DE4242676A1 - New polymeric porphyrin compounds useful in electrical and optical uses - Google Patents

New polymeric porphyrin compounds useful in electrical and optical uses

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Publication number
DE4242676A1
DE4242676A1 DE19924242676 DE4242676A DE4242676A1 DE 4242676 A1 DE4242676 A1 DE 4242676A1 DE 19924242676 DE19924242676 DE 19924242676 DE 4242676 A DE4242676 A DE 4242676A DE 4242676 A1 DE4242676 A1 DE 4242676A1
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porph
metal atom
compound according
polycyclic ring
compound
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Herbert Dr Naarmann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

A new polymeric cpd. contains units of formula (1): -(-porph(Me)-R1-C=C-C=CR2-)-n (1), where in (1) n = degree of polymerisation; R1,R2 = a direct bond, oxygen, imino, oxymethylene, or iminomethylene; porph(Me) = a polycyclic ring of porphyrin type with a central metal atom, with the metal atoms covalently bonded to the bridging group (2): -R1-C=C=C=C-R2- (2).Also claimed is the production of these polymers.The polycyclic ring is porphyrin, chlorin (sic), or corrin. The metal atom is silicon, germanium or aluminium. The ring system may be substd. with one or more gps. chosen from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, perylenyl, or substd. by a divalent gp.

Description

Die Erfindung betrifft neue polymere Verbindungen, die entlang der Kette abwechselnd Einheiten mit einer Porphinstruktur und des Diacetylens aufweisen.The invention relates to new polymeric compounds that run along the chain alternately units with a porphine structure and the Have diacetylene.

Der Erfindung liegt die Absicht zugrunde, neue Polymersysteme mit definierter Anordnung zu erzeugen nämlich makrocyclische Scheiben (Porphine), die zusammen mit Abstandshaltern (sog. Spacern) neu­ artige Strukturen und damit neue Eigenschaftsmerkmale aufweisen.The invention is based on the intention of using new polymer systems to produce a defined arrangement namely macrocyclic discs (Porphine), which together with spacers (so-called spacers) new like structures and thus have new characteristics.

Die neuen Verbindungen haben die allgemeine Formel I (vgl. unten) und können wie folgt erhalten werden:The new compounds have the general formula I (see below) and can be obtained as follows:

Dabei bedeutet n den Polymerisationsgrad und R1, R2 kann eine einfache Bindung, Sauerstoff, Oxymethylen, Imino oder Imino­ methylen sein.Here n is the degree of polymerization and R 1 , R 2 can be a simple bond, oxygen, oxymethylene, imino or imino methylene.

Als Makrozyklen Porph (Me) kommen in Frage:
Porphin (II), Chlorin (III) oder Corrin: (IV)Porph (Me) macrocycles are:
Porphin (II), Chlorin (III) or Corrin: (IV)

X = CH: Porphin-Derivate
X = N : Tetraazaporphin-Derivate.X = CH: porphine derivatives
X = N: tetraazaporphin derivatives.

Als Metallatome kommen vorzugsweise Si, Ge oder Al in Frage; statt Cl kann auch Br vorliegen.Si, Ge or Al are preferably suitable as metal atoms; Br can also be present instead of Cl.

Als Alkine sind geeignet: HO-CH2-C≡CH bzw. H2N-CH2-C≡CH sowie Alkine des Typs HO-R-C≡CH bzw. H2N-R-C≡CH.Suitable alkynes are: HO-CH 2 -C≡CH or H 2 N-CH 2 -C≡CH and alkynes of the type HO-RC≡CH or H2N-RC≡CH.

In der Formel II bedeutet R Wasserstoff oder Phenyl, Biphenylyl, Terphenylyl, Naphthyl, Ahthryl, Phenanthryl, Perylyl.In formula II, R denotes hydrogen or phenyl, biphenylyl, Terphenylyl, Naphthyl, Ahthryl, Phenanthryl, Perylyl.

Als Diine sind z. B. die folgenden Zwischenprodukte denkbar:
HO≡C-C≡C-OH, HO-C≡-C≡C-NH2 oder H2N-C≡C-C≡C-NH2, sowie entspre­ chend HO-CH2≡C-C≡C-CH2-OH usw.As diines are e.g. B. the following intermediates are conceivable:
HO≡CC≡C-OH, HO-C≡-C≡C-NH 2 or H 2 NC≡CC≡C-NH 2 , and accordingly HO-CH 2 ≡CC≡C-CH 2 -OH etc.

