Conjugated electroluminescent polymers and associated methods of preparation and use

A semiconductive composition, comprising at least one admixer and a polymer comprised of monomer units having the structure of formula (1)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• and
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

In a conductive composition comprised of a doped conjugated polymer, the improvement comprising employing a polymer or copolymer comprised of monomer units having the structure of formula (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene;
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged counterion.

In a field effect transistor comprising a gate electrode, a source electrode, a drain electrode, and a channel electrically connecting the source electrode and the drain electrode, the improvement which comprises employing a channel comprised of a polymer or copolymer comprised of monomer units having the structure of formula (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

In a photodetector device comprised of a semiconductive layer disposed between first and second electrodes, and a means for detecting a photocurrent flowing between the electrodes, the improvement which comprises employing a semiconductive layer comprised of a polymer or copolymer comprised of monomer units having the structure of formula (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkenylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

In a photovoltaic device useful for the generation of electrical power comprised of a first electrode, a semiconductive layer provided on the first electrode, and a second electrode provided on the light incidence surface of the semiconductive layer, the improvement which comprises employing a semiconductive layer comprised of a polymer or copolymer comprised of monomer units having the structure of formular (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

In a light-emitting electrochemical cell comprised of a conductive transparent or semitransparent substrate, a thin film of a conjugated polymer and an ionizable species deposited on the substrate, and an electrode deposited on the thin film, the improvement which comprises employing in the thin film a polymer or copolymer comprised of monomer units having the structure of formula (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

In an electrochemical sensor comprising a counter electrode, a working electrode, and a means for applying or measuring an electrical potential between the working and counter electrodes, the improvement which comprises employing on the surface of the working electrode a polymer or copolymer comprised of monomer units having the structure of formula (I)

• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

A cavity-emission electroluminescent device, comprising a layered structure of

• a hole-injection electrode layer,
• an electron-injection electrode layer, and
• a dielectric layer interposed between the hole-injecting and electron-injecting electrode layers and
• a cavity extending through at least the dielectric layer and one of the electrode layers and having an interior cavity surface comprising a hole-injection electrode region, an electron-injection electrode region and a dielectric region,
• wherein an electroluminescent coating material comprising a polymer or copolymer is in electrical contact with the hole-injection and electron-injection electrode regions of the interior cavity surface, and wherein said polymer or copolymer is comprised of monomer units having the structure of formula (I)
• wherein:
• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• L is alkylene, alkenylene, substituted alkylene, substituted alkenylene, heteroalkylene, heteroalkenylene, substituted heteroalkylene, substituted heteroalkenylene, arylene, heteroarylene, substituted arylene, or substituted heteroarylene,
• m is zero or 1;
• n is zero or 1;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, with the proviso that when m is 1, Q2 is other than H;
• and
• A− is a negatively charged conterion.

A conjugated polymer comprised of a poly(arylene)backbone containing repeating monomer units -[Ar1-Ar2]- and having a sidechain selected from —NQ1Q2 and —(N+Q1Q2Q3)A directly or indirectly bound to Ar1, wherein:

• Ar1 and Ar2 are independently selected from the group consisting of monocyclic, bicyclic and polycyclic arylene, heteroarylene, substituted arylene and substituted heteroarylene groups;
• Q1 is selected from the group consisting of aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• Q2 is selected from the group consisting of H, aryl, heteroaryl, substituted aryl, substituted heteroaryl, alkyl, and substituted alkyl;
• and
• Q3 is selected from the group consisting of alkyl and substituted alkyl, with the proviso that when the sidechain is —(N+Q1Q2Q3)A, then Q2 is other than H;
• and
• A- is a negatively charged counterion, and further wherein when said sidechain is directly bound to Ar1, then at least one of the following is satified:
• (a) the sidechain is —(N+Q1Q2Q3)A−;
• and
• (b) at least one of Ar1, Ar2, Q1, and Q2 is substituted with a substituent selected from —SO2H, —COOH, or —P(O)OH2 groups;
• C1-C20 hydrocarbyl or heteroatom-containing C1-C20 hydrocarbyl substituted with one or more —SO3H, —COOH, or —P(O)OH2 groups;
• or with organic or inorganic sulfonate, carboxylate or phosphonate salts;
• or a combination thereof.

A conjugated polymer comprised of a poly(paraphenylene) backbone containing repeating monomer units -[Ar1-Ar2]- and having a sidechain with the structure —NQ1Q2 directly or indirectly bound to Ar1, wherein:

• Ar1 and Ar2 are independently selected from the group consisting of phenylene and substituted phenylene;
• and
• Q1 and Q2 are independently selected from the group consisting of phenyl and substituted phenyl;
• and further wherein when said sidechain is directly bound to Ar1, then at least one of the following is satisfied:
• (a) the sidechain is —(N+Q1Q2Q3)A−, wherein Q3 is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, and substituted heteroalkyl, and A− is a negatively charged counterion;
• and
• (b) is least one of Ar1, Ar2, Q1, and Q2 is substituted with a substituent selected from —SO2H, —COOH, or —P(O)OH2 groups;
• C1-C20 hydrocarbyl or heteroatom-containing C1-C20 hydrocarbyl substituted with one or more —SO2H, —COOH, or —P(O)OH2 groups;
• or with organic or inorganic sulfonate, carboxylate or phosphonate salts;
• or a combination thereof.

A conjugated polymer having the structure

• wherein:
• Ar4 and Ar5 are independently selected from aryl, heteroaryl, substituted aryl and subustituted heteroaryl groups each containing one or two aromatic rings;
• X, Y, and Z are independently selected from the group consisting of N, CH, and CR1, wherein R1 is selected from the group consisting of —(Ar3)n-NAr4Ar5, C1-C12 alkyl, fluorinated C1-C12 alkyl, C1-C12 alkoxy, fluoro, cyano, nitro, —SO3H, —COOH, —O(PO)(OH)2, and organic and inorganic sulfonate, carboxylate and phosphonate salts;
• and
• W, X1, Y1, and Z1 are independently selected from the group consisting of N and CH.