Polymers comprising at least one unit of formulae

##STR00001##

and compounds of the formulae

##STR00002##

wherein, in formulae 1, 1′, 2 and 2′
n is 0, 1, 2, 3 or 4
m is 0, 1, 2, 3 or 4 M1 and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system;
X is at each occurrence selected from the group consisting of O, S, Se or Te,
Q is at each occurrence selected from the group consisting of C, Si or Ge
R is at each occurrence selected from the group consisting of hydrogen, C.sub.1-100-alkyl, C.sub.2-100-alkenyl, C.sub.2-100-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, a 5 to 20 membered heteroaryl, C(O)—C.sub.1-100-alkyl, C(O)—C.sub.5-12-cycloalkyl and C(O)—OC.sub.1-100-alkyl.
R.sup.2, R.sup.2′, R.sup.2″, R* are at each occurrence independently selected from the group consisting of hydrogen, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, 5 to 20 membered heteroaryl, OR.sup.21, OC(O)—R.sup.21, C(O)—OR.sup.21, C(O)—R.sup.21, NR.sup.21R.sup.22, NR.sup.21—C(O)R.sup.22, C(O)—NR.sup.21R.sup.22, N[C(O)R.sup.21][C(O)R.sup.22], SR.sup.21, halogen, CN, SiR.sup.SisR.sup.SitR.sup.Siu and OH,
L.sup.1 and L.sup.2 are independently from each other and at each occurrence selected from the group consisting of C.sub.6-30-arylene, 5 to 30 membered heteroarylene,

##STR00003##

The invention relates to novel organic semiconducting oligomers or polymers containing dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene units, methods for their preparation and educts or intermediates used therein, polymers, blends, mixtures and formulations containing them, the use of the oligomers, polymers, blends, mixtures and formulations as semiconductor in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these oligomers, polymers, blends, mixtures or formulations.

The invention relates to novel conjugated polymers containing one or more 5,6-difluoro-benzo[1,2,5]thiadiazole-4,7-diylunits (hereinafter referred to as “FF-BTZ” units) and two or more different bridged bithiophene units, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in, or for the preparation of, organic electronic (OE) devices, especially organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising, or being prepared from, these polymers, polymer blends, mixtures or formulations.

An organic compound comprising: ##STR00001## In this organic compound, W is selected from the group consisting of: S, Se, O, and N-Q; and Q is selected from the group consisting of: a straight-chain or branched carbyl, silyl, or hydrocarbyl, a branched or cyclic alkyl with 1 to 30 atoms, a fused substituted aromatic ring, and a fused unsubstituted aromatic ring. Additionally, in this organic compound Ar.sub.1 and Ar.sub.2 are independently selected from the group selected from: H, an aryl group, and a heteroaryl group.

A method of forming a polymer, the method comprising combining 4-bromo-7-[5-bromo-4-(alkyl)thiophen-2-yl]-6-chloro-5-fluoro-2,1,3-benzothiadiazole, (3,3′-difluoro-[2,2′-bithiophene]-5,5′-diyl)bis(trimethylstannane), [4-(alkyl)-5-[5-(trimethylstannyl)thiophen-2-yl]thiophen-2-yl]trimethylstannane, tris(dibenzylideneacetone), and dipalladium P(o-tol).sub.3 tris(2-methylphenyl)phosphane to form the polymer: ##STR00001##
In this polymer, W is selected from the group consisting of: S, Se, O, and N-Q. Additionally, Q is selected from the group consisting of: a straight-chain carbyl, silyl or hydrocarbyl, branched, cyclic alkyl with 1 to 30 atoms, and fused aromatic rings. Furthermore in this polymer, R.sub.1, and R.sub.4 are independently selected from the group consisting of: F, Cl, I, Br, CN, —NCO, —NCS, —OCN, —SCN, —OX, —SX, —NH.sub.2, —C(═O)X, —C(═O)—OX, —OX, —NHX, —NXX′, —C(═O)NHX, —C(═O)NXX′, —SO.sub.3X, —SO.sub.2X, —OH, —NO.sub.2, CF.sub.3, —SF.sub.5, a straight-chain or branched carbyl, silyl, or hydrocarbyl, a branched or cyclic alkyl with 1 to 30 atoms, a fused substituted aromatic ring, and a fused unsubstituted aromatic ring. This polymer can also have R.sub.2 and R.sub.3 are independently selected from F, Cl, Br and I. Additionally, in this polymer, the fused aromatic rings can be independently fused with groups consisting of: a straight-chain or branched carbyl, silyl, or hydrocarbyl, a branched or cyclic alkyl with 1 to 30 atoms, a fused substituted aromatic ring, and a fused unsubstituted aromatic ring. Lastly, in this polymer, h+j is between 0.2 to 0.6 and i+k is between 0.4 and 0.8.

The present invention discloses a terpolymer based on 2,5-bis(2-thienyl)thiazolo[5,4-d]thiazolyl. In the invention, by introducing 2,5-bis(2-thienyl)thiazolo[5,4-d]thiazole units, the conjugated length of the polymers is enlarged and the aggregation in solution becomes weak. The introducing of 2,5-bis(2-thienyl)thiazolo[5,4-d]thiazole unit can easily tune the photophysical properties and the aggregation structure of the terploymers, and the terpolymers show excellent photovoltaic performance. The terpolymers have the following general formula:

##STR00001##

The present invention generally relates to artificial photosystems and methods of their use, for example in artificial photosynthesis, wherein the artificial photosystems comprise one or more light-harvesting antenna (LHA) comprising a conjugated polyelectrolyte (CPE) complex (CPEC) comprising a donor CPE and an acceptor CPE, wherein the donor CPE and acceptor CPE are an electronic energy transfer (EET) donor/acceptor pair.

The present disclosure provides for the development and applications of monomeric, oligomeric and/or polymeric semiconductor materials comprising a five-membered heteroaromatic unit (e.g., thiophene; furan; selenophene; etc.) that includes an acrylyl or an acrylyl-like (—C═C—CO—) side chain. The semiconductor materials can be used as organic semiconductors for use in electronic, optical, or optoelectronic devices such as organic thin film transistors and organic photovoltaics. The disclosed semiconductor materials (e.g., semiconducting polymer compounds) can be used as high performance semiconductors (e.g., for organic solar cells or organic photovoltaics (OPVs)), and the disclosed semiconductor materials can be used for other devices (e.g., organic thin film transistors (OTFTs) and sensors, etc.).

The organic semiconductor polymers relate to polymers containing an indolo-naphthyridine-6,13-dione thiophene (INDT) chromophore. The organic semiconductor polymers are formed by polymerizing INDT monomer with thiophene to obtain a conjugated polymer of the chromophore linked by thiophene monomers (INDT-T), with phenyl to obtain a conjugated polymer of the chromophore linked by phenyl monomers (INDT-P), with selenophene to obtain a conjugated polymer of the chromophore linked by selenophene monomers (INDT-S), or with benzothiadazole to obtain a conjugated polymer of the chromophore linked by benzothiadazole monomers (INDT-BT).

The invention relates to a blend containing an electron acceptor and an electron donor, the acceptor being an n-type semiconductor which is a small molecule that does not contain a fullerene moiety, the electron donor being a p-type semiconductor which is a conjugated polymer comprising donor and acceptor units in random sequence, to a formulation containing such a blend, to the use of the blend in organic electronic (OE) devices, especially organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photodetectors (OPD) and organic light emitting diodes (OLED), and to OE, OPV, PSC, OPD and OLED devices comprising the blend.