Search Results (12)

In this study, we report the synthesis and characterization of three Cu(I) complexes bearing functionalized dipyridylamine ligands and DPEphos. Structural analysis confirms a distorted tetrahedral coordination environment around the metal center. Photophysical studies in DMSO show similar absorption profiles (λ_abs ≈ 341–343 nm) with ligand-centered and MLCT transitions, while emission spans the visible region (λ_emi = 410–483 nm) and is strongly influenced by ligand substitution, with the CF₃ derivative displaying a marked red shift. Emission is insensitive to oxygen and exhibits short lifetimes (τ ≈ 14.9–15.3 ns), suggesting short-lived ¹MLCT excited states. Biological evaluation in A375 melanoma cells reveals that all complexes exhibit low-micromolar cytotoxicity under dark conditions (IC₅₀ = 3.33–4.92 μM). Notably, only the CF₃-substituted complex shows a significant light-induced enhancement of activity upon irradiation at 390 nm (IC₅₀ = 1.18 μM), indicating photoactivation. Full article

The explorations of new three-dimensional (3D) microporous metal halides, especially the iodoargentate-based hybrids, and understanding of their structure-activity relationships are still quite essential but full of great challenges. Herein, with the aromatic 4,4′-dpa (4,4′-dpa = 4,4′-dipyridylamine) ligands as the structural directing agents, we solvothermal synthesized and structurally characterized a novel member of microporous iodoargentate family, namely [H₂-4,4′-dpa]Ag₆I₈ (1). Compound 1 possesses a unique and complicated 3D [Ag₆I₈]_n²ⁿ⁻ anionic architecture that was built up from the unusual hexameric [Ag₆I₁₃] secondary building units (SBUs). Research on optical properties indicated that compound 1 exhibited semiconductor behavior, with an optical band gap of 2.50 eV. Under the alternate irradiation of light, prominent photoelectric switching abilities could be achieved by compound [H₂-4,4′-dpa]Ag₆I₈, whose photocurrent densities (0.37 μA·cm⁻² for visible light and 1.23 μA·cm⁻² for full-spectrum) compared well with or exceeded those of some high-performance halide counterparts. Further theoretical calculations revealed that the relatively dispersed conduction bands (CBs) structures in compound 1 induced higher electron mobilities, which may be responsible for its good photoelectricity. Presented in this work also comprised the analyses of Hirshfeld surface, powder X-ray diffractometer (PXRD), thermogravimetric measurement, energy-dispersive X-ray spectrum (EDX) along with X-ray photoelectron spectroscopy (XPS). Full article

The aqueous solubility of solid-state pharmaceuticals can often be enhanced by cocrystallization with a coformer to create a binary cocrystal with preferred physical properties. Greater understanding of the internal and external forces that dictate molecular structure and intermolecular packing arrangements enables more efficient design of new cocrystals. Low-frequency (sub-200 cm⁻¹) Raman spectroscopy experiments and solid-state density functional theory simulations have been utilized together to investigate the crystal lattice vibrations of mycophenolic acid, an immunosuppressive drug, in its pure form and as a cocrystal with 2,2′-dipyridylamine. The lattice vibrations primarily consist of large-amplitude translations and rotations of the crystal components, thereby providing insights into the critical intermolecular forces governing cohesion of the molecular solids. The simulations reveal that despite mycophenolic acid having a significantly unfavorable conformation in the cocrystal as compared to the pure solid, the cocrystal exhibits greater thermodynamic stability over a wide temperature range. The energetic penalty due to the conformational strain is more than compensated for by the strong intermolecular forces between the drug and 2,2′-dipyridylamine. Quantifying the balance of internal and external energy factors in cocrystal formation indicates a path forward in the development of future mycophenolic acid cocrystals. Full article

