Structure-Property Relationship in Amber Color Light-Emitting Electrochemical Cell with TFSI Counteranion: Enhancing Device Performance by Different Substituents on N^N Ligand

PubMed: 336670702-s2.0-85103451693Amber color emitting novel Ir(III) complexes were synthesized: [Ir(Meppy)2(Fpbpy)][PF6] (1bPF6), [Ir(Meppy)2(Fpbpy)][TFSI] (1bTFSI), [Ir(Meppy)2(MeObpy)][PF6] (2bPF6) and [Ir(Meppy)2(MeObpy)][TFSI] (2bTFSI), where Meppy = 2-(p-methylphenyl)-pyridine (b), Fpbpy = 4,4?-bis(4-fluorophenyl)-2,2?-bipyridine (1), and MeObpy = 4,4?-bis(4-methoxy)-2,2?-bipyridine (2). The photophysical and X-ray results showed that the complexes have aggregation-induced phosphorescent emission (AIPE) and a salt-induced polymorphism effect. The highest photoluminescence intensity was observed in complex 2bTFSI compared to other complexes in the solid state. Their theoretical absorption and phosphorescence emission transitions in acetonitrile were also investigated by using double- and triple-? basis sets with B3LYP and PBE0 hybrid functional. The best light-emitting electrochemical cell (LEC) performance was exhibited by complex 2bTFSI, and the data obtained were as follows: Luminance, current density, luminous efficiency, turn-on time, power efficiency, and external quantum efficiency were measured as 16 156 cd/m2, 554 mA/cm2, 8.49 cd/A, 17 s, 3.95 lm/W and 6.37%, respectively. The investigation of crystallographic characteristics have shown that the LEC performance of these complexes depends on cationic-anionic interaction which has a significant influence on molecular stacking of the molecules. Because, complex 2bTFSI, with weak cationic-anionic interactions, shows strong ?···?stacking interactions between the adjacent molecules, it is the best lighting application candidate among the complexes. © 2021 American Chemical Society.17 GEE 004 16DPT002 Dokuz Eylül Üniversitesi: KB.FEN.13We thank the Ege University Solar Energy Institute for photophysical, NMR, CV analysis, and optoelectronic measurements (grant no. 17 GEE 004 and TUBITAK: 16DPT002). We also thank Izmir Katip Celebi University Central Research Laboratory for TGA analysis. We are grateful to Dokuz Eylul University for crystallographic measurements (Agilent Xcalibur Eos diffractometer, grant no. 2010.KB.FEN.13). We also thank Hacettepe University and TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA resources) for DFT and TD-DFT calculations

Expanding and Testing a Computational Method for Predicting the Ground State Reduction Potentials of Organic Molecules on the Basis of Empirical Correlation to Experiment

A method for predicting the ground state reduction potentials of organic molecules on the basis of the correlation of computed energy differences between the starting S-0 and one-electron-reduced D-0 species with experimental reduction potentials in acetonitrile has been expanded to cover 3.5 V of potential range and 74 compounds across 6 broad families of molecules. Utilizing the conductor-like polarizable continuum model of implicit solvent allows a global correlation that is computationally efficient and has improved accuracy, with r(2) \u3e 0.98 in all cases and root mean square deviation errors of(mean absolute deviationsmV) for either B3LYP/6-311+G(d,p) or B3LYP//6-31G(d) with an appropriate choice of radii (UAKS or UA0). The correlations are proven to be robust across a wide range of structures and potentials, including four larger (27-28 heavy atoms) and more conformationally flexible photochromic molecules not used in calibrating the correlation. The method is also proven to be robust to a number of minor student mistakes or methodological inconsistencies