Dissecting Tetra-N-phenylbenzidine: Biphenyl as the Origin of Room Temperature Phosphorescence.

Amorphous purely organic thin films are able to show efficient phosphorescence under ambient conditions at room temperature. This opens the perspective to a wide range of new applications, which have attracted lots of interest in the field of material science recently. Therefore, an increasing number of different molecules displaying room temperature phosphorescence (RTP) have already been reported. Whereas the efficiency, the lifetime, or the oxygen sensitivity is frequently discussed, the origin of RTP mainly remains vague. Often, material design rules tend to the development of increasingly complex structures. Here, the well-known tetra-N-phenylbenzidine (TPD), an archetypical material showing highly efficient fluorescence and RTP, is broken down to its fragments. As the complexity of the system decreases with the molecule's size, spectroscopic investigation of this molecular family enables a deeper understanding of the appearance of RTP. With spectral and time-resolved measurements, RTP can be detected for all compounds containing a biphenyl core, with lifetimes up to 0.9 s under inert gas conditions. These findings form the basis of a deeper understanding of the appearance of RTP in organic molecules and therefore allow for a more focused investigation of new materials.

Blue-Light-Absorbing Thin Films Showing Ultralong Room-Temperature Phosphorescence.

The development of organic materials displaying ultralong room-temperature phosphorescence (URTP) is a material design-rich research field with growing interest recently, as the luminescence characteristics have started to become interesting for applications. However, the development of systems performing under aerated conditions remains a formidable challenge. Furthermore, in the vast majority of molecular examples, the respective absorption bands of the compounds are in the near ultraviolet (UV) range, which makes UV excitation sources necessary. Herein, the synthesis and detailed analysis of new luminescent organic metal-free materials displaying, in addition to conventional fluorescence, phosphorescence with lifetimes up to 700 ms and tailored redshifted absorption bands, allowing for deep blue excitation, are reported. For the most promising targets, their application is demonstrated in the form of organic programmable tags that have been recently developed. These tags make use of reversible activation and deactivation of the URTP by toggling between the presence and absence of molecular oxygen. In this case, the activation can be achieved with visible light excitation, which greatly increases the use case scenarios by making UV sources obsolete.