We evaluate the effectiveness of chelating resins (CR) derived from Merrifield resin (MR) and 1,2-phenylenediamine (PDA), 2,2’-dipyridylamine (DPA), and 2-(aminomethyl)pyridine (AMP) as adsorbent dosimeters for Ag⁺, Cu²⁺, Fe³⁺, and Pb²⁺ cations from water under competitive and noncompetitive conditions. MR-PDA, MR-DPA, and MR-AMP were obtained in a 95–97% yield and characterized by IR, fluorescence, and SEM. The ability of CRs as adsorbents was determined by batch and flow procedures. MR-PDA showed a batch adsorption capacity order of Fe³⁺ (29.8 mg/g) > Ag⁺ (2.7 mg/g) > Pb²⁺ (2.6 mg/g) at pH 3.4. The flow adsorption showed affinity towards the Ag⁺ cation at pH 7 (18.4 mg/g) and a reusability of 10 cycles. In MR-DPA, the batch adsorption capacity order was Ag⁺ (9.1 mg/g) > Pb²⁺ (8.2 mg/g) > Cu²⁺ (3.5 mg/g) at pH 5. The flow adsorption showed affinity to the Cu²⁺ cation at pH 5 (2.2 mg/g) and a reuse of five cycles. In MR-AMP, the batch adsorption capacity was Ag⁺ (17.1 mg/g) at pH 3.4. The flow adsorption showed affinity to the Fe³⁺ cation at pH 2 (4.3 mg/g) and a reuse of three cycles. The three synthesized and reusable CRs have potential as adsorbents for Ag⁺, Cu²⁺, Fe³⁺, and Pb²⁺ cations and showed versatility in metal removal for water treatment. Full article

A series of six heteroleptic copper(II) complexes with 2′-hydroxy-4-(dimethylamino)chalcone (HL) with the composition [Cu(N-N)(L)]NO₃ (1–6), where N-N stands for dmbpy = 5,5′-dimethyl-2,2′-bipyridine (1), bphen = 4,7-diphenyl-1,10-phenanthroline (2), dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine (3), nphen = 5-nitro-1,10-phenanthroline (4), bpy = 2,2′-bipyridine, (5), and dpa = 2,2′-dipyridylamine (6), was prepared and thoroughly characterized. The in vitro cytotoxicity screening on eight human cancer cell lines identified complex 2, containing the bulkiest N-donor ligands (bphen) as highly cytotoxic against cancer cells, with IC₅₀ values ranking from 1.0 to 2.3 μM, with good selectivity and low toxicity against healthy human fetal lung fibroblasts MRC-5. The cell-based assays, involving the most effective complex 2 in A2780 cancer cells, revealed its strong pro-apoptotic effects based on the effective activation of caspases 3/7, ROS overproduction, and autophagy in the A2780 cells while not impeding the cell cycle and mitochondrial membrane functions. The cellular uptake studies in A2780 and 22Rv1 cells uncovered no intracellular transport of the cationic complex 2, supporting the hypothesis that the in vitro anticancer effects of complex 2 are based on the combined extrinsic activation of apoptosis and autophagy induction. Full article

Heteroleptic cyclometalated iridium (III) complexes (1–3) containing di-pyridylamine motifs were prepared in a stepwise fashion. The presence of the di-pyridylamine ligands tunes their electronic and optical properties, generating blue phosphorescent emitters at room temperature. Herein we describe the synthesis of the mononuclear iridium complexes [Ir(ppy)₂(DPA)][OTf] (1), (ppy = phenylpyridine; DPA = Dipyridylamine) and [Ir(ppy)₂(DPA-PhI)][OTf] (2), (DPA-PhI = Dipyridylamino-phenyliodide). Moreover, the dinuclear iridium complex [Ir(ppy)₂(L)Ir(ppy)₂][OTf]₂ (3) containing a rigid angular ligand “L = 3,5-bis[4-(2,2′-dipyridylamino)phenylacetylenyl]toluene” and displaying two di-pyridylamino groups was also prepared. For comparison purposes, the related dinuclear rhodium complex [Rh (ppy)₂(L)Rh(ppy)₂][OTf]₂ (4) was also synthesized. The x-ray molecular structure of complex 2 was reported and confirmed the formation of the target molecule. The rhodium complex 4 was found to be emissive only at low temperature; in contrast, all iridium complexes 1–3 were found to be phosphorescent in solution at 77 K and room temperature, displaying blue emissions in the range of 478–481 nm. Full article