Will man Verbindungen erhalten, in denen R1, R2 eine einfache Bin­ dung bedeutet, so geht man wie folgt vor:
Das vorgesehene Prophin wird in Form des Dichlorids mit 2 mol Trimethylsilylacetylen zum Porphin-diacetylen umgesetzt und das (monomere) Umsetzungsprodukt oxidativ gekuppelt oder man setzt das Dichlorid direkt mit vorgebildetem Bis-trimethylsilyldiacety­ len um.If you want to obtain connections in which R 1 , R 2 is a simple bond, proceed as follows:
The proposed propyne is reacted in the form of the dichloride with 2 mol of trimethylsilylacetylene to form porphine diacetylene and the (monomeric) reaction product is oxidatively coupled or the dichloride is reacted directly with preformed bis-trimethylsilyldiacetylene.

Der Halogenaustausch durch -C≡CH mit Hilfe der Trimethylsilylver­ bindung ist z. B. von T. Sakamoto et al. (Synthesis Comm., 1982, 312-314) und von S. Takushita et al. (Synthesis Comm. 1980, 627-630) beschrieben. The halogen exchange by -C≡CH using the trimethylsilylver bond is z. B. by T. Sakamoto et al. (Synthesis Comm., 1982, 312-314) and by S. Takushita et al. (Synthesis Comm. 1980, 627-630).  

Die Herstellung des Porphin-dihalogenids kann nach den Angaben in Inorganic Chemistry 4, (1965) p 128) geschehen; dort ist die Dar­ stellung von Dichlor(phthalocyanino)silicon beschrieben.The production of the porphine dihalide can be carried out according to the information in Inorganic Chemistry 4, (1965) p 128); there is the dar position of dichloro (phthalocyanino) silicon.

Die Synthese geht aus von 1,3-Diiminoisoindolenin, das in Chinolin mit SiCl4 umgesetzt wird:The synthesis starts from 1,3-diiminoisoindolenine, which is reacted in quinoline with SiCl 4 :

Die Umsetzungen des PcSiCl2 mit den Mono- bzw. Diinen erfolgt unter den klassischen Bedingungen einer nukleophilen Substitution, d. h. in Dimethylformamid, Toluol, Chinolin und Abpuffern mit einer Base, z. B. Triisopropylamin oder aber in Gegenwart von Kronenethern unter Phasentransfer-Bedingungen (Lit. Synthetic Metals 48, p 295 1992).The PcSiCl 2 is reacted with the mono- or diynes under the classic conditions of nucleophilic substitution, ie in dimethylformamide, toluene, quinoline and buffers with a base, e.g. B. triisopropylamine or in the presence of crown ethers under phase transfer conditions (Lit. Synthetic Metals 48, p 295 1992).

Die erhaltenen erfindungsgemäßen Produkte werden bei Verwendung von Monoalkinen oxidativ gekuppelt (Organ. Chemie 11, S. 341, 1983, N.Y.E. Breitmaier, G. Jung sowie T.X. Newton, G.M. Whitesides, J. Org. Chem. 53 (1988) 2489) oder geben direkt bei Verwendung der Diine die erfindungsgemäßen Polymere.The products according to the invention obtained are used oxidatively coupled by monoalkynes (Organ. Chemie 11, p. 341, 1983, N.Y.E. Breitmaier, G. Jung and T.X. Newton, G.M. Whitesides, J. Org. Chem. 53 (1988) 2489) or give directly when using the diines, the polymers according to the invention.

Aufgrund der ungewöhnlichen Struktur d. h. der Abfolge von Por­ phinscheibchen mit starren Dialkingruppen haben die neuen erfin­ dungsgemäßen Polymere überraschende Anwendungsbereiche: z. B. als NLO-Materialien, als Sensoren, Elektroden, elektrisch leitfähige Polymere, kooperative Materialien mit opto-elektronischen Effekten.Due to the unusual structure d. H. the sequence of por phis disks with rigid dialking groups have invented the new ones Polymers according to the invention have surprising areas of application: B. as NLO materials, as sensors, electrodes, electrically conductive Polymer, cooperative materials with opto-electronic Effects.

