Isolation of Fluorescent 2π-Aromatic 1,3-Disiladiboretenes.

Herein, we reported the isolation of 2π-aromatic disiladiboretenes (L2Si2B2Ph2) [L = ArC(NtBu)2, Ar = Ph (1), Mes (2)], which have been synthesized from the straightforward reduction of silylene-borane adducts (LSiX → BX2Ph) [X = Cl, Br] with potassium graphite (KC8). X-ray diffraction analysis of 1 and 2 revealed that the Si2B2 units are completely planar, and DFT calculations suggested delocalization of 2π-electrons over the Si2B2 rings. Moreover, their photophysical properties and reactivity toward sulfur were also investigated in detail.

Isolable Dibenzo[a,e]disilapentalene with a Dichotomic Reactivity toward CO2.

The first dibenzo[a,e]disilapentalene with two Si═C moieties in the heteropentalene core has been prepared. Its solid-state structure and density functional theory (DFT) calculations revealed that the Si═C bonds are involved in an expanded π-conjugated system. The Si═C bonds show a distinguished reactivity toward CO2, depending on the reaction conditions. While one product results from fixation of two CO2 molecules across one Si═C bond, two different products could be isolated from the reaction of three CO2 molecules with both Si═C bonds. The mechanism has been uncovered by DFT calculations.

Zwitterionic Inorganic Benzene Valence Isomer with σ-Bonding between Two π-Orbitals.

Despite the large number of plausible isomers of benzene (C6H6), only four valence isomers [(CH)6] have been experimentally detected, all of which are nonionic and possess skeletal frameworks built from localized C-C bonds. Herein, we present the isolation of a diazatetraborabenzene analogue of a hypothetical zwitterionic valence isomer of benzene. Therein, two electrons are delocalized over the four boron atoms in the six-membered B4N2 ring, which is a result of the σ-bonding interaction between two odd-electron B-B π-orbitals. Simple treatment with a crown ether leads to the formation of a paramagnetic potassium-doped radical ion pair that exhibits a thermally populated triplet character.

Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2-Diazaboroles.

Diverse skeletal transformations of 1,4,2-diazaboroles through ring expansion, photoisomerization, and retrocyclization led to the isolation of various B,N-dihydroindole (compounds 3 and 6), 1,3-azaborolidin-2-imine (compound 7), and 1,4,2-diazaborol-3-imine derivatives (compound 11).

Isolation and Reactivity of 1,4,2-Diazaborole.

An isolable 1,4,2-diazaborole derivative was synthesized and structurally characterized. X-ray diffraction analysis and computational studies revealed a delocalization of 6π-electrons over the BC2N2 five-membered ring, which thus indicates the aromatic property. The reactivity toward electrophiles such as MeOTf and selectfluor was also investigated.

Synthesis and spectroscopy of anionic cyclometalated iridium(III)-dithiolate and -sulfinates--effect of sulfur dioxygenation on electronic structure and luminescence.

A new anionic heteroleptic Ir(III)-dithiolate complex Ir(ppy)2(benzene-1,2-dithiolate) (ppy = 2-phenylpyridine, [IrSS](-)) undergoes very fast air oxidation to form a monosulfinate complex [IrSSO2](-), which can be further dioxygenated by O2 or H2O2 to give a disulfinate complex [IrSO2SO2](-), which has been characterized by X-ray crystallography. The dioxygenation is accompanied by changes in the electronic structures of the complexes, leading to blue shift of emission from [IrSS](-) (λ(max) = 665 nm) to [IrSSO2](-) (λ(max) = 556 nm) and to [IrSO2SO2](-) (λ(max) = 460 nm). The molecular and electronic structures of the complexes are probed by DFT calculations. Time-dependent DFT (TD-DFT) calculations show the lowest energy spin-allowed electronic transitions for [IrSS](-) and [IrSSO2](-) are mainly ligand (3p orbital of S)-to-ligand (π* orbitals of ppy)-charge-transfer transition, whereas the lowest energy electronic transition in [IrSO2SO2](-) is predominantly metal-to-ligand-charge transfer in nature.

Isolation of an imino-N-heterocyclic carbene/germanium(0) adduct: a mesoionic germylene equivalent.

An autoionization of germanium dichloride/dioxane complex with an imino-N-heterocyclic carbene ligand (L) afforded a novel germyliumylidene ion, [(L)GeCl](+)[GeCl3](-), which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [(L)Ge], which can be viewed as both a Ge(0) species and a mesoionic germylene. X-ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC2N2 five-membered ring. It was also confirmed that the nucleophilic behavior of [(L)Ge] as a two lone-pair donor.

Achieving pure room temperature phosphorescence (RTP) in phenoselenazine-based organic emitters through synergism among heavy atom effect, enhanced n → π* transitions and magnified electron coupling by the A-D-A molecular configuration.