Photodynamic therapy (PDT) is a cancer treatment still bearing enormous prospects of improvement. Within the toolbox of PDT, developing photosensitizers (PSs) that can specifically reach tumor cells and promote the generation of high concentration of reactive oxygen species (ROS) is a constant research goal. Mitochondria is known as a highly appealing target for PSs, thus being able to assess the biodistribution of the PSs prior to its light activation would be crucial for therapeutic maximization. Bifunctional Ir(III) complexes of the type [Ir(C^N)₂(N^N-R)]⁺, where N^C is either phenylpyridine (ppy) or benzoquinoline (bzq), N^N is 2,2′-dipyridylamine (dpa) and R either anthracene (1 and 3) or acridine (2 and 4), have been developed as novel trackable PSs agents. Activation of the tracking or therapeutic function could be achieved specifically by irradiating the complex with a different light wavelength (405 nm vs. 470 nm respectively). Only complex 4 ([Ir(bzq)₂(dpa-acr)]⁺) clearly showed dual emissive pattern, acridine based emission between 407–450 nm vs. Ir(III) based emission between 521 and 547 nm. The sensitivity of A549 lung cancer cells to 4 evidenced the importance of involving the metal center within the activation process of the PS, reaching values of photosensitivity over 110 times higher than in dark conditions. Moreover, complex 4 promoted apoptotic cell death and possibly the paraptotic pathway, as well as higher ROS generation under irradiation than in dark conditions. Complexes 2–4 accumulated in the mitochondria but species 2 and 4 also localizes in other subcellular organelles. Full article

Dihydrogen bonds attract much attention as unconventional hydrogen bonds between strong donors of H-bonding and polyhedral (car)borane cages with delocalized charge density. Salts of closo-borate anions [B₁₀H₁₀]²⁻ and [B₁₂H₁₂]²⁻ with protonated organic ligands 2,2’-dipyridylamine (BPA), 1,10-phenanthroline (Phen), and rhodamine 6G (Rh6G) were selectively synthesized to investigate N−H...H−B intermolecular bonding. It was found that the salts contain monoprotonated and/or diprotonated N-containing cations at different ratios. Protonation of the ligands can be implemented in an acidic medium or in water because of hydrolysis of metal cations resulting in the release of H₃O⁺ cations into the reaction solution. Six novel compounds were characterized by X-ray diffraction and FT-IR spectroscopy. It was found that strong dihydrogen bonds manifest themselves in FT-IR spectra that allows one to use this technique even in the absence of crystallographic data. Full article

Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M₃(dpa)₄]²⁺ (M = Co(II) and Ni(II); dpa = the anion of 2,2′-dipyridylamine). Enantiomeric resolution of a racemic mixture of [M₃(dpa)₄]²⁺ complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As₂(tartrate)₂]²⁻ or [Λ-As₂(tartrate)₂]²⁻ in N,N-dimethylformamide (DMF), affording crystalline coordination polymers formed from [(Δ-Co₃(dpa)₄)(Λ-As₂(tartrate)₂)]·3DMF (Δ-1), [(Λ-Co₃(dpa)₄)(Δ-As₂(tartrate)₂)]·3DMF (Λ-1), [(Δ-Ni₃(dpa)₄)(Λ-As₂(tartrate)₂)]·(4 − n)DMF∙nEt₂O (Δ-2) or [(Λ-Ni₃(dpa)₄)(Δ-As₂(tartrate)₂)]·(4 − n)DMF∙nEt₂O (Λ-2) repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species. The helicoidal [M₃(dpa)₄]²⁺ units that were obtained display high stability towards racemization as shown by the absence of an evolution of the dichroic signals after several days at room temperature and only a small decrease of the signal after 3 h at 80 °C. Full article

