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Unpaired Electron-Induced Wide-Range Light Absorption within Zn (or Cu) MOFs Containing Electron-Withdrawing Ligands: A Theoretical and Experimental Study
journal contribution
posted on 2020-06-23, 15:33 authored by Long Yang, Haijun Huang, Xuedan Luo, Huichao He, Fang Gao, Yong ZhouIn
photocatalysis, it is of general interest to understand and
design wide-range light-absorbing inorganic/organic hybrid materials
with an excellent photo-induced intramolecular charge-transfer (ICT)
effect. To verify the role of unpaired electrons in enhancing ICT
within electron-withdrawing ligand-based metal–organic frameworks
(MOFs), the molecular structure, density of states (DOS), and electronic
structure of strong electron-deficient pyridine-diketopyrrolopyrrole
(P-DPP)-based Zn (or Cu) MOFs were calculated in Gaussian
package to validate the unpaired electron ICT. The electron spin resonance
technique has detected the unpaired electrons for the coordination
systems containing Zn–O or Cu–O clusters and P-DPP ligand on photoexcitation. The estimated band gaps from the DOS
calculation for P-DPP-Cu and P-DPP-Zn are
1.4 and 2.4 eV, respectively, showing a good agreement with the experimental
UV–vis optical spectra. The partial DOS, dipole moment, and
frontier orbital analysis prove that the ICT should happen from Zn–O
or Cu–O clusters to P-DPP ligands. This research
may contribute to a comprehensive understanding of electron-withdrawing
ligand-induced ICT within MOFs and shed light on the design of light-absorbing
MOFs with excellent ICT or conductivity.
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Keywords
electron ICTMOFs Containing Electron-Withdrawing LigandsUnpaired Electron-Induced Wide-Range Light Absorptioncoordination systemsP-DPP ligandsresonance techniqueDOS calculationZnUVGaussian packagelight-absorbing MOFs2.4 eVphoto-induced intramolecular charge-transferelectron-deficient pyridine-diketopyrrolopyrroleelectron-withdrawing ligand-induced ICTCuExperimental Studydesign wide-range light-absorbingP-DPP ligandband gaps
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