[reaction: see text] A new sensing mechanism based on C=N isomerization, which shows a very significant fluorescence enhancement to the metal cations in a simple and efficient way, is demonstrated. A coumarin derivative (L) containing a C=N group was designed as an example for illustration. The free ligand L is almost nonfluorescent due to the isomerization of C=N double bond in the excited state. However, the solution of ligand shows about a 200-fold increase of fluorescence quantum yield (about 30%) upon addition of Zn(ClO4)2.

The recent introduction of thermally activated delayed fluorescence (TADF) emitters is regarded as an important breakthrough for the development of high efficiency organic light-emitting devices (OLEDs). The planar D and A groups are generally used to construct TADF emitters for their rigid structure and large steric hindrance. In this work, it is shown that many frequently used nonaromatic (noncontinuous conjugation or without satisfying Hückel's rule) planar segments, such as 9,9-dimethyl-9,10-dihydroacridine, are actually pseudoplanar segments and have two possible conformations-a planar form and a crooked form. Molecules constructed from pseudoplanar segments can thus have two corresponding conformations. Their existence can have significant impact on the performance of many TADF emitters. Two design strategies are presented for addressing the problem by either (1) increasing the rigidity of these groups to suppress its crooked form or (2) increasing the steric hindrance of the linked group to minimize energy of the emitters with the highly twisted form. Following these strategies, two new emitters are synthesized accordingly and successfully applied in OLEDs demonstrating high external quantum efficiencies (20.2% and 18.3%).

has been a challenge. [5,6] To enhance the absorption and photoresponse of graphene devices, researchers provide a series of strategies to interface graphene with light-absorbing semiconductors. [7][8][9][10][11][12][13][14][15][16] Early experimental studies on hybrid devices mainly focus on using one semiconductor layer, including colloidal quantum dots, [7,8] perov skites, [9] organic polymers, [10] single crystals, [16] 2D materials, [17] silicon, and other traditional materials. [11] More recently, improvement of device performance has been made by introducing PN junction bilayer absorbing layer. Incorporating graphene with a perovskite/ organic heterojunction or organic PN junction [14,15] is reported to improve both the photo responsivity and bandwidth. However, the limited narrow spectral range of light-absorbing layer causes ultrahigh photoconductive gain but at the same time sacrifices the detection spectral range. [18] In addition, a number of chemical approaches have been reported to synthesize the conjugated polymers/small molecules (typically with a bandgap of less than 1.6 eV) with appropriate energy gap and desirable photoelectric properties, but the device performance is still restricted. [19] So far the spectral range of graphene-based high gain photodetection is limited to typically 400-700 nm. [9,10,14,15,20,21] Herein, we explore a broadband (405-1550 nm) graphene/ organic semiconductor heterojunction phototransistors with bi-directional photoresponse (both positive and negative photocurrents) for the first time. Instead of broadening the absorption range of the semiconductor layer, our devices exploit ultrasensitive photoresponse at visible region, and the inverse photoresponse at near-infrared region without the need for cryogenics or adjusting gate voltage. Taking organic small molecule C 60 /pentacene heterojunction as the light-absorption layer, we achieve a highest responsivity of 9127 A W −1 , response time down to 275 µs, and external quantum efficiency up to 11.5% in visible regime and over 1800 A W −1 (0.063%) in near-infrared regime. Compared with previous work, our phototransistors not only have large built-in electric field at the C 60 /pentacene interface for high quantum efficiency, but also maintain an ultrasensitive response to the near-infrared region. The wavelength-dependent bi-directional response enables us to analyze the device mechanism. Our devices have potential applications in hyperspectral imaging.A graphene-semiconductor heterojunction is very attractive for realizing highly sensitive phototransistors due to the strong absorption of the semiconductor layer and the fast charge transport in the graphene. However, the photoresponse is usually limited to a narrow spectral range determined by the bandgap of the semiconductor. Here, an organic heterojunction (C 60 /pentacene) is incorporated on graphene to realize a broadband (405-1550 nm) phototransistor with a high gain of 5.2 × 10 5 and a response time down to 275 µs. The visible and near-infrared parts of the photor...