The weak spin-orbit coupling (SOC) in metal-free organic molecules poses a challenge in achieving phosphorescence emission. To attain pure phosphorescence in RTP organic emitters, a promising molecular design concept has been proposed. This involves incorporating n → π* transitions and leveraging the heavy atomic effect within the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC) mechanism of bipolar molecules. Following this design concept, two bipolar metal-free organic molecules (PhSeB and PhSeDB) with donor-acceptor (D-A) and acceptor-donor-acceptor (A-D-A) configurations have been synthesized. When the molecular configuration changes from D-A to A-D-A, PhSeDB exhibits stronger electron coupling and n → π* transitions, which can further enhance the spin-orbit coupling (SOC) together with the heave atom effect from the selenium atom. By the advanced synergism among enhanced n → π* transitions, heavy atom effect and magnified electron coupling to efficiently promote phosphorescence emission, PhSeDB can achieve pure RTP emission in both the solution and doped solid film. Thanks to the higher spin-orbit coupling matrix elements (SOCMEs) for T1 ↔ S0, PhSeDB attains the highest phosphorescence quantum yield (ca. 0.78) among all the RTP organic emitters reported. Consequently, the purely organic phosphorescent light-emitting diodes (POPLEDs) based on PhSeDB achieve the highest external quantum efficiencies of 18.2% and luminance of 3000 cd m-2. These encouraging results underscore the significant potential of this innovative molecular design concept for highly efficient POPLEDs.

Vehicle re-identification method based on multi-attribute dense linking network combined with distance control module.

Introduction: Vehicle re-identification is a crucial task in intelligent transportation systems, presenting enduring challenges. The primary challenge involves the inefficiency of vehicle re-identification, necessitating substantial time for recognition within extensive datasets. A secondary challenge arises from notable image variations of the same vehicle due to differing shooting angles, lighting conditions, and diverse camera equipment, leading to reduced accuracy. This paper aims to enhance vehicle re-identification performance by proficiently extracting color and category information using a multi-attribute dense connection network, complemented by a distance control module. Methods: We propose an integrated vehicle re-identification approach that combines a multi-attribute dense connection network with a distance control module. By merging a multi-attribute dense connection network that encompasses vehicle HSV color attributes and type attributes, we improve classification rates. The integration of the distance control module widens inter-class distances, diminishes intra-class distances, and boosts vehicle re-identification accuracy. Results: To validate the feasibility of our approach, we conducted experiments using multiple vehicle re-identification datasets. We measured various quantitative metrics, including accuracy, mean average precision, and rank-n. Experimental results indicate a significant enhancement in the performance of our method in vehicle re-identification tasks. Discussion: The findings of this study provide valuable insights into the application of multi-attribute neural networks and deep learning in the field of vehicle re-identification. By effectively extracting color information from the HSV color space and vehicle category information using a multi-attribute dense connection network, coupled with the utilization of a distance control module to process vehicle features, our approach demonstrates improved performance in vehicle re-identification tasks, contributing to the advancement of smart city systems.

PtII(C

A series of four-coordinated PtII(C^N)(N-donor ligand)Cl-type complexes have been synthesized through a combination of long-size C^N-type and N-donor ligands. In addition, by varying the coordinating site in the N-donor ligand, a distorted molecular configuration has been constructed in these complexes. Their photophysical features, aggregation-induced phosphorescence emission (AIPE) behaviors, electrochemical properties and electroluminescence (EL) performance have been investigated in detail. It has been found that their AIE behaviors can be enhanced by both employing long-size ligands, especially the N-donor ligand, and adopting a distorted molecular configuration, furnishing a high AIE factor (αAIE) of ca. 13.8. Critically, benefitting from their long-size C^N-type and N-donor ligands, these PtII(C^N)(N-donor ligand)Cl-type complexes can exhibit very sensitive AIE behaviors in a mixture of THF-H2O, indicated by their noticeable emission increase with a low H2O volumetric fraction (fw) of ca. 0.1 in their THF solution. In solution-processed organic light-emitting diodes (OLEDs), they can achieve a luminance of 6743 cd m-2 at 13.5 V, a maximum external quantum efficiency (ηext) of 13.8%, a maximum current efficiency (ηL) of 42.4 cd A-1 and a maximum power efficiency (ηP) of 34.4 lm W-1, respectively. Hence, this research can provide key information for developing phosphorescent complexes with a highly sensitive AIE response and impressive EL ability.

Viscoelasticity of children and adolescent brains through MR elastography.

