41 research outputs found
1-Phenyl-3-{4-[4-(4-undecyloxybenzoyloxy)phenyloxycarbonyl]phenyl}triazene 1-oxide
The X-ray crystallographic study of the title compound, C37H41N3O6, at 150 K establishes the N-oxide form of the triazene 1-oxide unit. There is one intramolecular N—H⋯O hydrogen-bonding interaction and the crystal packing is stabilized by one N—H⋯O, three C—H⋯O and three C—H⋯π intermolecular interactions. The dihedral angles between pairs of adjacent benzene rings are 14.9 (3), 56.3 (1) and 56.0 (1)
C(naphthyl)-H Bond Activation by Rhodium: Isolation, Characterization and TD-DFT Study of the Cyclometallates
The C1(naphthyl)-H, C2(naphthyl)-H, C3(naphthyl)-H and C8(naphthyl)-H bonds of the naphthyl group present in a group of naphthylazo-2\u27-hydroxyarenes (H 2L) have been activated by [Rh(PPh 3) 3Cl] in a toluene medium. Here the cyclometallation is accompanied by metal centered oxidation [Rh(i)?Rh(iii)]. All the resulting cyclometallates [Rh(PPh 3) 2(L)Cl] (2-5) have been isolated in a pure form. The characterization of the cyclometallates [Rh(PPh 3) 2(L)Cl] have been done on the basis of spectral (IR, UV-vis, and FAB mass) data. The structures of the representative cyclometallates 2a, 3a, 4a, 4b and 5b have been determined by X-ray diffraction. In all the cyclometallates, rhodium(iii) is coordinated to naphthylazo-2\u27-hydroxyarenes via terdentate C(naphthyl), N(diazene), O(phenolato/ naphtholato) donor centers & one chloride ion in a plane along with two axial trans PPh 3 molecules. Intermolecular association in the solid state is observed due to C-H...p and p...p interactions. Compounds show an oxidative response within 0.93 to 1.11 V (vs. SCE) and a reductive response at ~ -1.0 V (vs. SCE). Both the responses are based on the coordinated diazene function and are irreversible in nature, indicating limited stability of the oxidized and reduced species. The electronic structures of selected cyclometallates have been calculated using a TD-DFT model and the simulated spectra are consistent with the observed spectra of those cyclometallates
What Sketch Explainability Really Means for Downstream Tasks
In this paper, we explore the unique modality of sketch for explainability,
emphasising the profound impact of human strokes compared to conventional
pixel-oriented studies. Beyond explanations of network behavior, we discern the
genuine implications of explainability across diverse downstream sketch-related
tasks. We propose a lightweight and portable explainability solution -- a
seamless plugin that integrates effortlessly with any pre-trained model,
eliminating the need for re-training. Demonstrating its adaptability, we
present four applications: highly studied retrieval and generation, and
completely novel assisted drawing and sketch adversarial attacks. The
centrepiece to our solution is a stroke-level attribution map that takes
different forms when linked with downstream tasks. By addressing the inherent
non-differentiability of rasterisation, we enable explanations at both coarse
stroke level (SLA) and partial stroke level (P-SLA), each with its advantages
for specific downstream tasks.Comment: CVPR 202
Palladated azobenzenes and regiospecific aromatic metaloxylation
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