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Theoretical studies of ground and excited electronic States in a series of rhenium(i) bipyridine complexes containing diarylethynyl-based structure
- Source :
- Inorganic chemistry. 43(19)
- Publication Year :
- 2004
-
Abstract
- The photophysical properties, which vary as X is varied, of Re(I)-halide complexes (X2-bpy)ReICl(CO)3 (where X=ph, DAE, DNE, and DPE; ph = phenyl (1); DAE = di(amineoethynylbenzene) (2); DPE = di(phenylethynylbenzene) (3); DNE = di(nitroethynylbenzene) (4); bpy=2,2'bipyridine), are investigated using density functional theory (DFT). The electronic properties of the neutral molecules, in addition to the positive and negative ions, are studied using B3LYP functional. Excited singlet and triplet states are examined using time-dependent density functional theory (TDDFT). The low-lying excited-state geometries are optimized at the ab initio configuration interaction singlets level. As shown, the diarylethynyl-based structure is an integral component of the bpy pi-conjugated network, which results in a good planar structure. The occupied orbitals involved in the transitions have a significant mixture of metal Re and group Cl, and the lowest unoccupied orbital is a pi orbital, which extends from ligand bpy to diarylethynyl-based substituents. The luminescence for each complex originates from the lowest triplet excited states and is assigned to the mixing of MLCT and LLCT characters. Significant insights on the effects of these diarylethynyl conjugated structure and ending substituents (NH2, ph, and NO2) on absorption and emission spectra are observed by analysis of the results of the TDDFT method. The diarylethynyl-based pi-conjugated network makes both the absorption and emission spectra red-shifted compared with simple complex (bpy)ReICl(CO)3. Furthermore, an electron-releasing group (NH2) makes absorption and emission spectra blue-shift and an electron-withdrawing group (NO2) makes them red-shift.
- Subjects :
- Ab initio
chemistry.chemical_element
Time-dependent density functional theory
Rhenium
Configuration interaction
Inorganic Chemistry
Crystallography
Bipyridine
chemistry.chemical_compound
chemistry
Atomic orbital
Computational chemistry
Molecule
Density functional theory
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 00201669
- Volume :
- 43
- Issue :
- 19
- Database :
- OpenAIRE
- Journal :
- Inorganic chemistry
- Accession number :
- edsair.doi.dedup.....c3d8c91dbd05470ec17a7004a747ab85