Silylene-Copper-Amide Emitters: From Thermally Activated Delayed Fluorescence to Dual Emission.

Herein, we report the inaugural instance of NHSi-coordinated copper amide emitters (2-5). These complexes exhibit thermally activated delayed fluorescence (TADF) and singlet-triplet dual emission in anaerobic conditions. The NHSi-Cu-diphenylamide (2) complex demonstrates TADF with a very small ΔEST gap (0.01 eV), an absolute quantum yield of 11%, a radiative rate of 2.55×105 s-1, and a short τTADF of 0.45 µs in the solid state. The dual emissive complexes (3-5) achieve an absolute quantum yield of up to 20% in the solid state with a kISC rate of 1.82×108 s-1 and exhibit room temperature phosphorescence (RTP) with lifetimes up to 9 ms. The gradual decrease in the intensity of the triplet state of complex 3 under controlled oxygen exposure demonstrates its potential for future oxygen-sensing applications. Complexes 2 and 3 have been further utilized to fabricate converted LEDs, paving the way for future OLED production using newly synthesized NHSi-Cu-amides.

Activation of TADF in Photon Upconverting Crystals of Dinuclear Cu(I)-Iodide Complexes by Ligand Engineering.

This work reports that ligand engineering can modulate the triplet harvesting mechanism in iodide-bridged rhombic Cu2I2 complexes. Complex-1, with a smaller Cu-Cu distance, exhibits phosphorescence from 3(M+X)LCT and 3CC states with 66% quantum yield, whereas an increased Cu-Cu distance in complex-2 results in a switch of the emission from phosphorescence to TADF, which occurs via 1/3(M+X)LCT states with 83% quantum yield. The TADF property of complex-2 has been utilized for the fabrication of a pc-LED emitting efficient warm white light. Moreover, the high charge-transfer nature of these complexes leads to the emergence of third-harmonic generation (THG). Interestingly, complex-1 exhibits efficient third-harmonic generation with a χ(3) value of 1.15 × 10-18 m2 V-2 and LIDT value of 14.73 GW/cm2. This work aims to provide a structure-property relationship to achieve effective harvestation of triplet excitons in iodide-bridged rhombic Cu2I2 complexes and their effective utilization in OLED device fabrication and nonlinear photon upconversion processes.

Engineering TADF, mechanochromism, and second harmonic up-conversion properties in regioisomeric substitution space.

This research article explores the distinct TADF efficiency of three donor-acceptor based regio-isomers: DPAOCN (ortho-isomer), DPAMCN (meta-isomer), and DPAPCN (para-isomer). DPAPCN exhibits maximum TADF efficiency in both solution and solid-state with an impressive reverse inter-system crossing (RISC) rate of ∼106 s-1; the underlying cause being the minimum singlet-triplet splitting energy or ΔEST and maximum SOC (spin-orbit coupling) between the S1 & T1 states. Apart from TADF, differences in crystal packing of the regio-isomers result in intriguing bulk phase properties. DPAOCN, with its non-centrosymmetric P212121 space group and substantial crystal void volume, exhibits reversible tri-color mechanochromic luminescence behavior, while the meta and para isomers, due to their centrosymmetric packing and diminished crystal void volume, remain inert to mechanical pressure. Expanding the horizon of possibilities, the non-centrosymmetric nature of ortho-isomer further renders it an excellent SHG material, with a χ(2) value of 0.19 pm V-1 at 1220 nm and a laser-induced damage threshold (LIDT) value of 13.27 GW cm-2. Overall, a comprehensive investigation into the regio-isomers has been carried out, encompassing their TADF, SHG, and mechanochromic luminescent properties.

Luminescent magnesium complexes with intra- and inter-ligand charge transfer.

Herein, we report two 2,2'-pyridylpyrrolide (PyPyrH) ligand supported magnesium complexes (1 and 2), which demonstrate bright luminescence with a quantum yield of 22% and 14% in the solid state, respectively. Theoretical calculations reveal that their emissive properties originate from the intra- and inter-ligand charge transfer.

Where to display vital information? ERP evidence for background changes.

