d ]-Carbon-carbon double bond engineering in diazaphosphepines: a pathway to modulate the chemical and electronic structures of heteropines

Chemical Science
Yi RenYueh-Lin Loo

Abstract

We have designed and synthesized the first examples of 7-membered diazaphosphepines using phosphorus-amine (P-N) chemistry. Different from previous functional protocols of heteropines, the installation of π-conjugated substituents having diverse chemistries at the [d]-C[double bond, length as m-dash]C double bond position of heteropine core allows us to effectively control the chemical and electronic structures in both the ground and excited states of these diazaphosphepines. This functionalization has led to a diverse set of crystal structures, which has in turn provided access to rich photophysical and redox properties. Of particular interest is the evidence for planar π-conjugated backbone in our non-aromatic heteropine and twisted intramolecular charge transfer, which have never been reported for heteropines. The introduction of electron-accepting substituents at [d]-position of diazaphosphepines results in heteropines that are more electron deficient than any heteropine reported to-date. As proof of concept, we have fabricated organic solar cells with heteropines as non-fullerene acceptors.

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Citations

Sep 12, 2018·Angewandte Chemie·Qi ZhongHua Zhang
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Dec 19, 2019·The Journal of Organic Chemistry·Elzbieta RegulskaCarlos Romero-Nieto

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