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Excited state mixed valence in a dual‐bridged three‐chromophore system
Author(s) -
Dibrelle Marcelle,
Hoekstra Ryan,
Weaver Michael N.,
Okada Keiji,
Nelsen Stephen F.,
Zink Jeffrey I.
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.2920
Subject(s) - chemistry , excited state , chromophore , raman spectroscopy , resonance raman spectroscopy , atomic orbital , valence (chemistry) , resonance (particle physics) , molecular orbital , absorption spectroscopy , spectroscopy , molecular physics , vibronic coupling , molecule , atomic physics , photochemistry , optics , physics , organic chemistry , quantum mechanics , electron
The optical and resonance Raman spectra of the 2,2′: 6′,2″:6″,6‐trioxytriphenyl‐amine cation are measured and interpreted. This molecule contains two simultaneous types of coupling between three chromophores and two types of bridging atoms. The first and conventional coupling involves a single nitrogen bridge that couples all three aryl groups. The second is provided by the three oxygen atoms, each of which bridges two adjacent aryl groups. There are two bands in the visible region of the optical absorption spectrum; their assignment and the interpretation of the contributing orbitals and electronic states are described in terms of the neighboring orbital model that explains the effects of the two types of coupling. The bonding changes that take place in the excited electronic states are probed by resonance Raman spectroscopy intensities and analyzed using the time‐dependent theory of resonance Raman spectroscopy. The optical absorption spectrum was fit using the measured vibrational frequencies and excited state distortions. The distortions correlate well with the bonding changes predicted by the neighboring orbital model. The resonance Raman data and neighboring orbital model analysis reveal that the two optical absorption bands correspond to charge transfers from aryl groups with different nodal structures in their pi orbitals. Copyright © 2012 John Wiley & Sons, Ltd.