Critical decision systems require expeditious and accurate responses to the displayed information. In addition to content, location and background are equally important. Several visual search studies have pointed out the differences and compared modes of top-down attention allocation: distractor suppression and attentional capture. Previous studies have used color (mainly) and shape as a feature but have overlooked luminance as a feature for studying underlying attention mechanisms. The present study attempts to bridge this gap. In this study, participants performed a target-distractor discrimination task by identifying a randomly appearing target from the pool of distractors based on defined luminance levels. Background change was noticed by manipulating the task such as making visible quadrant boundaries over the screen. The preliminary evidence suggested that displaying information at the top-left of the screen had higher percentage accuracy; whereas, response time (RT) remained unaffected. Improvement in RT and percentage accuracy was observed with task manipulation. Event-related potential (ERP) analysis revealed elicited Distractor Positivity (PD), providing evidence for the distractor suppression hypothesis. Further, differences emerged in the topographic plot of N2pc and PD. In sum, the result contributes to classic debate of capture vs. suppression and provides a crucial connection between display design and electrophysiological indices, emphasizing locations and background as equally important factors.

Intrinsic-to-extrinsic emission tuning in luminescent Cu nanoclusters by in situ ligand engineering.

Enhancement of the emission quantum yield and expansion of the emission tunability spectrum are the key aspects of an emitter, which direct the evolution of future generation light harvesting materials. In this regard, small molecular ligand-protected Cu nanoclusters (SLCuNCs) have emerged as prospective candidates. Herein, we report the broadband emission tunability in a SLCuNC system, mediated by in situ ligand replacement. 1,6-Hexanedithiol-protected blue emissive discrete Cu nanoclusters (CuNCs) and red emissive CuNC assemblies have been synthesized in one pot. The red emissive CuNC assemblies were characterized and found to be covalently-linked nanocluster superstructures. The blue emissive CuNC was further converted to a green-yellow emissive CuNC over time by a ligand replacement process, which was mediated by the oxidized form of the reducing agent used for synthesizing the blue emissive nanocluster. Steady-state emission results and fluorescence dynamics studies were used to elucidate that the ligand replacement process not only modulates the emission color but also alters the nature of emission from metal-centered intrinsic to ligand-centered extrinsic emission. Moreover, time-dependent blue to green-yellow emission tunability was demonstrated under optimized reaction conditions.

Emergence of Aggregation Induced Emission (AIE), Room-Temperature Phosphorescence (RTP), and Multistimuli Response from a Single Organic Luminogen by Directed Structural Modification.

Multifunctional organic luminogens exhibiting simultaneous aggregation induced emission (AIE), room-temperature phosphorescence (RTP), and mechanochromism have recently attracted considerable attention owing to their potential applications in optoelectronics and bioimaging. However, a comprehensive correlation among these three distinguished properties is yet to be unveiled, which will help to decipher defined methodologies to design future generation multifunctional organic materials. Herein, we have demonstrated a route to obtain a multifunctional organic luminogen, starting from an ACQphore (TPANDI) by simple structural engineering. We have shown that a slight reduction in length of the planar acceptor moieties can effectively inhibit the undesirable π-π stacking interaction between molecules in the condensed state and thereby cause an ACQ to AIE type transformation from TPANDI to TPANMI and TPAPMI. Both TPANMI and TPAPMI exhibit RTP properties (even in ambient condition) because of the presence of a reasonably low singlet-triplet energy gap (ΔEST). In our study, these two luminogens were found to be mechano-inactive. Interestingly, an insertion of cyano-ethylene group and benzene linker in between the triphenylamine and phthalimide moieties introduced another luminogen TPACNPMI, which can simultaneously exhibit AIE, RTP, and mechanochromic properties.

Liver transplantation in Indian Armed Forces-initial experience.

BACKGROUND: This study retrospectively analyses the initial experience of liver transplantation (LT) in the Indian Armed Forces. METHODS: Fifty-three patients underwent LT at Army Hospital (R&R) Delhi Cantt. between March 2007 and March 2011. Of these 35 patients underwent deceased donor liver transplantation (DDLT) and living donor liver transplantation (LDLT) was carried out in 18 patients. The surgical techniques, complications and mortality were analysed. RESULTS: A high consent rate of 35.9% for organ donation was achieved by the Armed Forces Organ Retrieval and Transplantation Authority (AORTA). Biliary complications occurred in five patients (9.4%). However, most of them could be managed by endoscopic interventions. Hepatic artery thrombosis (HAT) occurred in five patients (9.4%). Of these, two DDLT grafts were revascularised following HAT, by creating extra-anatomic arterial conduits with excellent outcome. The overall mortality was 18.8% (n = 10). There was no significant difference in the overall complications or mortality in patients undergoing DDLT or LDLT. CONCLUSION: The overall survival and morbidity in this study is comparable to those from other centres. Urgent revascularisation of grafts following HAT should be attempted as it can salvage grafts with satisfactory outcome. There is a reduction in the incidence of biliary complications with refinements in surgical techniques.