Strategic Design of Hemi-Isoindigo Polymer for a Highly Sensitive and Selective All-Printed Flexible Nitrogen Dioxide Chemiresistive Sensor.

The study has developed two hemi-isoindigo (HID)-based polymers for printed flexible resistor-type nitrogen oxide (NO 2 ) sensors: poly[2-ethylhexyl 3-((3'",4'-bis(dodecyloxy)-3,4-dimethoxy-[2,2':5',2'"-terthiophen]-5-yl)methylene)-2-oxoindoline-1-carboxylate] (P1) and poly[2-ethylhexyl 2-oxo-3-((3,3'",4,4'-tetrakis(dodecyloxy)-[2,2':5',2'"-terthiophen]-5-yl)methylene)indoline-1-carboxylate] (P2). These polymers feature thermally removable carbamate side chains on the HID units, providing solubility and creating molecular cavities after thermal annealing. These cavities enhance NO 2 diffusion, and the liberated unsubstituted amide ─C(═O)NH─ groups readily form robust double hydrogen bonds (DHB), as demonstrated by computer simulations. Furthermore, both polymers possess elevated highest occupied molecular orbital (HOMO) energy levels of -4.74 and -4.77 eV, making them highly susceptible to p-doping by NO 2 . Gas sensors fabricated from P1 and P2 films, anneal under optimized conditions to partially remove carbamate side chains, exhibit remarkable sensitivities of +1400% ppm -1 and +3844% ppm -1 , and low detection limit (LOD) values of 514 ppb and 38.9 ppb toward NO 2 , respectively. These sensors also demonstrate excellent selectivity for NO 2 over other gases.