Phosphorus as a carbon copy and as a photocopy: New conjugated materials featuring multiply bonded phosphorus

Simpson, M. Cather; Protasiewicz, John D.

doi:10.1351/PAC-CON-12-09-13

Pure Appl. Chem., 2013, Vol. 85, No. 4, pp. 801-815

http://dx.doi.org/10.1351/PAC-CON-12-09-13

Published online 2013-03-13

Phosphorus as a carbon copy and as a photocopy: New conjugated materials featuring multiply bonded phosphorus

M. Cather Simpson¹ and John D. Protasiewicz²*

¹ Photon Factory, School of Chemical Sciences and Department of Physics, The University of Auckland, Auckland, New Zealand
² Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106, USA

Abstract: Phosphaalkenes (RP=CR₂) and diphosphenes (RP=PR) are main group analogues of alkenes (R₂C=CR₂). Molecules featuring such multiply bonded phosphorus functionalities often display structural features and chemical reactivities that mimic their purely organic counterparts, lending credence to the claim that these compounds are “carbon copies”. We have been expanding this analogy to include oligomers and polymers with extended conjugation that directly involve P=C and P=P units. Many of these materials, however, display little or no photoluminescence (PL). This article summarizes our efforts to understand P=C and P=P photobehavior and to produce materials having significant PL that mimic or “photocopy” the PL properties of the phosphorus-free systems. Recent materials based on benzoxaphospholes (BOPs), benzobisoxaphospholes (BBOPs), and higher analogues having significant fluorescence quantum yields are covered.