Twisting the phenyls in aryl diphosphenes (Ar-P=P-Ar). Significant impact upon lowest energy excited states.

ABSTRACT: Aryl diphosphenes (Ar-P=P-Ar) possess features that may make them useful in photonic devices, including the possibility for photochemical E-Z isomerization. Development of good models guided by computations is hampered by poor correspondence between predicted and experimental UV/vis absorption spectra. A hypothesis that the phenyl twist angle (i.e., PPCC torsion) accounts for this discrepancy is explored, with positive findings. DFT and TDDFT (B3LYP) were applied to the phenyl-P=P-phenyl (Ph-P=P-Ph) model compound over a range of phenyl twist angles, and to the Ph-P=P-Ph cores of two crystallographically characterized diphosphenes: bis-(2,4,6-tBu(3)C(6)H(2))-diphosphene (Mes*-P=P-Mes*) and bis-(2,6-Mes(2)C(6)H(3))-diphosphene (Dmp-P=P-Dmp). A shallow PES is observed for the model diphosphe

SUBMITTER: Peng HL 

PROVIDER: S-EPMC2756825 | biostudies-literature | 2009 Jun

REPOSITORIES: biostudies-literature