Issue 18, 2003
From the journal:

Physical Chemistry Chemical Physics

Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study†

Igor Reva,*a   Leszek Lapinski,ab   Nitin Chattopadhyayc  and  Rui Faustoa  

* Corresponding authors

a Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal
E-mail: reva@qui.uc.pt

b Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw, Poland

c Department of Chemistry, Jadavpur University, Calcutta, India

Abstract

Theoretical optimization of triphenylamine geometry, carried out at DFT(B3LYP) level using 6-31G** and aug-cc-pVDZ basis sets, predicted a propeller-like structure of the compound with D3 overall symmetry. In this structure, the central NCCC atoms are coplanar and the phenyl rings are symmetrically twisted from this plane by 41.5° (6-31G**) or 41.6° (aug-cc-pVDZ). The experimental FTIR spectrum of triphenylamine monomers isolated in an argon matrix was measured and interpreted by comparison with theoretical spectra calculated at the DFT(B3LYP) level with 6-31G** or aug-cc-pVDZ basis sets. The good agreement between the experimental and theoretical spectra allowed a positive assignment of the observed infrared absorption bands. Conformational flexibility of triphenylamine was investigated by carrying out a series of theoretical scans of the potential energy hypersurface of the system. Special attention was granted to the minimal energy pathway between the left-hand rotating and right-hand rotating symmetry identical structures of the compound. A route conserving a C2 symmetry axis was identified as implying an energy barrier of 20 kJ mol−1 only, whereas the calculated barrier for the concerted twist of all the phenyl rings (the route with conservation of the C3 symmetry axis) was as high as 54 kJ mol−1.

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/B306489A
Article type
Paper
Submitted
10 Jun 2003
Accepted
08 Jul 2003
First published
06 Aug 2003

Phys. Chem. Chem. Phys., 2003,5, 3844-3850

Permissions

Request permissions

Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study

I. Reva, L. Lapinski, N. Chattopadhyay and R. Fausto, Phys. Chem. Chem. Phys., 2003, 5, 3844 DOI: 10.1039/B306489A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements