10.1021/cg400420h.s001
Brendan F. Abrahams
Brendan F.
Abrahams
Robert W. Elliott
Robert W.
Elliott
Timothy A. Hudson
Timothy A.
Hudson
Richard Robson
Richard
Robson
PtS-Related {[Cu<sup>I</sup>(F<sub>4</sub>TCNQ<sup>II–</sup>)]<sup>−</sup>}<sub>∞</sub> Networks
American Chemical Society
2016
phenyl group
phenyl groups
phosphonium cation
dianionic form
framework
NMe
compound
PtS topology
quaternary ammonium
quaternary phosphonium cations
2016-02-19 04:24:06
Journal contribution
https://acs.figshare.com/articles/journal_contribution/PtS_Related_Cu_sup_I_sup_F_sub_4_sub_TCNQ_sup_II_sup_sup_sup_sub_sub_Networks/2399344
A series
of compounds of composition A[Cu<sup>I</sup>(F<sub>4</sub>TCNQ<sup>II–</sup>)] (A = a quaternary ammonium
or phosphonium cation, F<sub>4</sub>TCNQ<sup>II–</sup> = the dianionic form of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane)
have been synthesized and structurally characterized. In each structure,
an anionic [Cu<sup>I</sup>(F<sub>4</sub>TCNQ<sup>II–</sup>)]<sup>−</sup> framework possessing the topology of PtS is
formed with the Cu(I) center serving as a tetrahedral 4-connecting
center and the F<sub>4</sub>TCNQ<sup>2–</sup> anion acting
as a planar 4-connecting unit. Although a PtS topology is observed
for six different compounds, the anionic framework shows significant
geometric variation depending upon the identity of the cation. Very
similar structures are obtained when the organic cation is NMe<sub>4</sub><sup>+</sup>, NMe<sub>2</sub>Pr<sub>2</sub><sup>+</sup>, or NMe<sub>2</sub>Bu<sub>2</sub><sup>+</sup>. A distorted
anionic structure possessing the same connectivity is generated when
the cation is NEt<sub>4</sub><sup>+</sup>, and anionic frameworks
with a different connectivity, but still related to PtS, are obtained
when the much larger quaternary phosphonium cations are employed.
Of interest in the structures containing quaternary phosphonium cations
are π-stacking interactions involving phenyl groups of the cation
and F<sub>4</sub>TCNQ<sup>2–</sup> ligands. These face-to-face
interactions between the electron-rich F<sub>4</sub>TCNQ<sup>2–</sup> ligands and a phenyl group of the cation appear to
be responsible for the color exhibited by these compounds.