Structural and Photophysical Properties of Various Polypyridyl Ligands: A Combined Experimental and Computational Study

Autor: Pascal Van Der Voort, Michel Waroquier, Veronique Van Speybroeck, Jonas Everaert, Liesbeth De Bruecker, Christian V. Stevens
Rok vydání: 2020
Předmět:
ORGANIC FRAMEWORKS
time-dependent functional theory
Materials science
Technology and Engineering
DENSITY FUNCTIONALS
Electronic structure
02 engineering and technology
Dihedral angle
010402 general chemistry
01 natural sciences
Article
polypyridyl ligand
chemistry.chemical_compound
Molecular dynamics
Ultraviolet visible spectroscopy
Computational chemistry
Atomic and Molecular Physics
CRYSTAL-STRUCTURE
Physical and Theoretical Chemistry
WAVE-FUNCTION METHODS
Triazine
Rational design
Optics
Articles
021001 nanoscience & nanotechnology
UV-Vis spectroscopy
Atomic and Molecular Physics
and Optics
PYRIDINE
0104 chemical sciences
3. Good health
COVALENT TRIAZINE FRAMEWORKS
NITROGEN
covalent triazine framework
Chemistry
chemistry
Physics and Astronomy
EXCITED-STATES
Excited state
Density functional theory
COMPLEXES
ELECTRONIC-ABSORPTION-SPECTRA
0210 nano-technology
photocatalysis
Zdroj: Chemphyschem
CHEMPHYSCHEM
ChemPhysChem
ISSN: 1439-7641
1439-4235
Popis: Covalent triazine frameworks (CTFs) with polypyridyl ligands are very promising supports to anchor photocatalytic complexes. Herein, we investigate the photophysical properties of a series of ligands which vary by the extent of the aromatic system, the nitrogen content and their topologies to aid in selecting interesting building blocks for CTFs. Interestingly, some linkers have a rotational degree of freedom, allowing both a trans and cis structure, where only the latter allows anchoring. Therefore, the influence of the dihedral angle on the UV‐Vis spectrum is studied. The photophysical properties are investigated by a combined computational and experimental study. Theoretically, both static and molecular dynamics simulations are performed to deduce ground‐ and excited state properties based on density functional theory (DFT) and time‐dependent DFT. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π‐system and a higher π‐electron deficiency. We found that the position of the main absorption peak among the different ligands studied in this work can amount to 271 nm; which has a significant impact on the photophysical properties of the ligands. This broad range of shifts allows modulation of the electronic structure by varying the ligands and may help in a rational design of efficient photocatalysts.
The photophysical properties of various polypyridyl ligands have been investigated by a combined computational and experimental study in order to select interesting building blocks for covalent triazine frameworks. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π ‐system and a higher π ‐electron deficiency. The shift can amount to 271 nm among the different ligands; which has a significant impact on the photophysical properties.
Databáze: OpenAIRE
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