Direct and selective access to amino-poly(phenylene vinylenes)s with switchable properties by dimerizing polymerization of aminoaryl carbenes

Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. In this work, we exploit the capability of purposely designed mono- and bis-acyclic amino(aryl)carbenes to selectively dimerize as a general strategy to access diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s (N-PPV's). The unique selectivity of the dimerization of singlet amino(aryl)carbenes, relative to putative C-H insertion pathways, is rationalized by DFT calculations. Of particular interest, unlike classical PPV's, the presence of amino groups in alpha -position of C=C double bonds in N-PPV's allows their physico-chemical properties to be manipulated in different ways by a simple protonation reaction. Hence, depending on the nature of the amino group (iPr(2)N vs. piperidine), either a complete loss of conjugation or a blue-shift of the maximum of absorption is observed, as a result of the protonation at different sites (nitrogen vs. carbon). Overall, this study highlights that singlet bis-amino(aryl)carbenes hold great promise to access functional polymeric materials with switchable properties, through a proper selection of their substitution pattern. Despite the ubiquity of singlet carbenes in chemistry, their utility as true monomeric building blocks for the synthesis of functional organic polymers has been underexplored. Here the authors show mono- and bis-acyclic amino(aryl)carbenes selectively dimerize to form diaminoalkenes and hitherto unknown amino-containing poly(p-phenylene vinylene)s.

Automated summary

The research demonstrates that mono- and bis-acyclic amino(aryl)carbenes selectively dimerize to form diaminoalkenes and previously unknown amino-containing poly(p-phenylene vinylene)s. By a simple protonation reaction, the physico-chemical properties of these polymers with amino groups in the α-position of C=C double bonds can be manipulated in different ways.