Synthesis of Donor-σ-Perylenebisimide-Acceptor Molecules Having PEG Swallowtails and Sulfur Anchors

• Published in: Journal of organic chemistry Vol. 77; no. 21; pp. 9641 - 9651
• Main Authors: Kota, Rajesh, Samudrala, Ramakrishna, Mattern, Daniell Lewis
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 02-11-2012
• Subjects: Chemistry; Condensed benzenic and aromatic compounds; Electrochemistry; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Organic chemistry; Preparations and properties; Monolayer; Gold; Thiol; Transition element complexes; Ether; Pyrene derivatives; Transition metal; Metallocene; Organic sulfide; Perylene derivatives; Ferrocene; Characterization; Electrodes; Ethylene oxide polymer; Iron Organic compounds; Imide; Organic disulfide; Alkane; Aromatic compound; Chemical synthesis
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo301701a

Donor-σ-Acceptor (D-σ-A) molecules, arrayed in a monolayer between electrodes, can serve as molecular rectifiers. Using perylene-3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor allows the attachment of the donor group to one imide nitrogen and a solubilizing swallowtail, normally a long (e.g., C19) alkane connected at midchain, on the other. Such an alkyl tail facilitates the formation of Langmuir–Blodgett (LB) monolayers. We have employed several modified swallowtails to make new D-σ-A molecules: poly(ethylene glycol) (PEG) swallowtails with 6 ether oxygens or with 4 ether oxygens to promote hydrophilicity in orienting LB monolayers, and alkyl swallowtails ending with sulfur anchors (thioacetate, thiol, or methyl disulfide) to stabilize attachment of the D-σ-A molecules to gold electrodes. The preparation and characterization of D-σ-A molecules containing combinations of these swallowtails with pyrene, ferrocene, and tetramethylphenylenediamine donor groups is described.