Electronic Structure of Covalent Organic Frameworks COF66 and COF366: from Monomers to Two-Dimensional Framework

doi:10.6023/A23040134

Abstract

Two-dimensional covalent organic frameworks (COFs) are an emerging important class of porous materials with periodically ordered structures consisting of core and linker units held together by strong covalent bonds. Their well-designed architecture, tunable functional properties and good thermal stabilities provide great potential for applications in photoenergy conversion and semiconductors. For the aim to explore the relationship between the structure and properties of COFs, which should be very useful for the design of new type of such attractive photo functional materials, the energy character of organic building units, fragment molecules and periodic two-dimensional planar structures are analyzed for COF66 and COF366. The results show that the structure of periodic planar frameworks will be influenced by the geometry of organic building units. Moreover, the relative energy level of the frontier orbitals of the organic building blocks will affect the ionization potential and electron affinity. And the electronic properties of the COFs are also in the same case. Therefore, the electronic property of organic building units is a key factor for determining the electronic structure of periodic structure of COFs. In addition, the electronic coupling of COFs will be larger if the conjugation of the organic building blocks is better. Then, the valence band maximum and conduction band minimum will be more dispersive, and the charge carrier mobility will get larger.

Key words: organic units available, two-dimensional covalent organic framework, electronic structure, density functional theory

Cite this article

Xuefeng Liang, Jian Jing, Xin Feng, Yongze Zhao, Xinyuan Tang, Yan He, Lisheng Zhang, Huifang Li. Electronic Structure of Covalent Organic Frameworks COF66 and COF366: from Monomers to Two-Dimensional Framework[J]. Acta Chimica Sinica, 2023, 81(7): 717-724.

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Fig. & Tab. 11

Figure 1. Illustration of the chemical structures for COF66 and COF366

Figure 2. Optimized geometry structures of TBPP and TAPP monomers, THAn-TBPP and TPAL-TAPP dimers, as well as TBPP-THAn-TBPP and TAPP-TPAL-TAPP trimers obtained at the DFT/PBE-D3 level (H is represented in white, B in pink, C in gray, N in blue and O in red)

	COF66				COF366
	THAn	TBPP	Dimer	Trimer	TPAL	TAPP	Dimer	Trimer
LUMO＋1	－1.37	－2.06	－2.67	－2.79	－1.20	－1.64	－3.04	－2.96
LUMO	－2.57	－3.09	－3.20	－3.23	－2.21	－2.89	－3.65	－3.37
HOMO	－4.47	－4.46	－4.52	－4.57	－3.97	－4.12	－4.31	－4.13
HOMO－1	－5.07	－4.83	－4.93	－4.96	－6.18	－4.64	－4.79	－4.69

Table 1. HOMO and LUMO energies for COF monomers and fragments, obtained at the DFT/PBE-D3 level

Figure 3. Contour plots of frontier orbitals and their energy gaps of the COF66 monomers and fragment obtained at the DFT/PBE-D3 level

Figure 4. Contour plots of frontier orbitals and their energy gaps of the COF366 monomers and fragment obtained at the DFT/PBE-D3 level

Porphyrin	TBPP	Dimer	Trimer	COF66	TAPP	Dimer	Trimer	COF366
NBO	－0.04	－0.03	－0.04	—	－0.09	－0.07	－0.09	—
Hirshfeld-I	－0.19	－0.18	－0.19	－0.16	－0.25	－0.22	－0.26	－0.20

Table 2. Charge distribution of porphyrin ring included in core molecules and frameworks (in |e|)

Figure 5. 1×1 unit cell of the optimized structure of a free-standing COF66/COF366 monolayer

Figure 6. Projected density of states and band structure of a freestanding COF66/COF366 monolayer (The red curve represents the PDOS of TBPP/TAPP core whereas the blue curve represents the PDOS of THAn/TPAL linker)

Figure 7. Partial charge density plot of two nearly degenerate states at the valence-band maximum and two nearly degenerate states at the conduction-band minimum for COF66 (the isosurface is 0.0002 e/nm)

	Hole		Electron
	M→X	M→X′	M→X	M→X′
COF-66	9.11	9.21	2.04	2.63
COF-366	0.68	0.68	0.46	0.74

Table 3. Calculated effective masses (in m0) and their directions for the 2D COFs

Figure 8. Partial charge density plot of two nearly degenerate states at the valence-band maximum and two nearly degenerate states at the conduction-band minimum for COF366 (the isosurface is 0.0002 e/nm)

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共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物