Oligophenylene monomers and polymeric precursors for producing graphene nanoribbons

A process for the preparation of an oligophenylene monomer of formula I

• by Diels-Alder reaction of 4,4′-dibromo-2,2′-diethynyl-1,1′-biphenyl
• with tetraphenylcyclopentadienone
• wherein
• R1, R2, R3 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.

A process for the preparation of an oligophenylene monomer of formula II

• by Diels-Alder reaction of 4,4′-dibromo-2,2′-diethynyl-1,1′-biphenyl
• with phencyclone
• wherein
• R1, R2, R3 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.

A process for the preparation of a monomer of formula IIIa

• wherein X=halogen
• by Diels-Alder reaction of
• wherein X is halogen,
• with tetraphenylcyclopentadienone
• wherein
• R1, R2, R3 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.

A process for the preparation of a monomer of formula IIIb

• wherein Y=halogen,
• by Diels-Alder reaction of
• wherein Y=halogen,
• with tetraphenylcyclopentadienone
• wherein
• R1, R2 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.

A process for the preparation of a monomer of formula IVa

• wherein X=halogen,
• by Diels-Alder reaction of
• wherein X=halogen,
• with phencyclone
• wherein
• R1, R2, R3 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.

A process for the preparation of a monomer of formula IVb

• wherein Y=halogen,
• by Diels-Alder reaction of
• wherein Y=halogen,
• with phencyclone
• wherein
• R1, R2 are each independently H, halogen, —OH, —NH2, —CN, —NO2, a linear or branched, saturated or unsaturated C1-C40 hydrocarbon residue, optionally substituted 1- to 5-fold with halogen, —OH, —NH2, —CN and/or —NO2, and wherein one or more CH2-groups can be replaced by —O—, —S—, —C(O)O—, —O—C(O)—, —C(O)—, —NH— or —NR—, wherein R is an optionally substituted C1-C40 hydrocarbon residue, or an optionally substituted aryl, alkylaryl or alkoxyaryl residue.