Magnetic Resonance Elastography (MRE) is an elasticity imaging technique that allows a safe, fast, and non-invasive evaluation of the mechanical properties of biological tissues in vivo. Since mechanical properties reflect a tissue's composition and arrangement, MRE is a powerful tool for the investigation of the microstructural changes that take place in the brain during childhood and adolescence. The goal of this study was to evaluate the viscoelastic properties of the brain in a population of healthy children and adolescents in order to identify potential age and sex dependencies. We hypothesize that because of myelination, age dependent changes in the mechanical properties of the brain will occur during childhood and adolescence. Our sample consisted of 26 healthy individuals (13 M, 13 F) with age that ranged from 7-17 years (mean: 11.9 years). We performed multifrequency MRE at 40, 60, and 80 Hz actuation frequencies to acquire the complex-valued shear modulus G = G' + iG″ with the fundamental MRE parameters being the storage modulus (G'), the loss modulus (G″), and the magnitude of complex-valued shear modulus (|G|). We fitted a springpot model to these frequency-dependent MRE parameters in order to obtain the parameter α, which is related to tissue's microstructure, and the elasticity parameter k, which was converted to a shear modulus parameter (µ) through viscosity (η). We observed no statistically significant variation in the parameter µ, but a significant increase of the microstructural parameter α of the white matter with increasing age (p < 0.05). Therefore, our MRE results suggest that subtle microstructural changes such as neural tissue's enhanced alignment and geometrical reorganization during childhood and adolescence could result in significant biomechanical changes. In line with previously reported MRE data for adults, we also report significantly higher shear modulus (µ) for female brains when compared to males (p < 0.05). The data presented here can serve as a clinical baseline in the analysis of the pediatric and adolescent brain's viscoelasticity over this age span, as well as extending our understanding of the biomechanics of brain development.

Germylone-bridged bimetallic Ir and Rh complexes.

The reactions of germylone 1 with one equivalent of [M(COD)Cl]2 (M = Ir, Rh) afforded the germylone-bridged bimetallic complexes 2 and 3, which have been spectroscopically and structurally characterized. Density functional theory (DFT) studies reveal the relatively strong interactions between the Ge atom and these metals. By the reaction of [Rh(COD)Cl]2 with CO followed by addition of 1, a complex 4 involving a Rh-Ge-Rh-Ge-Rh chain was also synthesized.

Factors influencing infarct growth including collateral status assessed using computed tomography in acute stroke patients with large artery occlusion.

In major ischemic stroke caused by a large artery occlusion, neuronal loss varies considerably across individuals without revascularization. This study aims to identify which patient characteristics are most highly associated with this variability. Demographic and clinical information were retrospectively collected on a registry of 878 patients. Imaging biomarkers including Alberta Stroke Program Early CT score, noncontrast head computed tomography infarct volume, perfusion computed tomography infarct core and penumbra, occlusion site, collateral score, and recanalization status were evaluated on the baseline and early follow-up computed tomography images. Infarct growth rates were calculated by dividing infarct volumes by the time elapsed between the computed tomography scan and the symptom onset. Collateral score was graded into four levels (0, 1, 2, and 3) in comparison with the normal side. Correlation of perfusion computed tomography and noncontrast head computed tomography infarct volumes and infarct growth rates were estimated with the nonparametric Spearman's rank correlation. Conditional inference trees were used to identify the clinical and imaging biomarkers that were most highly associated with the infarct growth rate and modified Rankin Scale at 90 days. Two hundred and thirty-two patients met the inclusion criteria for this study. The median infarct growth rates for perfusion computed tomography and noncontrast head computed tomography were 11.2 and 6.2 ml/log(min) in logarithmic model, and 18.9 and 10.4 ml/h in linear model, respectively. Noncontrast head computed tomography and perfusion computed tomography infarct volumes and infarct growth rates were significantly correlated (rho=0.53; P < 0.001). Collateral status was the strongest predictor for infarct growth rates. For collateral=0, the perfusion computed tomography and noncontrast head computed tomography infarct growth rate were 31.56 and 16.86 ml/log(min), respectively. Patients who had collateral >0 and penumbra volumes>92 ml had the lowest predicted perfusion computed tomography infarct growth rates (6.61 ml/log(min)). Collateral status was closely related to the diversity of infarct growth rates, poor collaterals were associated with a faster infarct growth rates and vice versa.

Synthesis, characterization, and electronic structures of a methyl germyliumylidene ion and germylone-group VI metal complexes.

The reaction of germylone (L)Ge (1) [L = 3-Ad-1-{C((t)Bu) = N(Mes)}C3H4N2] with 1 equivalent of MeOTf afforded a germyliumylidene ion [(L)GeMe](+)OTf(-) (2), while reactions with M(CO)5(thf) (M = Cr, Mo, W) gave the corresponding germylone-metal complexes [(L)Ge]M(CO)5 (3-5). The former possesses a pyramidal Ge center, whereas the latter display a planar geometry around the Ge atom. Computational studies showed a unique bonding interaction between 1 and the M(CO)5 unit, which involves a σ-donation as well as a weak π-back-donation.