Synthesis
and Characterization of Electron Donor–Acceptor
Platinum(II) Complexes Composed of <i>N</i>,<i>N</i>‑Diphenylpyridineamine and Triphenylamine Ligands
Zhi Dai
Alejandro J. Metta-Magaña
Jose E. Nuñez
10.1021/ic500290m.s002
https://acs.figshare.com/articles/dataset/Synthesis_and_Characterization_of_Electron_Donor_Acceptor_Platinum_II_Complexes_Composed_of_i_N_i_i_N_i_Diphenylpyridineamine_and_Triphenylamine_Ligands/2272447
The 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 <i>meta-</i> and <i>para-</i> 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 (<b>6a</b>,<b>b</b> and <b>7a</b>,<b>b</b>), 2.038–2.320 eV for the
TPA complexes (<b>8a</b>,<b>b</b> and <b>9a</b>),
2.301 eV for organic molecule <b>10a</b>, and 1.997 eV for <b>10b</b>. All compounds are stable, exhibiting no decomposition
in the solid indefinitely, and only minor decomposition in solution.
All compounds were characterized by <sup>1</sup>H and <sup>13</sup>C nuclear magnetic resonance, infrared spectroscopy, and electrospray
mass spectrometry. All complexes were also characterized by <sup>31</sup>P nuclear magnetic resonance and elemental analysis of CHN; determination
of Ag content for <b>6a</b>,<b>b</b> and <b>7a</b>,<b>b</b> (carried through the synthetic steps) was determined
by inductively coupled plasma optical emission spectrometry. The <i>para-</i>pyridine-derivatized complex of 2,1,3-benzothiadiazole
(<b>6a</b>) was further characterized by X-ray crystallography
as a AgNO<sub>3</sub> clathrate. X-ray quality crystals were grown
from a solution of hexanes/CH<sub>2</sub>Cl<sub>2</sub> and from diffusion
of hexanes into a CH<sub>2</sub>Cl<sub>2</sub> solution of the complex,
providing a solvent-free crystal and a solvate of CH<sub>2</sub>Cl<sub>2</sub>, respectively.
2014-07-21 00:00:00
electrospray mass spectrometry
TPA analogs
13 C
CHN
CH 2Cl solution
2.705 eV
molecule 10
CH 2Cl
alkynyl derivatives
Triphenylamine LigandsThe synthesis
UV
10 b
AgNO 3 clathrate
photovoltaic materials
cyclic voltammetry show
electron acceptors
Ag content
1 H
31 P
1.997 eV
complex
emission spectrometry