Journal
JOURNAL OF MATERIALS CHEMISTRY C
Volume 6, Issue 2, Pages 380-387Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7tc04655c
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Funding
- University Grants Commission (UGC), New Delhi
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Synthesizing graphdiyne analogues with a well-defined structure and desirable band gap is a challenging task. Herein, we present a novel, well-defined and highly structured crystalline pi-conjugated nanowall framework, called pyrediyne (pyrene + diyne = pyrediyne), with large in-plane periodicity. The bulk synthesis of the two-dimensional (2D) ultrathin polymeric framework of pyrediyne is achieved via a modified-Glaser-Hay coupling reaction using 1,3,6,8-tetraethynylpyrene. The ultrathin p-conjugated crystalline pyrediyne nanowall is well characterized by Raman, SEM, AFM, HR-TEM and XPS techniques. Electronic structure information reveals the p-conjugated framework to be completely planar with a C-s point group, where a tunable band gap of E-g similar to 1.17 eV can be achieved depending on the number of pyrene units. The electrostatic potential maps reveal complete pi-delocalization of the electron cloud throughout the framework with a high electronegative potential at the acetylenic linkages. This through-bond charge coupling via the conjugated network in conjunction with the charge delocalization via the pi...pi interactions in space accounts for the significant electrical conductivity {sigma = 1.23(+/- 0.1) x 10(-3) S m(-1)} of the organic material.
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