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Synthesis of bis-4,5-diazafluoren-9-one silver(I) nitrate I (dafone = 4,5-diazafluoren-9-one) and the low temperature X-ray single crystal structure of [Ag(4,5-diazafluoren-9-one)(2)NO(3)], crystal form 1, and a re-determination of [Ag(4,5-diazafluoren-9-one)(2)]NO(3)center dot H(2)O, crystal form 2 are presented. Crystal form 1 has a distorted tri...
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... Å), whose positive charge is balanced by ClO 4 − ions occupying voids in between adjacent 1D chains (Scheme 2). The propensity of silver(I) to give linear coordination environment with pyridine [37][38][39] or nitrogen ligands [40][41][42][43] is reported, and in this case the high basicity of the pyridyl ring given by the releasing electronic effect of the attached phenyl ring [34] might convey enough donor power to only two nitrogen atoms in order to satisfy the coordinative electronic demand of silver(I). ...
In continuation of our work on supramolecular architectures of single-molecule magnets (SMMs) as a promising strategy in developing their magnetic performance, in this paper we report the synthesis and single crystal X-ray structure of the centered triangular tetrairon(III) SMM, [Fe4(PhpPy)2(dpm)6], Fe4 (Hdpm = dipivaloylmethane, H3PhpPy = 2-(hydroxymethyl)-2-(4-(pyridine-4-yl)phenyl)propane-1,3-diol), and its assembly in the coordination polymer {[Fe4(PhpPy)2(dpm)6Ag](ClO4)}n, Fe4Ag, upon reaction with silver(I) perchlorate. Thanks to the presence of the pyridyl rings on the two tripodal ligands, Fe4 behaves as divergent ditopic linker, and due to the Fe4:AgClO4 1:1 ratio, Fe4Ag probably possesses a linear arrangement in which silver(I) ions are linearly coordinated by two nitrogen atoms, forming 1D chains whose positive charge is balanced by the perchlorate anions. The stabilization of such a polymeric structure can be ascribed to the long distance between the two donor nitrogen atoms (23.4 Å) and their donor power. Fe4Ag shows slow relaxation of the magnetization which follows a thermally activated process with Ueff/kB = 11.17(18) K, τ0 = 2.24(17) 10−7 s in zero field, and Ueff /kB = 14.49(5) K, τ0 = 3.88(8) 10−7 s in 1-kOe applied field, in line with what reported for tetrairon(III) SMMs acting as building blocks in polymeric structures.
... On other hand, there is increasing interest in the biological activity of silver and its compounds as potent antibacterial and antifungal agents [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. The structural chemistry of silver (I) complexes is also interesting, as Ag(I) could adopt variable coordination numbers (n = 2-6). ...
The synthesis and structural aspects of a new dinuclear silver (I) complex with malonamide type ligand (L) is reported. Each Ag ion in the [Ag₂L₂(NO₃)₂]·H₂O complex is coordinated to two ligands, L, each acting as a bridged ligand via its two pyridine arms; Ag(I) acts as a connector between them. Two types of Ag-ligands close contacts were detected: Ag-N1, Ag-N4 from the two L units, and Ag-O5, Ag-O6 from the two nitrate anions, wherein both the nitrate ions are inside the cage formed by the [Ag₂L₂] unit. The coordination geometry around each Ag(I) is a distorted tetrahedron. The [Ag₂L₂(NO₃)₂] complex units are connected by weak intermolecular C-H…O interactions. The different intermolecular interactions were quantified using Hirshfeld surface analysis. Using two DFT methods (B3LYP and WB97XD), the nature and strength of the Ag-N and Ag-O interactions were described using atoms in molecules (AIM) and natural bond orbital (NBO) analyses. Topological parameters indicated that the strength of the two Ag-N bonds was similar, while that of the two Ag-O interactions were significantly different. Moreover, the Ag-N interactions have a predominant covalent character, while the Ag-O interactions are mainly ionic. The NBO analysis indicated that the most important anti-bonding Ag-orbital in these interactions has an s-orbital character.
... Silver(I) complexes attracted the attention of many research groups due to their fascinating structure aspects as well as their interesting biological activity as antimicrobial and antifungal agents [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. The complexation between the organic ligand and silver(I) is considered an improvement for the ligand biological activity [20]. ...
