Organophosphorus Polymers

Abstract

This article discusses polymers containing phosphorus centers that impart essential properties, functions, and responses to the discussed materials. By incorporating this heteroelement, the toolbox for tailoring optical, electronic, and structural properties as well as chemical reactivity is greatly expanded over “carbon” analogs. We discuss unsaturated (e.g., phosphaalkenes), saturated (e.g., phosphine oxides), and cyclic (e.g., phospholes) phosphorus motifs incorporated into conjugated polymers. Such organophosphorus systems are believed to have a bright future in optoelectronic devices, with this being demonstrated in organic light‐emitting diodes as acceptor and emitter materials, and in fundamental studies as responsive sensor systems. Saturated organophosphorus polymers allow for chemical transformations at the phosphorus centers by means of oxidation, metal (Lewis acid) coordination, quaternization, and so on. These modifications and transformations are used in sensing, scavenging, and catalytic systems. Moreover, in this article, we cover selected inorganic polymers, that is, polymers having exclusively inorganic skeletal atoms. These mainly include the polyphosphine and phosphinoborane classes of materials, for which recent fundamental studies have illustrated their potential as ceramic precursors. Polymerization methods are often similar to those applied in organic polymers, but a large variety of polymerizations have also been specifically developed for phosphorus and other pnictogens, and these have also been employed to synthesize these fascinating materials.

Core and Double Bond Functionalization of Cyclopentadithiophene- Phosphaalkenes

“…[AuCl*A]: P1-C1 1.668(7), P1-C10 1.800(6), P1-Au1 2.2130 (15), C1-P1-C1 108. 3(3), P1-Au1-Cl1 178.16 (8). 8: P1-O1 1.489 (3), P2-O2 1.578 (3), P2-Au1 2.232(1), Au1-Cl1 2.298 (1).…”

“…the imine derivatives, hold promising developments for the heavier pnictaalkene systems. Interesting approaches have been already pursued to translate the molecular phosphaalkene motifs into polymeric materials, 8 both by keeping the P=C motif intact and using it as polymerizable unit. 9 Furthermore, the lone pair at the phosphaalkene can easily be functionalized by metal coordination allowing for catalytic applications, 10 but also altering the opto-electronic properties.…”

Core and double bond functionalisation of cyclopentadithiophene-phosphaalkenes

“…the imine derivatives, hold promising developments for the heavier pnictaalkene systems. Interesting approaches have already been pursued to translate the molecular phosphaalkene motifs into polymeric materials, 12 both by keeping the PvC motif intact and using it as polymerizable unit. [13][14][15][16][17] Furthermore, the lone pair at the phosphaalkene can easily be functionalised by metal coordination allowing for catalytic applications, [18][19][20] but also altering the opto-electronic properties.…”