Journal article Open Access

A π-conjugated, covalent phosphinine framework

Huang, Jieyang; Tarábek, Ján; Kulkarni, Ranjit; Wang, Cui; Dračínský, Martin; Smales, Glen J.; Tian, Yu; Ren, Shijie; Pauw, Brian R.; Resch-Genger, Ute; Bojdys, Michael J.


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    <subfield code="a">A π-conjugated, covalent phosphinine framework</subfield>
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    <subfield code="a">&lt;p&gt;Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si and S have found their way into their building blocks so far. Here, we expand the toolbox available to polymer and materials chemists by one additional nonmetal, phosphorus. Starting with a building block that contains a &amp;lambda;&lt;sup&gt;5&lt;/sup&gt;-phosphinine (C&lt;sub&gt;5&lt;/sub&gt;P) moiety, we evaluate a number of polymerisation protocols, finally obtaining a &amp;pi;-conjugated, covalent phosphinine-based framework (CPF-1) &lt;em&gt;via&lt;/em&gt; Suzuki-Miyaura coupling. CPF-1 is a weakly porous polymer glass (72.4&amp;nbsp;m&lt;sup&gt;2&lt;/sup&gt;&amp;nbsp;g&lt;sup&gt;-1&lt;/sup&gt; N&lt;sub&gt;2&lt;/sub&gt; BET at 77&amp;nbsp;K) with green fluorescence (&amp;lambda;&lt;sub&gt;max&lt;/sub&gt; 546&amp;nbsp;nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co-catalyst at a rate of 33.3&amp;nbsp;&amp;mu;mol&amp;nbsp;h&lt;sup&gt;-1&lt;/sup&gt;&amp;nbsp;g&lt;sup&gt;-1&lt;/sup&gt;. Our results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine-based frameworks show promising electronic and optical properties that might spark future interest in their applications in light-emitting devices and heterogeneous catalysis.&lt;/p&gt;</subfield>
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