In den folgenden Beispielen werden Synthese und Eigenschaften der neuen Polymeren vorgestellt. The following examples illustrate the synthesis and properties of the presented new polymers.  

Beispiel 1example 1 a) Umsetzungsprodukt von Dichlor(phthalocyanino)silicon (PcSiCl2) mit Propargylalkohol (molar 1 : 1)a) Reaction product of dichlor (phthalocyanino) silicon (PcSiCl 2 ) with propargyl alcohol (molar 1: 1) Cl-Porph(Si)-Cl + HO-CH2-C≡C-H → Cl-Porph(Si)-O-CH2-C≡CH (1)Cl-Porph (Si) -Cl + HO-CH 2 -C≡CH → Cl-Porph (Si) -O-CH 2 -C≡CH (1)

6,8 g PcSiCl2 (0,01 n) in 100 ml Dimethylformamid (DMF) wurden mit 0,56 g (0,01 n) Proparylalkohol versetzt, 15 h bei 60°C gerührt, anschließend wurde bei 0,1 mbar 50°C DMF abge­ zogen und das Produkt aus Chlornaphthalin umkristallisiert.6.8 g of PcSiCl 2 (0.01 n) in 100 ml of dimethylformamide (DMF) were mixed with 0.56 g (0.01 n) of proparyl alcohol, stirred for 15 h at 60 ° C, then 50 at 0.1 mbar ° C DMF deducted and the product recrystallized from chloronaphthalene.

Ausbeute: 4,3 g (1)
Fp: 290°C (Zer)Yield: 4.3 g (1)
Mp: 290 ° C (Zer)

Elementaranalyse:
Ber.: C 60,29; H 4,2; O 2,29; N 24,1; Cl 5,08; Si 4,02%
Gef.: C 60,5; H 4,6; O - ; N 24,5; Cl 4,9; Si 3,8%Elemental analysis:
Calculated: C 60.29; H 4.2; O 2.29; N 24.1; Cl 5.08; Si 4.02%
Found: C 60.5; H 4.6; O -; N 24.5; Cl 4.9; Si 3.8%

Molgewicht:
Ber.: 697,2
Gef.: 705 (osmometr.)Molecular weight:
Calculated: 697.2
Found: 705 (osmometr.)

b) Oxidative Kupplung des Reaktionsprodukts aus a) zum Diinb) Oxidative coupling of the reaction product from a) to the diyne

700 mg (1 mM) wurde in Aceton (100 ml) mit 250 mg CuCl und 2,5 und N,N,N′,N′-Tetramethylethyldiamin versetzt und bei Raumtemperatur ein intensiver Luftstrom durch die Lösung ge­ leitet (1 l Luft/min) 30 Minuten.700 mg (1 mM) was dissolved in acetone (100 ml) with 250 mg CuCl and 2.5 and N, N, N ', N'-tetramethylethyl diamine added and at At room temperature, an intense air flow through the solution conducts (1 l air / min) 30 minutes.

Das Reaktionsprodukt wurde abfiltriert, mit je 100 ml Aceton 3 mal gewaschen und bei 50°C und 0,1 mbar 12 Stunden getrock­ net.The reaction product was filtered off, each with 100 ml of acetone Washed 3 times and dried at 50 ° C and 0.1 mbar for 12 hours net.

Ausbeute: 650 mg
Fp: 320°C (Zer)Yield: 650 mg
Mp: 320 ° C (Zer)

Elementaranalyse:
Ber.: C 60,38; H 4,05; O 2,3; N 24,14; Cl 5,09; Si 4,02%
Gef.: C 60,5; H 3,9; O -; N 23,8; Cl 5,2; Si 3,9%Elemental analysis:
Calc .: C 60.38; H 4.05; O 2.3; N 24.14; Cl 5.09; Si 4.02%
Found: C 60.5; H 3.9; O -; N 23.8; Cl 5.2; Si 3.9%

Molgewicht:
Ber.: 1392,5
Gef.: 1450 (osmometr.)Molecular weight:
Calculated: 1392.5
Found: 1450 (osmometr.)