Halogenido and carboxylato Ru(II) half-sandwich complexes of the general composition [Ru(η⁶-p-cym)(dpa)X]PF₆ (1–5) were prepared and thoroughly characterized with various techniques (e.g., mass spectrometry, NMR spectroscopy and X-ray analysis); dpa = 2,2′-dipyridylamine; p-cym = p-cymene; X = Cl⁻ (for 1), Br⁻ (for 2), I⁻ (for 3), valproate(1−) (for 4) or 4-phenylbutyrate(1−) (for 5). A single-crystal X-ray analysis showed a pseudo-octahedral piano-stool geometry of [Ru(η⁶-p-cym)(dpa)I]PF₆ (3), with a η⁶-coordinated p-cymene, bidentate N-donor dpa ligand and iodido ligand coordinated to the Ru(II) atom. The results of the ¹H-NMR solution behaviour studies proved that the complexes 1–5 hydrolyse were in the mixture of solvents used (10% MeOD-d₄/90% D₂O). Complexes 1–5 were in vitro inactive against the A2780 human ovarian carcinoma cell line, up to the highest tested concentration (IC₅₀ > 100 μM). Full article

An unsymmetrical trinickel metal complex, [Ni₃(dpa)₄(4-sb)(H₂O)]×3H₂O (1), where dpa is a 2,2’-dipyridylamine anion and 4-sb is 4-sulfobenzoate dianion, was synthesized and characterized by X-ray crystallography, IR, elemental analysis, fluorescence, and cyclic voltammetry. The molecular structure of 1 is a cluster with a linear trimer. The extended structure is a 3D architecture assembled by hydrogen bonds. The 4-sulfobenzoate axial replacement leads to the change of Ni-Ni distances, the shift of the fluorescence emission, and the reversible one-electron reduction process without oxidation process. Full article

The syntheses and single-crystal structures of Mo(CO)₃(phen)(dipy) (1), Mo(CO)₃(biquin)(dipy) (2) and Mo(CO)₃(dpme)(dipy) (3), (phen = 1,10-phenanthroline, C₁₂H₈N₂; dipy = 2,2'-dipyridylamine, C₁₀H₉N₃; biquin = 2,2'-biquinoline, C₁₈H₁₂N₂; dpme = 2,2'-dipyridylmethane, C₁₁H₁₀N₂) are described. In each case, distorted fac-MoC₃N₃ octahedral coordination geometries arise for the metal atoms. Short intramolecular N–H…C interactions from the dipy N–H group to a carbonyl carbon atom occur in each structure. Crystal data: 1 (C₂₅H₁₇MoN₅O₃), M_r = 531.38, monoclinic, P2₁/n (No. 14), Z = 4, a = 11.0965 (5) Å, b = 13.0586 (6) Å, c = 16.6138 (8) Å, b = 108.324 (1)°, V = 2285.31 (18) ų, R(F) = 0.035, wR(F²) = 0.070. 2 (C₃₁H₂₁MoN₅O₃), M_r = 607.47, monoclinic, P2₁/n (No. 14), Z = 4, a = 11.4788 (6) Å, b = 19.073 (1) Å, c = 11.9881 (6) Å, b = 95.179 (1)°, V = 2613.9 (2) ų, R(F) = 0.030, wR(F²) = 0.076. 3 (C₂₄H₁₉MoN₅O₃), M_r = 521.38, monoclinic, P2₁/n (No. 14), Z = 4, a = 8.4222 (3) Å, b = 21.5966 (9) Å, c = 12.5011 (5) Å, b = 94.065 (1)°, V = 2268.12 (15) ų, R(F) = 0.025, wR(F²) = 0.065. Full article