TY - JOUR
T1 - Small-Molecule Mixed Ionic-Electronic Conductors for Efficient N-Type Electrochemical Transistors
T2 - Structure-Function Correlations
AU - Cho, Yongjoon
AU - Gao, Lin
AU - Yao, Yao
AU - Kim, Jaehyun
AU - Zhang, Dayong
AU - Forti, Giacomo
AU - Duplessis, Isaiah
AU - Wang, Yuyang
AU - Pankow, Robert M.
AU - Ji, Xudong
AU - Rivnay, Jonathan
AU - Marks, Tobin J.
AU - Facchetti, Antonio
N1 - Publisher Copyright:
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2025/1/10
Y1 - 2025/1/10
N2 - The fundamental challenge in electron-transporting organic mixed ionic-electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6-type/U-shaped non-fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U-shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion-electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~106, and a turn-on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY-based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long-range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small-molecule-based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small-molecule OMIECs.
AB - The fundamental challenge in electron-transporting organic mixed ionic-electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6-type/U-shaped non-fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1 g to 3 g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U-shaped/planar core, close π–π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion-electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high transconductance of 16.5 mS, an on/off current ratio of ~106, and a turn-on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY-based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long-range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small-molecule-based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small-molecule OMIECs.
KW - electrochemical transistor
KW - ion transport
KW - mesh-like crystal
KW - n-type small molecule
KW - organic mixed ionic-electronic conductor
UR - http://www.scopus.com/inward/record.url?scp=85207800958&partnerID=8YFLogxK
U2 - 10.1002/anie.202414180
DO - 10.1002/anie.202414180
M3 - Article
C2 - 39312509
AN - SCOPUS:85207800958
SN - 1433-7851
VL - 64
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 2
M1 - e202414180
ER -