Polydopamine and Its Derivative Materials: Synthesis and Promising Applications in Energy, Environmental, and Biomedical Fields

6.4. Polyynes 3123 6.5. Using R-Hydroxy Stannanes 3124 6.6. Using the Hurtley Reaction 3124 6.7. Using a Methylenation Reaction 3125 7. Conclusions and Future Prospects 3125 8. Uncommon Abbreviations 3125 9. Acknowledgments 3125 10. Note Added in Proof 3125 11. References 3126 * Authorstowhomcorrespondenceshouldbeaddressed(evano@chimie.uvsq.fr, nicolas.blanchard@uha.fr). † Université de Versailles Saint Quentin en Yvelines. ‡ Université de Haute-Alsace. Chem. Rev. 2008, 108, 3054–3131 3054

Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis.

“All new is well-forgotten old”, the proverb goes. The current “fluorine boom” is news only to a novice in the field: the exceptional importance of fluorinated organic compounds in numerous areas has been known for a long time. The sharpest increase in the number of fluorine-containing pharmaceuticals and agrochemicals is dated back to 30 years ago. Also around that time (1979), the first monograph devoted to industrial applications of organofluorine compounds was published, covering not only fluorine-containing biologically active materials but also refrigerants, propellants, surfactants, textile chemicals, polymers, and dyes. The increasingly broad realization of the key role of organofluorine compounds in numerous areas has recently attracted many new scientists to the field. The development of new methods for the selective introduction of fluorine and fluorinecontaining groups into organic molecules for biologically active and other useful materials has become a hot area. Over 100 reviews, book chapters, and highlights on this subject have appeared in the literature in the past few years. As citing all of these publications in this review article is impossible, we provide references to only the most recent, general, and comprehensive ones. Molecules bearing a trifluoromethyl group constitute one of the most important classes of selectively fluorinated compounds. As early as 1928, Lehmann reported his observations of biological activity of some trifluoromethylated organic derivatives and already in 1959 Yale published a detailed review article entitled “The Trifluoromethyl Group in Medicinal Chemistry”. Since then, numerous books and reviews have appeared in the literature covering various aspects of trifluoromethylated organic and organometallic compounds. Within this family, derivatives bearing the CF3 group on aromatic rings are particularly numerous and important. Some examples of such compounds used as active ingredients of pharmaceuticals and agrochemicals are shown in Scheme 1. Trifluoromethylated building blocks and intermediates are clearly needed to make such molecules. The simplest trifluoromethylated aromatic compound, benzotrifluoride, was originally prepared by Swarts at the end of the 19th century. In his work, Swarts treated benzotrichloride with “two thirds of its weight of antimony fluoride” to obtain a mixture of PhCF2Cl and PhCF3, from which the two were separated and isolated pure by distillation. In the early 1930s, two industrial groups, one from Kinetic Chemicals, Inc. and one from I. G. Farbenindustrie AG patented their discoveries on the successful use of HF instead of SbF3 for the Swarts reaction. These inventions were the starting point for the modern large-scale manufacturing of trifluoromethylated aromatics. Other methods have been developed for conversion of various C1 units on the ring to CF3 with a variety of fluorinating agents. While representing an outstanding discovery and a classic of organic and organofluorine chemistry, the Swarts reaction is nonetheless neither atom-economical nor environmentally benign, as it deals with stoichiometric quantities of hazardous chemicals and generates large amounts of chlorine waste. To convert a CH3 group on the ring to CF3, the methyl is first exhaustively chlorinated to produce 3 equiv of HCl as a

Aromatic Trifluoromethylation with Metal Complexes

White organic light emitting diodes (WOLEDs) are promising devices for application in low energy consumption lighting since they combine the potentialities of high efficiency and inexpensive production with the appealing features of large surfaces emitting good quality white light. However, lifetime, performances and costs still have to be optimized to make WOLEDs commercially competitive as alternative lighting sources. Development of efficient and stable emitters plays a key role in the progress of WOLED technology. This tutorial review discusses the main approaches to obtain white electroluminescence with organic and organometallic emitters. Representative examples of each method are reported highlighting the most significant achievements together with open issues and challenges to be faced by future research.

Electroluminescent materials for white organic light emitting diodes

Fluorinated organic materials for electronic and optoelectronic applications: the role of the fluorine atom

Dr. M. Ambrico , Dr. P. F. Ambrico CNR-Istituto di Metodologie Inorganiche e dei Plasmi-UOS di Bari70125 Bari, Italy E-mail: marianna.ambrico@ba.imip.cnr.it Dr. A. Cardone , Dr. S. R. Cicco CNR-Istituto di Chimica dei Composti OrganoMetallici-UOS di Bari70125 Bari, Italy Ligonzo , Dr. . T Prof. Augelli . V Dipartimento Interateneo di FisicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy Dr. R. Di Mundo , Prof. G. M. arinola F Dipartimento di ChimicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy

Melanin Layer on Silicon: an Attractive Structure for a Possible Exploitation in Bio-Polymer Based Metal- Insulator-Silicon Devices

Synthesis of Poly(arylenevinylene)s with Fluorinated Vinylene Units

Hysteresis-type current–voltage characteristics in Au/eumelanin/ITO/glass structure: Towards melanin based memory devices

The third-order nonlinear optical properties of a series of copoly(2, 3, 5, 6-tetrafluoro-1, 4-phenylenevinylene-2, 5-dioctyloxy-1, 4-phenylenevinylene) that contain variable ratios of two differently substituted monomers have been studied in chloroform solutions at l=1064 nm by the picosecond Z-scan technique. Nonlinear refractive index n(2) of the samples investigated has been found to be negative, and a strong dependence of its magnitude on the copolymer's composition has been observed. The highest third-order nonlinear optical susceptibility, |x((3))|=(6 +/- 2)x 10(-10) esu, was measured for a copolymer obtained by reaction of equimolar quantitites of the parent monomers.

High third-order nonlinear optical susceptibility in new fluorinated poly(p-phenylenevinylene) copolymers measured with the Z-scan technique

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (e), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient e of over 14,000 M–1 cm–1 and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient e > 42,000 M–1 cm–1), until reaching the higher value (e > 69,000 M–...

Antonio Cardone

Papers

Melanin Layer on Silicon: an Attractive Structure for a Possible Exploitation in Bio-Polymer Based Metal- Insulator-Silicon Devices

Synthesis of Poly(arylenevinylene)s with Fluorinated Vinylene Units

Hysteresis-type current–voltage characteristics in Au/eumelanin/ITO/glass structure: Towards melanin based memory devices

High third-order nonlinear optical susceptibility in new fluorinated poly(p-phenylenevinylene) copolymers measured with the Z-scan technique

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells