Time-dependent density functional theory study of the spectroscopic properties related to aggregation in the platinum(II) biphenyl dicarbonyl complex
Stoyanov, Stanislav R. Villegas, John M. Rillema, D. Paul
Stoyanov, Stanislav R.
Villegas, John M.
Rillema, D. Paul
Citations
Altmetric:
Location
Time Period
Advisors
Original Date
Digitization Date
Issue Date
2003-12-01
Type
Article
Genre
Keywords
Subjects (LCSH)
Citation
Inorganic chemistry. 2003 Dec1; 42(24): 7852-60.
Abstract
Singlet ground-state geometry optimization of the monomer, four dimers, and the trimer of [Pt(bph)(CO)(2)], where bph = biphenyl dianion, was performed at the B3LYP level of density functional theory (DFT) with a mixed basis set (6-311G** on C, O, and H atoms; the Stuttgart/Dresden (SDD) effective core potential (ECP) on the Pt core; [6s5p3d] on the Pt valence shell). The aggregation was based on Pt[bond]Pt binding as well as on pi[bond]pi and electrostatic interactions. The lowest-lying triplet-state geometries of the monomer, one dimer, and the trimer of the complex were also optimized using the above theory. Significant shortening of the Pt[bond]Pt bond was recorded in the triplet state compared to the singlet one. A number of low-energy singlet and triplet allowed excited states were calculated using time-dependent density functional theory (TDDFT) and analyzed with respect to absorption, excitation, and emission spectra collected under various conditions. Simulated spectra of the monomer and dimer based on the singlet excited states were correlated with the absorption spectrum. The emission in concentrated solution was due to the triplet dimer, and the emitting states were (3)MLCT and Pt-centered states.
Table of Contents
Description
Click on the DOI link below to access the article (may not be free).
Publisher
American Chemical Society
Journal
Book Title
Series
Inorganic chemistry
Inorg Chem
Inorg Chem
Digital Collection
Finding Aid URL
Use and Reproduction
Archival Collection
NLM
PubMed ID
DOI
ISSN
0020-1669