Abstract
ABSTRACT
Conducting coordination polymers (
CPs
) have emerged as promising materials for chemiresistive gas sensing at ambient conditions. In this work, we report three ionic semiconducting Cu(I)
CPs
constructed from (pyridin‐4‐yl)‐
N
‐(4
H
‐1,2,4‐triazol‐4‐yl)methenamine (PTMA), oxydi(2,1‐phenylene)bis(diphenylphosphine), incorporating BF
4
−
(
CP1,
C
44
H
35
BCuF
4
N
5
OP
2
), PF
6
−
(
CP2,
C
44
H
35
CuF
6
N
5
OP
3
), and ClO
4
−
(
CP3,
C
44
H
35
ClCuN
5
O
5
P
2
) counteranions. Among these,
CP1
shows outstanding dual‐gas sensing capability toward SO
2
and NO
2
at ambient conditions, achieving strong chemiresistive responses with excellent selectivity, fast response–recovery behavior and stable cycling performance. Comparative studies using
CP2
and
CP3
reveal minimal counteranion influence, indicating that the sensing response is predominantly driven by interactions at the Cu–ligand framework. Complementary experimental measurements and theoretical calculations reveal that adsorption of electron‐accepting analytes perturbs the electron density on Cu(I), inducing partial oxidation of Cu(I) to Cu(II) and modulating charge transfer along the polymer backbone without disrupting structural stability, thereby accounting for the observed resistance modulation. Overall, these findings highlight the potential of Cu(I) systems as a high‐efficiency platform for room‐temperature dual‐gas sensing.