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Organic semiconductors provide the potential of biodegradable technologies, but prototypes do only rarely exist. Transparent, ultrathin programmable luminescent tags (PLTs) are presented for minimalistic yet efficient information storage that are fully made from biodegradable or at least industrially compostable, ready-to-use materials (bioPLTs). As natural emitters, the quinoline alkaloids show sufficient room temperature phosphorescence when being embedded in polymer matrices with cinchonine exhibiting superior performance. Polylactic acid provides a solution for both the matrix material and the flexible substrate. Room temperature phosphorescence can be locally controlled by the oxygen concentration in the film by using Exceval as additional oxygen blocking layers. These bioPLTs exhibit all function-defining characteristics also found in their regular nonenvironmentally degradable analogs and, additionally, provide a simplified, high-contrast readout under continuous-wave illumination as a consequence of the unique luminescence properties of the natural emitter cinchonine. Limitations for flexible devices arise from limited thermal stability of the polylactic acid foil used as substrate allowing only for one writing cycle and preventing an annealing step during fabrication. Few-cycle reprogramming is possible when using the architecture of the bioPLTs on regular quartz substrates. This work realizes the versatile platform of PLTs with less harmful materials offering more sustainable use in future., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Herein, a simple way of tuning the optical and structural properties of porphyrin-based hydrogen-bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB-5 (p-H 8 -TPPA (5,10,15,20-Tetrakis[p-phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu-, Ni-, Pd-, and Zn-GTUB-5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal-induced structural changes, viz., changes in the metal-to-nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu-, Zn-, and Pd- GTUB-5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π- orbitals on the porphyrin linkers, while that of Ni-GTUB-5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal-insertion can be used to optimize HOFs for optoelectronics and small-molecule capture applications., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D-PPQV1 and 2D-PPQV2, via the Horner-Wadsworth-Emmons (HWE) reaction of C 2 -symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4'-bis(diethylphosphonomethyl)biphenyl with C 3 -symmetric 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino[2,3-a:2',3'-c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C-C single bond formation for the synthesis of crystalline 2D CPs. Powder X-ray diffraction (PXRD) studies and nitrogen adsorption-desorption measurements demonstrate the formation of proclaimed crystalline, dual-pore structures with surface areas of up to 440 m 2  g -1 . More importantly, the optoelectronic properties of the obtained 2D-PPQV1 (E g =2.2 eV) and 2D-PPQV2 (E g =2.2 eV) are compared with those of cyano-vinylene-linked 2D-CN-PPQV1 (E g =2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, E g =2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction., (© 2020 Wiley-VCH GmbH.)

In recent years, there has been a growing interest in purely organic materials showing ultralong room-temperature phosphorescence with lifetimes in the range of seconds. Still, the longest known phosphorescence lifetimes are only achieved with crystalline systems so far. Here, a rational design of a completely new family of halogen-free organic luminescent derivatives in amorphous matrices, displaying both conventional fluorescence and phosphorescence is reported. Hydrogen bonding between the newly developed emitters and an ethylene-vinyl alcohol copolymer (Exceval) matrix, which efficiently suppresses vibrational dissipation, enables bright long-lived phosphorescence with lifetimes up to 2.6 s at around 480 nm. The importance of the chosen matrix is shown as well as the implementation in an organic programmable luminescent tag., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)