ic500290m_si_002.cif (34.47 kB)
Synthesis and Characterization of Electron Donor–Acceptor Platinum(II) Complexes Composed of N,N‑Diphenylpyridineamine and Triphenylamine Ligands
dataset
posted on 2014-07-21, 00:00 authored by Zhi Dai, Alejandro J. Metta-Magaña, Jose E. NuñezThe synthesis and electronic properties
of a series of platinum(II)
complexes composed of electron-donor and electron-acceptor components
as potential photovoltaic materials is reported. The complexes are
composed of triphenylamines (TPA) and pyridine-derivatized TPAs as
the electron-donating components, and alkynyl derivatives of 2,1,3-benzothiadiazole
and cyclopentadithiophenone as the electron acceptors. The complexes
containing the pyridine-derivatized ligands were prepared to examine
the effect that direct coordination of a heteroatom-modified TPA may
have on the electronic properties of donor–acceptor (D–A)
complexes. Four complexes composed of meta- and para- pyridine-derivatized TPAs were prepared, and their
electronic properties were compared with three structurally similar
complexes composed of TPA, as well as with purely organic D–A
compounds. Data collected from UV–vis and cyclic voltammetry
show minor differences on the properties of the complexes containing
the pyridine-derivatized ligands when compared to the TPA analogs,
exhibiting similar highest occupied molecular orbital–lowest
unoccupied molecular orbital bandgaps ranging from 2.156 to 2.705
eV for the pyridine-derivatized complexes (6a,b and 7a,b), 2.038–2.320 eV for the
TPA complexes (8a,b and 9a),
2.301 eV for organic molecule 10a, and 1.997 eV for 10b. All compounds are stable, exhibiting no decomposition
in the solid indefinitely, and only minor decomposition in solution.
All compounds were characterized by 1H and 13C nuclear magnetic resonance, infrared spectroscopy, and electrospray
mass spectrometry. All complexes were also characterized by 31P nuclear magnetic resonance and elemental analysis of CHN; determination
of Ag content for 6a,b and 7a,b (carried through the synthetic steps) was determined
by inductively coupled plasma optical emission spectrometry. The para-pyridine-derivatized complex of 2,1,3-benzothiadiazole
(6a) was further characterized by X-ray crystallography
as a AgNO3 clathrate. X-ray quality crystals were grown
from a solution of hexanes/CH2Cl2 and from diffusion
of hexanes into a CH2Cl2 solution of the complex,
providing a solvent-free crystal and a solvate of CH2Cl2, respectively.