Beispiel 2Example 2 a) Umsetzungsprodukt von Dichlor(phthalocyamino)silicon mit Pro­ pargylalkohol (molar 2 : 1)a) Reaction product of dichlor (phthalocyamino) silicon with Pro pargyl alcohol (molar 2: 1) Cl-Porph(Si)-Cl + 2HO-CH2-C≡CH → HC≡C-CH2-O-Porph(Si)-O-CH2-C≡CH (3)Cl-Porph (Si) -Cl + 2HO-CH 2 -C≡CH → HC≡C-CH 2 -O-Porph (Si) -O-CH 2 -C≡CH (3)

Versuchsbedingungen entsprechend Beispiel 1a):Test conditions according to Example 1a):

Einsatzmengen:
6,8 g PcSiCl2 (0,01 M) + 1,12 g Proparylalkohol (0,02 M)Amounts used:
6.8 g PcSiCl 2 (0.01 M) + 1.12 g proparyl alcohol (0.02 M)

Ausbeute: 4,8 g
Fp: 275-290°C (Zer)Yield: 4.8 g
Mp: 275-290 ° C (Zer)

Elementaranalyse:
Ber.: C 63,67; H 4,5; O 4,46; N 23,45; Cl 3,92; Si - %
Gef.: C 63,4; H 4,6; O -; N 23,1; Cl 3,6; Si < 0,1%Elemental analysis:
Calculated: C 63.67; H 4.5; O 4.46; N 23.45; Cl 3.92; Si -%
Found: C 63.4; H 4.6; O -; N 23.1; Cl 3.6; Si <0.1%

Molgewicht:
Ber.: 716,8 Gef.: 740 (osmometr.)Molecular weight:
Calc .: 716.8 found: 740 (osmometr.)

b) Umsetzung (oxidative Kupplung) von 2a) zum Polymeren (4)b) conversion (oxidative coupling) of 2a) to the polymer (4)

Versuchsbedingungen entsprechend Beispiel 1b):Test conditions according to Example 1b):

Einsatzstoffmengen:
717 mg (3), 100 ml Aceton, 250 mg CuICl, 2,5 ml TetramethylethyldiaminAmounts of feed:
717 mg (3), 100 ml acetone, 250 mg CuICl, 2.5 ml tetramethylethyl diamine

Ausbeute: 690 mg
Fp: 340°C (Zer. spontan)Yield: 690 mg
Mp: 340 ° C (cer.spontaneous)

Elementaranalyse:
Ber.: C 63,38; H 4,23; O 4,48; N 23,51; Si 3,93%
Gef.: C 63,6; H 4,3; O -; N 23,1; Si 3,7%Elemental analysis:
Calc .: C 63.38; H 4.23; O 4.48; N 23.51; Si 3.93%
Found: C 63.6; H 4.3; O -; N 23.1; Si 3.7%

Molgewicht:
(4) ist unlöslich, aufgrund von C13 Festkörper NMR (Vorliegen von C≡C-ProtonenMolecular weight:
(4) is insoluble due to C 13 solid-state NMR (presence of C≡C protons

HC≡C-CH2O-Porph(Si)-O-CH2-C≡CHC≡C-CH 2 O-Porph (Si) -O-CH 2 -C≡C

[-C≡C-CH2-O-Porph(Si)-O-CH2-C≡C-]n [-C≡C-CH 2 -O-Porph (Si) -O-CH 2 -C≡C-] n

Hier null Gefunden: ca. 0,1 , d. h. n 20Found here: approx. 0.1, d. H. n 20

Beispiel 3Example 3 Umsetzung von Dichlor (Phthalocyanino)silicon mit Hexadiindiol molar 1 : 1Reaction of dichlor (phthalocyanino) silicon with hexadiindiol molar 1: 1 Cl-Porph(Si)-Cl + HO-CH2-C≡C-C≡C-CH2-OH → -O-CH2C≡C-C≡C-CH2O-Porph(Si)-O-CH2-C≡C-C≡C-CH2O-Porph(Si)-Cl-Porph (Si) -Cl + HO-CH 2 -C≡CC≡C-CH 2 -OH → -O-CH 2 C≡CC≡C-CH 2 O-Porph (Si) -O-CH 2 - C≡CC≡C-CH 2 O-Porph (Si) -

Versuchsbedingungen entsprechend Beispiel 1a):Test conditions according to Example 1a):

