Reversible Transformation between Azo and Azonium Bond Other than Photoisomerization of Azo Bond in Main-Chain Polyazobenzenes

Although side-chain polyazobenzenes have been extensively studied, main-chain polyazobenzenes (abbreviated MCPABs) are rarely reported due to the challenges associated with difficulty in synthetic chemistry and photoisomerization of azo bonds in MCPABs. Thus, it is highly demanded to develop new mechanisms other than photoisomerization of azo bonds in MCPABs to extend their applications. In this work, we created a new series of N-linked MCPABs via fast NaBH₄-mediated reductive coupling polymerization on N-substituted bis­(4-nitrophenyl)­amines. The structure of MCPABs has been characterized by comprehensive solid-state NMR experiments such as CPMAS ¹³C NMR with long and short contact times, cross-polarization polarization-inversion (CPPI), and cross-polarization nonquaternary suppressed (CPNQS). The azo bonds in MCPABs were found to be promising for acid vapor sensing, being acidified to form azonium ion with significant color change from red to green. And the azonium of MCPABs turned from green to red when exposed to base vapor, thus suitable for base vapor sensing.