Described herein is a stable complex, Pt(mpzpyOczpy-mesi), embodying efficient, narrow blue emission. The highly twisted structure of the complex improves the stability and efficiency of photo- and electroluminescence by reducing the intermolecular interactions. The complex in solution shows high photoluminescence efficiency (>95%) and radiative decay rate (Kr = 2.9 × 105 s-1) with a narrow emission spectrum. The bottom-emitting phosphorescent device, BE1, exhibits durable deep blue emission with CIE coordinates of (0.145, 0.166) and 5.2 h of LT50 at an initial luminance of 685 cd/m2. Top-emitting devices, TE1 and TE2, achieve ultrapure blue color with CIEx,y values of (0.141, 0.068) and (0.140, 0.071), respectively. TE4 shows high brightness of 3405 cd m-2 at 50 mA m-2, EQE of 10.2% at 1000 cd/m2, and almost negligible color deviation around (0.135, 0.096) at viewing angles of 0°-60°.

Ultrapure Blue Phosphorescent Organic Light-Emitting Diodes Employing a Twisted Pt(II) Complex

Organic room temperature phosphorescence (RTP) has been widely investigated to realize long-lifetime luminescent materials and improvement in their efficiency is a key focus of research, especially for red and near-infrared (NIR) RTP molecules. However, due to the lack of systematic studies on the relationship between basic molecular structures and luminescence properties, both the species and amounts of red and NIR RTP molecules remain far from meeting the requirements of practical applications. Herein, based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations, the photophysical properties of seven red and NIR RTP molecules in tetrahydrofuran (THF) and in the solid phase were theoretically studied. The excited state dynamic processes were investigated by calculating the intersystem crossing and reverse intersystem crossing rates considering the surrounding environmental effects in THF and in the solid phase using a polarizable continuum model (PCM) and quantum mechanics and molecular mechanics (QM/MM) method, respectively. The basic geometric and electronic data were obtained, Huang-Rhys factors and reorganization energies were analyzed, and natural atomic orbital was used to calculate the orbital information of the excited states. Simultaneously, the electrostatic potential distribution on molecular surfaces was analyzed. Further, intermolecular interactions were visualized using the molecular planarity binding independent gradient model based on Hirshfeld partition (IGMH). The results showed that the unique molecular configuration has the potential to achieve red and NIR RTP emission. Not only did the substitutions of halogen and sulfur make the emission wavelength red-shifted, but also linking the two cyclic imide groups could further make the emission wavelength longer. Moreover, we found that the emission characteristics of molecules in THF had a similar trend as in the solid phase. Based on this point, two new RTP molecules with long emission wavelengths (645 nm and 816 nm) are theoretically proposed and their photophysical properties are fully analyzed. Our investigation provides a wise strategy to design efficient and long-emission RTP molecules with an unconventional luminescence group.

Role of halogen effects and cyclic imide groups in constructing red and near-infrared room temperature phosphorescence molecules: theoretical perspective and molecular design.

Purely aromatic hydrocarbon materials with ultralong room-temperature phosphorescence (RTP) were reported recently, but which is universally recognized as unobservable. To reveal the inherent luminescent mechanism, two compounds, i.e., PT with a faint RTP and HD with strong RTP featured by nonplanar geometry, were chosen as a prototype to study their excited-state electronic structures by using quantum mechanics/molecular mechanics (QM/MM) model. It is demonstrated that the nonplanar ethylene brides can offer sigma-electron to strengthen spin-orbit coupling (SOC) between singlet and triplet excited states, which can not only promote intersystem crossing (ISC) of S1->Tn to increase the population of triplet excitons, but also accelerate the radiative decay rate of T1->S0, and thus improving RTP. Impressively, the nonradiative decay rate only has a small increase, owing to the synergistic effect between the increase of SOC and the reduction of reorganization energy of T1->S0 caused by the restricted torsional motions of aromatic rings. Therefore, a bright and long-lived RTP was obtained in aromatic hydrocarbon materials with twisted structure. This work provided a new insight into the ultralong RTP in pure organic materials.

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Jia Gao

Papers

Theoretical Insight Into the Ultralong Room-Temperature Phosphorescence of Nonplanar Aromatic Hydrocarbon.