Related Experiment Video
Updated: Aug 7, 2026
07:24
Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals
Published on: April 14, 2020
Structure-optical property relationships in organometallic sydnones
Thomas M Cooper1, Benjamin C Hall, Daniel G McLean
1Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433, USA. Thomas.Cooper@wpafb.af.mil
The Journal of Physical Chemistry. A
|July 13, 2006
Summary
This study introduces novel platinum acetylide oligomers with sydnone groups, revealing their unique electronic properties and charge-transfer interactions. The sydnone moiety significantly influences excited-state polarity and energy levels in these platinum complexes.
Area of Science:
- Organometallic Chemistry
- Materials Science
- Spectroscopy
Background:
- Developing spectroscopic structure-property relationships is crucial for designing advanced materials.
- Platinum acetylide oligomers are of interest due to their unique electronic and photophysical properties.
Purpose of the Study:
- To synthesize and characterize novel mesoionic bidentate platinum(II) complexes containing sydnone groups.
- To investigate the spectroscopic and electronic effects of the sydnone moiety on platinum acetylide oligomers.
- To establish a spectroscopic structure-property relationship for these compounds.
Main Methods:
- Synthesis of sydnone-containing ligands (Syd-PEn-H) and their platinum complexes (Syd-PEn-Pt).
- Characterization using X-ray diffraction, 13C NMR, UV-Vis absorption, fluorescence, phosphorescence, and laser flash photolysis.
- Analysis of spectroscopic data to determine excited-state properties and energy levels.
Main Results:
- The sydnone group was found to polarize adjacent acetylenes and exhibit charge-transfer interaction with the platinum center.
- Syd-PE1-Pt showed an excited state less polar than its ground state, contrasting with PE1-Pt.
- The sydnone group lowered singlet energy E(S) by ~0.1 eV and raised triplet energy E(T) by ~0.1 eV, reducing singlet-triplet splitting Delta E(ST) by ~0.2 eV.
Conclusions:
- The sydnone group significantly impacts the electronic structure and photophysical properties of platinum acetylide oligomers.
- The observed effects suggest a charge-transfer interaction and localization of molecular orbitals on the sydnone moiety.
- These findings contribute to understanding structure-property relationships in platinum-based materials.
Related Concept Videos
02:52Stereoisomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
01:23Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
02:34Structural Isomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
01:29UV–Vis Spectroscopy: Woodward–Fieser Rules
UV–Visible absorption spectra of conjugated dienes arise from the lowest energy π → π* transitions. The light-absorbing part of the molecule is called the chromophore, and the substituents directly attached to the chromophore are called auxochromes. A strong correlation exists between the absorption maxima, λmax, and the structure of a conjugated π system. The Woodward–Fieser rules predict the value of λmax for a given structure by adding the contributions...
02:37Structure and Physical Properties of Alkynes
Introduction:
In nature, compounds containing both carbon and hydrogen are known as "hydrocarbons". Aliphatic hydrocarbons are compounds whose molecules contain saturated single bonds (i.e., alkanes) or unsaturated double or triple bonds. Alkenes contain carbon–carbon double bonds and have a structural formula CnH2n. Unsaturated hydrocarbons containing carbon–carbon triple bonds are called "alkynes" and are structurally represented by the formula CnH2n-2.
The simplest alkyne is ethyne, or...
In nature, compounds containing both carbon and hydrogen are known as "hydrocarbons". Aliphatic hydrocarbons are compounds whose molecules contain saturated single bonds (i.e., alkanes) or unsaturated double or triple bonds. Alkenes contain carbon–carbon double bonds and have a structural formula CnH2n. Unsaturated hydrocarbons containing carbon–carbon triple bonds are called "alkynes" and are structurally represented by the formula CnH2n-2.
The simplest alkyne is ethyne, or...
02:39Nomenclature of Alkynes
Alkynes are unsaturated hydrocarbons characterized by the presence of carbon-carbon triple bonds and have a general formula CnH2n-2. The nomenclature of alkynes follows a set of rules similar to alkanes and alkenes; however, alkynes bear the suffix "-yne" instead of "-ane" or "-ene." There are two approaches to naming alkynes: