科研之友
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摘要
Boron-nitrogen doping of polyaromatic hydrocarbon (PAH) materials can be used to tune their electronic properties while preserving the structural characteristics of pure hydrocarbons. Many multicycle PAHs can be synthesized photochemically; in contrast, very little is known about the photochemistry of their BN-doped counterparts. We present results of fs, ns, and mu s time-resolved spectroscopic studies on the photoinduced dynamics of hexaphenyl benzene and hexaphenyl borazine in order to examine how BN doping alters photochemical C-C bond formation via 6 pi electrocyclization as well as the stability of resulting cychzed structures. Ultrafast measurements reveal photoinduced behaviors reflecting differences in excited-state decay pathways for the two molecules, with hexaphenyl borazine relaxing from its excited state with a rate that is 2 orders of magnitude faster than that of hexaphenyl benzene (3.0 vs 428 ps). Tetraphenyl dihydrotriphenylene generated from hexaphenyl benzene is observed to reopen with a similar to 2 mu s lifetime controlled by entropic stabilization of the cyclized structure; in contrast, photoinduced dynamics appear to be complete within 100 ps after excitation of hexaphenyl borazine. This significant difference in photochemical dynamics is reflected in the cyclodehydrogentation yields obtained for the two reactants (25 vs 0% for hexaphenyl benzene and borazine, respectively). Quantum-chemical computations predict that BN doping gives rise to energetic destabilization and increased singlet diradical character in cyclized structures. These findings indicate that the polarized BN bonds of the borazine core adversely impact photochemical bond formation relative to analogous hydrocarbons.
- 出版日期2017-11-9
