Titanocene as a New Acceptor (A) for Arylamine Donors (D) in D-pi-A Chromophores

Pienkos J. A. , Agakidou A. D. , Trindle C. O. , Herwald D. W. , ALTUN Z. , Wagenknecht P. S.

ORGANOMETALLICS, cilt.35, sa.16, ss.2575-2578, 2016 (SCI İndekslerine Giren Dergi) identifier

  • Cilt numarası: 35 Konu: 16
  • Basım Tarihi: 2016
  • Doi Numarası: 10.1021/acs.organomet.6b00518
  • Sayfa Sayıları: ss.2575-2578


Charge transfer (CT) transitions are relevant in the fields of solar energy conversion and nonlinear optical materials. Herein, a series of complexes with an alkynyl linkage between an aryl amine donor and a Ti-IV (titanocene) acceptor is reported. Each complex displays a strong (15000 < epsilon < 24,000 M(-1)cm(-1)), low-energy (520 < lambda < 560 nm) absorption ascribed to an amine to Ti-IV ligand-to-metal CT. This characterization is supported by UV-vis spectroscopy, cyclic voltammetry, and TD-DFT calculations. These complexes are not photostable; therefore, an alternate architecture, wherein the amine donor is appended to the titanocene cyclopentadienyl ligand, has been designed. The molar absorptivity of the amine to Ti-IV CT in this latter architecture is lower (2100 M-1 cm(-1)), indicating weaker donor-acceptor coupling. This architecture is indeed much more photostable.