Officer, D. L. (2010). Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions. Macromolecules, 43 (8), 3817-3827. Indanedione-substituted poly(terthiophene)s: Processable conducting polymers with intramolecular charge transfer interactions AbstractThe electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of II D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedione-substituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The electronic conjugation of the produced polymers was characterized by Raman frequency dispersion experiments and show dispersion rate parameters similar to those observed for other substituted polythiophenes. ABSTRACT: The electrochemical and chemical syntheses of poly(terthiophene)s bearing an indanedione pendant group and displaying intramolecular charge transfer interactions have been achieved. The nature of the charge transfer interaction is characterized through DFT calculations and experimental studies, including resonance Raman spectroscopy and absorption and emission data through a Lippert-Mataga analysis. It is found that the low-energy transition present in the indanedione-bearing monomer species has considerable charge transfer character with a dipole change of 11 D. Decomposition of the indanedione group occurred during hydrazine reduction after chemical polymerization. A soluble, low molecular weight indanedionesubstituted polymer (weight average 4500 Da) was nonetheless obtained following the use of a milder reducing agent, triethanolamine. To the best of our knowledge, this is the first example of the use of triethanolamine for the reduction of an oxidized polythiophene, providing a milder and safer alternative to hydrazine. In an attempt to produce higher molecular weight processable polymers with intramolecular charge transfer interactions, a copolymer of the indanedione-substituted terthiophene and a dihexylterthiophene was synthesized. The ...

A new method for evaluating surface passivation of silicon surfaces using a strongly adsorbing and fluorescing perylenediimide (PDI) dye is reported. Silanes containing differing reactive groups delivering a trimethylsilyl moiety were investigated for their ability to passivate glass surfaces, both from solution and in the vapor phase, as a function of temperature and concentration. Among the silanizing agents used in this study were 1,1,1,3,3,3-hexamethyldisilazane ( HMDS), allyltrimethylsilane ( TMS-A), chlorotrimethylsilane ( TMS-Cl), N-(trimethylsilyl)imidazole ( TMS-Im), and N, N-dimethylaminotrimethylsilane ( TMS-DMA). Surface coverage was determined using fluorescence intensity. The highest surface coverage films were obtained on glass treated with HMDS vapor at 280 degrees C or with solutions of TMS-Im or TMS-DMA at 105 degrees C. These studies provide important insight into the optimal methods for surface passivation.

Chemical immobilization of a triethoxysilyl-functionalized hydrogen-bonding ureido-[2-(4-pyrimidone)] tetraplex produced interaction sites on a glass substrate that allowed association with a perylenediimide-functionalized tetraplex, providing noncovalent links of the fluorophore to the surface. The association between the self-complementary molecules was exceptionally strong, both in solution and at the surface, such that effective hydrogen-bonding was retained after repeated solvent washes.