Einsatzstoffmengen:
6,8 h PcSiCl2 (= 0,1 M), 1,1 g Hexadiindiol (0,01 M)Amounts of feed:
6.8 h PcSiCl 2 (= 0.1 M), 1.1 g hexadiindiol (0.01 M)

Ausbeute:
6,8 g eines unlöslichen Polymeren ca. 1 g lösliche Produkte, die durch Extraktion mit Chlornaphthalin abgebaut werden.
Fp: 290°C (Zer)Yield:
6.8 g of an insoluble polymer approx. 1 g of soluble products, which are broken down by extraction with chloronaphthalene.
Mp: 290 ° C (Zer)

Elementaranalyse:
Ber.: C 63,85; H 4,2; O 4,4; N 23,5; Si 3,93; Cl - %
Gef.: C 63,2; H 4,3; O - ; N 23,6; Si 3,5; Cl < 0,1%Elemental analysis:
Calc .: C 63.85; H 4.2; O 4.4; N 23.5; Si 3.93; Cl -%
Found: C 63.2; H 4.3; O -; N 23.6; Si 3.5; Cl <0.1%

Molgewicht:
Bestimmung analog Beispiel 2.Molecular weight:
Determination analogous to example 2.

AnwendungsbeispieleExamples of use

Die Reaktionsprodukte aus Beispiel 1, 2 und 3 wurden jeweils mit einer 10%igen FeCl3 Lösung in Acetonitril versetzt (je 50 mg Sub­ stanz, 4 Tage bei Raumtemperatur, dann abfiltriert und getrocknet 3 h 0,1 Torr 70°C) die Messung der elektrischen Leitfähigkeit in einer Mikromeßapparatur (Verwendung von gepreßten Probekörpern ⌀ 4 mm, Dicke 1,5 mm) ergab die folgenden Werte:The reaction products from Examples 1, 2 and 3 were each mixed with a 10% FeCl 3 solution in acetonitrile (50 mg substance each, 4 days at room temperature, then filtered off and dried for 3 h 0.1 Torr 70 ° C.) the measurement The electrical conductivity in a micro measuring apparatus (using pressed test specimens ⌀ 4 mm, thickness 1.5 mm) gave the following values:

σ [S/cm]
(1) 2·10-1
(2) 4,5·10⁺1
(3) 7·10⁺1
(4) 2,5·10⁺1
(5) 3·10⁺1.σ [S / cm]
(1) 2 · 10 -1
(2) 4.5 · 10⁺ 1
(3) 7 · 10⁺ 1
(4) 2.5 · 10⁺ 1
(5) 3 · 10⁺ 1 .

Anmerkungannotation

Das Reaktionsprodukt des Beispiels 3 isomerisiert beim Lagern (< 3 Tage bei Raumtemperatur) oder Tempern (z. B. 10 Min < 100°C) und bilden en-in-Strukturen d. h.The reaction product of Example 3 isomerizes on storage (<3 days at room temperature) or tempering (e.g. 10 min <100 ° C) and form en-in structures d. H.

-Porph(Si)-O-CH2-C≡C-C≡C-CH2-O-Porph(Si)--Porph (Si) -O-CH 2 -C≡CC≡C-CH 2 -O-Porph (Si) -

geht über in:merges into:

-Porph(Si)-OCH=CH-C≡C-CH=CH-O-Porph(Si)--Porph (Si) -OCH = CH-C≡C-CH = CH-O-Porph (Si) -

Claims (7)