The synthesis, single crystal X-ray diffraction (SC-XRD) characterization and Hirshfeld topology analysis of molecular packing of the coordination polymer [Ag2L(H2O)2(ClO4)2]n, where L = 2,4,6-trimorpholino-1,3,5-triazine were discussed. The asymmetric unit comprises one Ag2L(H2O)2(ClO4)2 unit. The coordination geometries around the two silver atoms are different where Ag(1) is hexa-coordinated with one L, two bridged water, and two bridged perchlorate augmented with one strong Ag-O interaction from the morpholine O-atom of another ligand (L) unit. The coordination environment is more like to a distorted octahedral arrangement according to the criteria of continuous shape measurements. Ag(2) is coordinated to one L, one terminal water and one terminal perchlorate leading to a distorted trigonal planar arrangement around Ag(2). Hirshfeld analysis of molecular packing indicated that the most important intermolecular contacts affect the molecular packing of the studied complex are the H…H and the O…H interactions. Atoms in molecules (AIM) and natural bond orbital (NBO) analyses were used to describe the strength and nature of the Ag-O and Ag-N interactions.
... These coordination polymers have captivated attention of researchers due to the high flexibility of silver(I) coordination sphere and geometries of corresponding complexes. Silver(I)-pyridinyl coordination polymers possess interesting properties such as antimicrobial activity [124,125], enhanced luminescence [126], liquid crystalline properties [127], and silver(I) induced emissions in condensed phases [128]. Most common pyridinyl ligands that have been used to prepare silver(I) coordination polymers include bipyridines, pyridinyltetrazines, 2,2′-biquinolines, terpyridines and their derivatives where the pyridinylnitrogen donor sites are separated by alkyl or aryl spacers. ...
Possible coordination modes of silver(I) by pyridinyl ligands and Ag⋯Ag interactions. This review highlights some structural features and luminescent properties of homo-and hetero-multinuclear silver(I)–pyridinyl complexes. It focuses on the coordination and geometry of the silver (I) ions to the pyridinyl-nitrogen. For this reason, we have considered only pyridinyl-N–Ag(I) complexes whose crystal data are available. In addition, this review does not consider mononuclear sil-ver(I)–pyridinyl complexes as these have been reviewed elsewhere. This is motivated by the fact that multinuclear silver(I)–pyridinyl complexes have been shown to be more stable in solution, possess enhanced properties, and have fascinating structures compared to their mononuclear counterparts. The introduction highlights pyridinyl ligands used in complexation of silver(I) ions. The main body highlights complexation of silver(I) through pyridinyl nitrogen and the interactions found in the multinuclear silver(I)–pyridinyl complexes as well as the coordination number and geometry of silver(I) centers. Though silver(I) has been flaunted to prefer linear twofold coordination geometry, from this review, it is clear that higher coordination numbers in varied geometries are possible. These include distorted trigonal planar, T-shaped, distorted tetrahedral, trigonal bipyramidal, and octahedral geometries. Coordination of silver(I) to pyridinyl ligands and their metalloligands has been observed to impart or enhance luminescent properties in the ensuing complexes.
... The nitrate coordination to the Ag(I) centres in (1) is stabilizing the sheets formed in the solid-state with the stoichiometry 2:1 (Ag:L) while in solution the nitrates have been solvated giving the ligand more chance to directly attack the half naked [ ] + (Ag:L = 1:2) were found [30]. Similarly, the ESI-MS for the compound [Ag(4,5-diazauoren-9-one) 2 ]NO 3 [21] showed only one strong peak representing the complex [Ag(L) 2 ] + with (Ag: L = 1:2). On the contrary, the ESI-MS for a solution containing AgBF 4 and excess bidentate 1,12-diazaperylene ligand indicate the formation of the 1:1 (90%) Ag:L complex while the expected 1:2 complex is only observed as a minor peak (10%) [31]. ...
Synthesis and X-ray single crystal structure analysis of the compound {[Ag(2)(mu(2)-bpym)(mu-O-NO(3))(2)]}(n), (1), (where bpym = 2,2'-bipyrimidine) are presented. Compound (1) has a (6,3)-2D honeycomb structure with a tetrahedral coordination geometry around the Ag(I) ion. In contrary to the solid state structural investigation, ESI-MS for (1) in solution shows a strong peak at m/z 423.0269 which indicates that the [Ag(bpym)(2)](+) cation is dominating instead of [Ag(2)(bpym))(2+). The anti-microbial activity of (1) was screened against 15 multi-drug resistant bacteria in comparison to silver(I) sulphadiazine and it showed a high activity against Burkholderia mallei which causes glanders; with a MIC value of 4 mu g/ml. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.
Compounds [Ag(5NO2Qu)2]BF4 (1) and [Ag(Qu3CN)(H2O)]BF4 (2) were prepared and studied from a structural perspective and screened for antimicrobial activity. The Ag(I) in the monomeric complex 1 is coordinated to two...
