Diradicals acting through diamagnetic phenylene vinylene bridges: Raman spectroscopy as a probe to characterize spin delocalization

We present a complete Raman spectroscopic study in two structurally well-defined diradical species of different lengths incorporating oligo p-phenylene vinylene bridges between two polychlorinated triphenylmethyl radical units, a disposition that allows sizeable conjugation between the two radicals...

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Bibliographic Details
Published in:The Journal of chemical physics 2014-04, Vol.140 (16), p.164903-164903
Main Authors: González, Sandra Rodríguez, Nieto-Ortega, Belén, González Cano, Rafael C, Lloveras, Vega, Novoa, Juan J, Mota, Fernando, Vidal-Gancedo, José, Rovira, Concepció, Veciana, Jaume, del Corro, Elena, Taravillo, Mercedes, Baonza, Valentín G, López Navarrete, Juan T, Casado, Juan
Format: Article
Language:English
Subjects:
Conjugation
COUPLING
Coupling (molecular)
Diamagnetism
Electron spin
ELECTRONS
Espectroscòpia Raman
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERACTIONS
Magnetic properties
Molecular Conformation
Molecular structure
Organic chemistry
Polarization (spin alignment)
Pressure dependence
PROBES
Propietats magnètiques
Quantum chemistry
Química quàntica
RADICALS
RAMAN SPECTROSCOPY
Spectrum analysis
Spectrum Analysis, Raman
SPIN
SPIN ORIENTATION
Temperature
TEMPERATURE DEPENDENCE
Trityl Compounds - chemistry
Vinyl Compounds - chemistry
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Summary:We present a complete Raman spectroscopic study in two structurally well-defined diradical species of different lengths incorporating oligo p-phenylene vinylene bridges between two polychlorinated triphenylmethyl radical units, a disposition that allows sizeable conjugation between the two radicals through and with the bridge. The spectroscopic data are interpreted and supported by quantum chemical calculations. We focus the attention on the Raman frequency changes, interpretable in terms of: (i) bridge length (conjugation length); (ii) bridge conformational structure; and (iii) electronic coupling between the terminal radical units with the bridge and through the bridge, which could delineate through-bond spin polarization, or spin delocalization. These items are addressed by using the "oligomer approach" in conjunction with pressure and temperature dependent Raman spectroscopic data. In summary, we have attempted to translate the well-known strategy to study the electron (charge) structure of π-conjugated molecules by Raman spectroscopy to the case of electron (spin) interactions via the spin delocalization mechanism.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4871895