Tuning Thiophene with Phosphorus: Synthesis and Electronic Properties of Benzobisthiaphospholes. Issue 25 (9th May 2014)

• Record Type: Journal Article
• Authors: Qiu, Yunyan; Worch, Joshua C.; Chirdon, Danielle N.; Kaur, Aman; Maurer, Andrew B.; Amsterdam, Samuel; Collins, Christopher R.; Pintauer, Tomislav; Yaron, David; Bernhard, Stefan; Noonan, Kevin J. T.
• Is Part Of: Chemistry. Volume 20:Issue 25(2014)
• Page Start: 7746
• Page End: 7751
• Publication Date: 2014-05-09
• Subjects: fused‐ring systems -- heterocycles -- n‐type acceptors -- organic electronics -- phosphorus heterocycles; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402561
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 1, 4‐Dimercapto‐2, 5‐diphosphinobenzene and 3, 6‐bis(hexyloxy)‐1, 4‐dimercapto‐2, 5‐diphosphinobenzene were synthesized and combined with various acid chlorides to obtain a series of benzobisthiaphospholes. Electrochemical and photophysical properties of the substituted benzobisthiaphospholes have been evaluated, and the observed reductions are more facile than the related benzothiaphospholes and 2, 6‐diphenylbenzobisthiazole. A benzobisthiaphosphole with C6 H4 ‐ p ‐CN substituents was reduced at E 1/2 =−1.08 V (vs. saturated calomel electrode (SCE)). X‐ray diffraction data for several of these phosphorus heterocycles has been obtained, and DFT calculations at the B3LYP level have been performed. Abstract : Fused‐ring systems : Energetic tuning of conjugated building blocks can be achieved by atomic modulation of aromatic architectures. A phosphorus mimic of benzodithiophene and benzobisthiazole has been synthesized and structurally characterized (see figure). The UV/Vis spectrum of the phosphorus heterocycle is significantly redshifted compared to its organic counterparts. The redox properties of the benzobisthiaphospholes have been probed and revealed reversible reductions in THF.