Abstract
Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873–1073 K. In addition, the porphyrin’s Ni–N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.
Highlights
Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks
Ni2-CPDPy comprises two Ni-porphyrins linked by two butadiyne moieties through phenyl groups; each porphyrin includes two meso-pyridyl groups
Ni2-CPDPy and H4-CPDPy afforded high yields (91% and 77%, respectively, 1073 K). Their carbonization processes were further analysed by temperature-programmed desorption (TPD) with thermogravimetry/photoionization mass spectrometry (TG-PI-MS, Supplementary Fig. 1)
Summary
Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. We report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks. Organic precursors are thermally converted into aggregations of imperfect graphene fragments via intermediates of polycyclic aromatic compounds[1] Despite their complicated and random structures, carbonaceous materials possess many advantageous properties (electrical conductivity, chemical and thermal stability, light weight). Ni2-CPDPy does not contain volatile fragments[1], a high carbon yield essential to retain the overall framework morphology of the precursor crystal is predicted
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