We describe the synthesis of new cationic tricoordinated copper complexes bearing bidentate pyridine-type ligands and N-heterocyclic carbene as ancillary ligands. These cationic copper complexes were fully characterized by NMR, electrochemistry, X-ray analysis, and photophysical studies in different environments. Density functional theory calculations were also undertaken to rationalize the assignment of the electronic structure and the photophysical properties. These tricoordinated cationic copper complexes possess a stabilizing CH-π interaction leading to high stability in both solid and liquid states. In addition, these copper complexes, bearing dipyridylamine ligands having a central nitrogen atom as potential anchoring point, exhibit very interesting luminescent properties that render them potential candidates for organic light-emitting diode applications.
This study presents the influence of various substituents on the photophysical features of heteroleptic copper(I) complexes bearing both N-heterocyclic carbene (NHC) and dipyridylamine (dpa = dipyridylamine skeleton corresponding to ligand L1) ligands. The luminescent properties have been compared to our recently reported archetypal blue emitting [Cu(IPr)(dpa)][PF6] complex. The choice of the substituents on both ligands has been guided to explore the effect of the electron donor/acceptor and "push-pull" on the emission wavelengths and photoluminescence quantum yields. A selection of the best candidates in terms of their photophysical features were applied for developing the first blue light-emitting electrochemical cells (LECs) based on copper(I) complexes. The device analysis suggests that the main concern is the moderate redox stability of the complexes under high applied driving currents, leading to devices with moderate stabilities pointing to a proof-of-concept for further development. Nevertheless, under low applied driving currents the blue emission is stable, showing performance levels competitive to those reported for blue LECs based on iridium(III) complexes. Overall, this work provides valuable guidelines to tackle the design of enhanced NHC copper complexes for lighting applications in the near future.
Recent developments of plastic scintillators are reviewed, from 2000 to March 2014, distributed in two different chapters. First chapter deals with the chemical modifications of the polymer backbone, whereas modifications of the fluorescent probe are presented in the second chapter. All examples are provided with the scope of detection of various radiation particles. The main characteristics of these newly created scintillators and their detection properties are given.
This article presents the synthesis and the blend of bismuth complexes in polystyrene based plastic scintillators. A specific design has enabled the fabrication of a scintillator loaded with up to 17 wt% of bismuth. Tri-carboxylate and triaryl bismuth compounds were used to explore and understand the influence of bismuth loading on the two main criteria of plastic scintillation: light yield and detection efficiency of g-rays. For gamma radiation with an energy <200 keV, bismuth loaded scintillators demonstrate the ability to produce a photoelectric peak (total absorption peak) in pulse height spectra.The increase of interactions due to bismuth doping was quantified and fitted with standard models.Finally the performance of our bismuth loaded scintillators was evaluated to be better than that of a commercial lead loaded counterpart.
Organometallic chemistry has recently gained a lot of attention in the domain of plastic scintillators.Homogenously dispersed metal complexes in a polymer matrix can afford plastic scintillators with unseen abilities. Heavy atom loading is very attractive as it gives access to plastics with increased sensitivity towards elusive radiations such as gamma and neutron. But this comes with a drawback, as heavy atoms tend to quench fluorescence, hence decreasing the scintillation yield. We present here a comprehensive study of this phenomenon with bismuth and gadolinium complexes. We investigate the influence of the ligand nature by varying organometallic and fluorophore concentration to probe their interaction. We also propose an explanation of the difference in behavior between these two metals. These results were applied to the fabrication of large volume loaded plastic scintillators (4100 cm 3 ). Bismuth loaded scintillators displayed characteristics equivalent to lead loaded commercial materials, and gadolinium samples proved to be able to capture thermal neutrons and release gamma rays. of our optimization, large scale loaded PSs (4100 cm 3 ) were synthesized and characterized.
Two new series of cyclometalated iridium(III) complexes bearing a dipyridylamine as the N^N ligand have been prepared and fully characterized. After investigation of their photophysical properties, their catalytic activities have been evaluated in a model photoredox reaction and compared with the commercially available [Ir( ppy) 2 (dtbbpy)][PF 6 ] complex.
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