1. Polymere Verbindung, aufgebaut aus Einheiten der allgemeinen Formel I wobei n den Polymerisationsgrad, R1, R2 eine einfache Bindung, Sauerstoff, Imino, Oxymethylen oder Iminomethylen und Porph(Me) einen ein zentrales Metallatom aufweisenden poly­ cyclischen Ring vom Porphintypus bedeutet, der über kovalente Bindungen des Metallatoms an die Brückenglieder -R1-C≡C-C≡C-R2- der polymeren Verbindung gebunden ist.1. Polymeric compound composed of units of the general formula I where n is the degree of polymerization, R 1 , R 2 is a simple bond, oxygen, imino, oxymethylene or iminomethylene and porph (Me) is a polycyclic ring of the porphine type which has a central metal atom and which is linked to the bridge members -R 1 via covalent bonds of the metal atom -C≡CC≡CR 2 - the polymeric compound is bound. 2. Verbindung nach Anspruch 1, deren polycyclischer Ring ausge­ wählt ist aus - gegebenenfalls substituierten - Porphin, Chlorin und Corrin.2. A compound according to claim 1, the polycyclic ring out selects from - optionally substituted - porphin, Chlorin and corrin. 3. Verbindung nach Anspruch 2, deren Metallatome ausgewählt sind aus Silicium, Germanium oder Aluminium.3. A compound according to claim 2, the metal atoms of which are selected made of silicon, germanium or aluminum. 4. Verbindung nach Anspruch 2, deren Porphinring einbindig sub­ stituiert ist durch einen oder mehrere Substituenten, ausge­ wählt aus Phenyl, Biphenylyl, Terphenylyl, Naphthyl, Anthryl, Phenanthryl, Perylyl oder zweibindig durch entsprechende zweiwertige Reste, wobei jeweils die Verknüpfung auch über Methylen bewirkt sein kann.4. A compound according to claim 2, the porphine ring monovalent sub is substituted by one or more substituents selects from phenyl, biphenylyl, terphenylyl, naphthyl, anthryl, Phenanthryl, perylyl or divalent by appropriate divalent residues, the link also via Methylene can be effected. 5. Verbindung nach Anspruch 2, enthaltend weiterhin einpolymeri­ sierte Einheiten ausgewählt aus Phenylen, Biphenylen, Napthy­ len, Anthrylen.5. A compound according to claim 2, further comprising einpolymeri units selected from phenylene, biphenylene, naphthy len, anthrylene. 6. Verfahren zur Herstellung von Verbindungen I nach Anspruch 1, dadurch gekennzeichnet, daß ein Dihalogenid eines das zen­ trale Metallatom aufweisenden Porphins mit jeweils zwei Äqui­ valenten Propargylalkohol und/oder Propargylamin umgesetzt und das gebildete Diin durch oxidative Kupplung polyaddiert wird.6. A process for the preparation of compounds I as claimed in claim 1, characterized in that a dihalide of the zen Porphins with trale metal atom, each with two equi valence propargyl alcohol and / or propargylamine implemented and the diyne formed is added by oxidative coupling becomes. 7. Abänderung des Verfahrens nach Anspruch 6 zur Herstellung von Verbindungen I, dadurch gekennzeichnet, daß man je zwei Äquivalente Propargylalkohol und/oder Propargylamin oxidativ zum Diol, Aminoalkohol bzw. Diamin kuppelt und das Produkt mit dem Dihalogenid zur Verbindung I umsetzt.7. Modification of the method according to claim 6 for the production of Compounds I, characterized in that two Equivalent propargyl alcohol and / or propargylamine oxidative couples to the diol, amino alcohol or diamine and the product reacted with the dihalide to give compound I.
DE19924242676 1992-12-17 1992-12-17 New polymeric porphyrin compounds useful in electrical and optical uses Withdrawn DE4242676A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1594876A1 (en) * 2003-01-31 2005-11-16 University of Wollongong Conducting polymers with porphyrin cross-linkers
WO2014030768A1 (en) * 2012-08-22 2014-02-27 Canon Kabushiki Kaisha Phthalocyanine pigment and pigment dispersion, ink and color filter resist composition containing same
CN109867770A (en) * 2019-03-11 2019-06-11 吉林大学 Conjugation microporous polymer and the preparation method and application thereof based on porphyrin functional group

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1594876A1 (en) * 2003-01-31 2005-11-16 University of Wollongong Conducting polymers with porphyrin cross-linkers
EP1594876A4 (en) * 2003-01-31 2008-07-09 Univ Wollongong Conducting polymers with porphyrin cross-linkers
WO2014030768A1 (en) * 2012-08-22 2014-02-27 Canon Kabushiki Kaisha Phthalocyanine pigment and pigment dispersion, ink and color filter resist composition containing same
CN104583336A (en) * 2012-08-22 2015-04-29 佳能株式会社 Phthalocyanine pigment, and pigment dispersion, ink and color filter resist composition containing same
CN109867770A (en) * 2019-03-11 2019-06-11 吉林大学 Conjugation microporous polymer and the preparation method and application thereof based on porphyrin functional group
CN109867770B (en) * 2019-03-11 2021-11-30 吉林大学 Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof

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