yield) value used is an average of the values reported in Table II.

(B) Luminescence dipole intensity = <μ> _chromophore / <μ> _reference . The value of <μ> was determined using equation (5). The light emission energy used for this calculation corresponds to the frequency that divides the intensity of the integrated light emitting oscillator into blue and red components having equivalent areas. For Compound 1-12, emission dipole strengths are based both derived from ethyne as a TPPZn and appropriate standards (porphinato) zinc (II) monomers.

(C) For meso-meso and meso-β cross-linked sequence compounds, compound 1 acts as a porphyrin chromophore incorporating standard ethyne, and for β-β cross-linked compounds (porphinate) zinc ( II) Species 3 was used as a reference for the conjugated pigment.

  (D) Determined by van Grondelle.

Claims (16)

Conjugated compound comprising at least two covalently bonded substructures, and absorbs and emits light at a wavelength at which the compound cannot substantially react with the compound and the compound absorbs and emits light Characterized in that it comprises a dye solution disposed in a resonant cavity comprising a non-aqueous solvent substantially impossible to do, and a pumping energy source that produces stimulated emission in the dye solution laser. Conjugated compounds comprising at least two covalently bonded substructures, and hosts that cannot chemically react with the compounds and cannot absorb and emit light at wavelengths where the compounds absorb and emit light A laser comprising: a solid comprising a polymer; and an energy source coupled to the solid to generate light in the solid. Conjugated compounds comprising at least two covalently bonded substructures, and hosts that cannot chemically react with the compounds and cannot absorb and emit light at wavelengths where the compounds absorb and emit light A laser comprising: a solid containing a polymer; and an energy source coupled to the host polymer to generate light in the host polymer.   An optical amplifier comprising a conjugated compound comprising a polymeric optical waveguide and at least two covalently bonded substructures.   An electroconductive organic polymer body defining a porous network having an open porous network configuration and creating voids with an extended surface area, and the porous network A weight comprising an active electronic material comprising a conjugated compound comprising at least two covalently bonded substructures disposed within at least a portion of a defined void space Combined lattice.   6. The polymer lattice of claim 5, wherein the conductive organic polymer comprises a conjugated compound comprising at least two covalently bonded partial structures.   An electrically conductive organic polymer body electrically connected to an electrical coupler, the body having the form of an open porous network and having an expanded surface area A body of electrically conductive organic polymer defining a porous network that forms a substrate, and at least two shares disposed within at least a portion of a void space defined by the porous network A polymer lattice electrode comprising an active electronic material comprising a conjugated compound comprising a bonded partial structure.   A triode of a solid polymer lattice with a first electrode and a second electrode spaced apart from each other, the open pores between the first electrode and the second electrode Sandwiched by a polymer lattice comprising a body of electrically conductive organic polymer defining a porous network that forms voids with an extended surface area in the form of a quality network A triode of polymer lattice, wherein the conductive organic polymer comprises a conjugated compound comprising at least two covalently bonded partial structures.   A triode of a luminescent polymer lattice comprising a first electrode and a second electrode spaced apart from each other, the open porous being between the first electrode and the second electrode A polymer lattice comprising a body of an electrically conductive organic polymer defining a porous network that forms a void having an extended surface area and having a network structure is disposed between In addition, a light-emitting semiconductor electronic material having an activity of transporting charge carriers between the first and second electrodes is inserted between the first and second electrodes. The carrier is affected by the polymer lattice such that when a voltage is applied between the first and second electrodes, a charge carrier is injected and light is emitted. Emissive semiconductor electronic material with at least two covalent bonds Triode luminescent polymer lattice which is characterized in that it comprise a conjugated compound comprising a partial structure. A conductive first layer having a high work function;
A second layer of semiconductor comprising a conjugated compound comprising at least two covalently bonded substructures in contact with the first layer; and a conductive third layer in contact with the second layer A diode comprising:
A source of reverse bias across the diode;
A source that impinges light on the diode;
A light-responsive diode system comprising a source for detecting a current generated by a diode when the diode is reverse-biased and light collides with the diode. A conductive first layer having a high work function;
A second layer of semiconductor comprising a conjugated compound comprising at least two covalently bonded substructures in contact with the first layer; and a conductive third layer in contact with the second layer A diode comprising an inorganic semiconductor doped to produce a conductive state in the third layer;
A source of reverse bias across the diode;
A source that impinges light on the diode;
A light-responsive diode system comprising a source for detecting a current generated by a diode when the diode is reverse-biased and light collides with the diode. A conductive first layer having a high work function;
A second layer of semiconductor comprising a conjugated compound comprising at least two covalently bonded substructures in contact with the first layer; and a conductive third layer in contact with the second layer A diode comprising:
A source of reverse bias across the diode;
A source that impinges light on the diode;
A dual-function light-emitting and light-responsive input comprising a source for detecting a current generated by the diode when a reverse bias is applied to the diode and light collides with the diode. Output diode system. A conductive first layer having a high work function;
A second layer of semiconductor comprising a conjugated compound comprising at least two covalently bonded substructures in contact with the first layer; and a conductive third layer in contact with the second layer A diode comprising:
A source of reverse bias across the diode;
A source that strikes the diode with an input signal or light;
A source for detecting the current produced by the diode when a reverse bias is applied and the light input signal impinges on the diode;
A source for stopping reverse biasing; and a source for applying an output signal with a forward bias suitable for causing the output signal to emit an optical output signal from the diode across the diode. A light-emitting and light-responsive input / output diode system having a dual function. A conductive first layer having a high work function;
A second layer of semiconductor comprising a conjugated compound comprising at least two covalently bonded substructures in contact with the first layer; and a conductive third layer in contact with the second layer In an input / output method having a dual function using a light emitting and photoresponsive input / output diode system comprising a diode comprising:
Reverse bias across the diode to impinge the light input signal on the diode;
Detecting a current or voltage generated by the diode as an input electrical signal when the diode is reverse-biased and a light input signal collides with the diode;
Stop applying the reverse bias,
Applying a positively biased output signal across the diode to cause an optical output signal to be emitted from the diode in response to an input to the diode. An article of manufacture comprising an integrated source of solid-state electromagnetic radiation, the source having two spaced apart conjugated compounds comprising at least two covalently bonded substructures A non-coherent electromagnetic radiation of a first wavelength is emitted from the compound of claim 1 comprising a layered structure comprising a number of layers including a disposed conductive layer, and further passing an electric current between the conductive layers. In products with contact points
The layered structure further comprises first and second cladding areas having a core area therebetween, and is disposed to receive at least a portion of the non-coherent electromagnetic radiation having a first wavelength. Have
The core region absorbs the non-coherent electromagnetic radiation having a first wavelength and is responsive to the absorbed non-coherent electromagnetic radiation and has a second wavelength longer than the first wavelength. A product characterized in that it comprises a second layer of organic material selected to emit strong electromagnetic radiation. Creating a conjugated compound comprising at least two covalently linked substructures,
Exposing the compound to an energy source under such effective conditions for a time effective for the compound to emit light having a wavelength of 650-2000 nm;
Determining whether the emitted light has an intensity greater than the sum of the light emitted by the substructure.

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