One-Dimensional Fullerene/Porphyrin Cocrystals: Near-Infrared Light Sensing through Component Interactions

Abstract

Recently, organic donor−acceptor (D−A) cocrystals have attracted special interest as functional materials because of their unique chemical and physical properties that are not exhibited by simple mixtures of their components. Herein, we report the preparation of one-dimensional novel D−A cocrystals from C 60 and 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin (3,5-TPP); these cocrystals have near-infrared (NIR) light-sensing abilities, despite each of their component molecule individually having no NIR light-sensing properties. Micrometer-sized rectangular columnar C 60 -3,5-TPP cocrystals were produced by a simple liquid−liquid interfacial precipitation method. The cocrystals exhibit a new strong transition in the NIR region indicative of the existence of chargetransfer interactions between C 60 and 3,5-TPP in the cocrystals. The C 60 -3,5-TPP cocrystals showed n-type transport characteristics with NIR light-sensing properties when the cocrystals were incorporated in bottom-gate/bottom-contact organic phototransistors, revealing that organic cocrystals with suitable charge-transfer interaction are useful as functional materials for the creation of novel NIR-light-sensing devices.

Multifunctional Features of Organic Charge‐Transfer Complexes: Advances and Perspectives

“…The presence of the porphyrin center metal ion was believed to play a crucial role in the strong D‐A interaction with C 60 and greatly reduce the π–π stacking distance between porphyrin and C 60 . Moreover, the C 60 /3,5‐TPP micrometer‐sized co‐crystals, prepared through a liquid–liquid interfacial precipitation method, revealed n‐type transport characteristic with NIR light‐sensing properties, which were achieved by CT forces and/or π–π interactions in the ground state [85] . A new black co‐crystal based on La@C 82 and [NiII (OEP)] was obtained by solution diffusion method with the highest electron mobility up to 0.9 cm 2 V −1 s −1 , measured by fast flash solution time‐resolved microwave conductivity (TRMC) measurement [86] …”

Organic Cocrystals: Recent Advances and Perspectives for Electronic and Magnetic Applications

“…The increasing current at 810 nm was attributed to the CT state in the C 60 /3,5-TPP cocrystals were excited to generate excitons that subsequently separated. Due to the CT absorption band and component bands, the phototransistor based on the C 60 /3,5-TPP cocrystal exhibited a strong photoresponse at 660 nm, and the measured photosensitivity was 4.5 (0.05 mW/cm 2 ) ( Figure 6D ) ( Wakahara et al, 2020 ).…”

“…(C) Wavelength dependence of the output characteristics of a C 60 /3,5-TPP phototransistor at V G = 80 V when illuminated with different LEDs (E ligh t = 0.1 mW/cm 2 ). (D) Output characteristic curves of the phototransistor based on C 60 /3,5-TPP at V G = 80 V when illuminated with 660 nm light of different intensities (E light ) (Reproduced from Wakahara et al (2020) with permission from American Chemical Society, Copyright 2020.).…”

Ambipolar to unipolar irreversible switching in nanosheet transistors: the role of ferrocene in fullerene/ferrocene nanosheets

“…6 Following these earlier studies, various FETs based on D-A cocrystals were reported. [7][8][9][10][11] There are many reports on ambipolar FETs based on novel organic semiconductors, however, the preparation of these semiconductors usually requires complex organic syntheses. One of the advantages of the cocrystallization process, which can be conducted by simply mixing two (or more) molecules together, is the possibility to avoid such complex synthesis pathways.…”