A new mixed-ligand Ag(I) complex, [Ag(daf)(phen)]NO3 (daf = 4,5-diazafluoren-9-one and dian = N-(4,5-diazafluoren-9-ylidene)aniline), was synthesized. The elemental analysis, FTIR, 1HNMR, UV-Vis spectroscopy, cyclic voltammetry, and DFT (Density Functional Theory) geometry optimization method were applied in order to predict the Ag(I) complex structure which concluded to a distorted tetrahedral N4 coordination around the Ag(I) center. A detailed in silico analysis of the bioaffinity of the complex to DNA and human DNA-Topoisomerase I was conducted using molecular docking simulations and ONIOM (Our own N-layered Integrated molecular Orbital and molecular Mechanics) techniques. In this overall scenario, the results suggest the dominance of π-π stacking interactions of the heteroaromatic ligands in the intercalating pocket of DNA and the active site of the enzyme and the rational correlation between being a good intercalator and a potent Topoisomerase I inhibitor. In vitro DNA-binding experiments by spectrophotometric, spectrofluorometric, Voltammetric, and viscometric techniques at physiological pH also confirmed the computational results. The complex inhibited MCF-7 cell growth in a dose-dependent manner while being nontoxic on HUVEC normal cells.
The two silver(I) complexes [Ag(3CNPy)2(CF3COO)]n (1) and [Ag(4BzPy)2]2(CF3COO)2 (2) where 3CNPy and 4BzPy are 3-cyanopyridine and 4-benzoylpyridine, respectively, were synthesized and characterized using elemental analysis, FTIR spectra and single crystal X-ray diffraction. Complex 1 is a 1D coordination polymer through the bridging and the highly symmetric CF3COO¯ group while 2 is a dinuclear complex through strong argentophilic interaction connecting the two [Ag(4BzPy)2] cationic units. In both complexes, the pyridine ligands are acting as monodentate N-donor. Hirshfeld surface analysis revealed the importance of the polar N•••H (29.9%) and H•••F (10.3%) hydrogen bonds in the molecular packing of 1. For 2, the nonpolar C•••H (26.2%) and the polar O•••H (15.6%) interactions dominate the crystal packing. Furthermore, both complexes showed π-π stacking interactions. Antimicrobial screening revealed that 3CNPy has no activity against all tested pathogens, while 1 has good antibacterial activity. Both Ag(I) complexes and 4BzPy showed remarkable antifungal activities against A. fumigatus and C. albicans compared to Ketoconazole as control.
Designing and constructing hierarchical and stimuli-responsive motorized nanocar systems to perform useful tasks on-demand is highly imperative towards molecular nanotechnology. In this work, a most simplified two-wheel nanocar was successfully prepared through a facile strategy of coordination-directed self-assembly. The nanocar meso-AgL2 features a central pseudo square-planar Ag(I) which was bridged by two enantiomeric motors as the wheels that ensure the car moves in the same direction when observed externally. Thanks to the electronic push-pull characteristic of L and 3ILCT triplet sensitization, this nanocar can be driven by visible light up to 500 nm. Furthermore, it could be disassembled into individual motor elements through the addition of pyridine, thus allowing dynamic regulation over the function of the nanocar. Importantly, our STM imaging results showed very organized tilted layered structures for meso-AgL2 on highly oriented pyrolytic graphite (HOPG) that are quite similar to its crystalline ones, paving the way for future single molecule manipulations. The nanocar reported here represents the first example of integrating individual motors into a hierarchical motorized nanocar system via the facile coordination-directed self-assembly method and may offer a good starting point to realize its robotic functions, e.g., metal transportation and release.
Nano silver‐based inorganic structure with the chemical formulation of [Ag(dafo)2(NO3)] (1), dafo=4,5‐diazafluoren‐9‐one, was synthesized using sonochemical method. Three different ultrasonic generator output powers of 30 W, 60 W, 90 W, each in two different reaction temperature ranges of 0–10 °C and 25–35 °C, were our sonochemical reaction conditions. After preparing compound 1 with differently‐sized nanoparticles under the sonochemical reaction conditions, we conducted an evaluation study into the optical, anti‐cancer, and thermal activities of the compound. High ultrasonic generator output power and low reaction temperature were the two prevailing conditions that affected the size and purity of the nanoparticles of compound 1. Based on our identifying methods, nanoparticles of 90 W at 0–10 °C showed the lowest particles size among other nanoparticles. The best optical, anticancer, and thermal activities appertained to the nanoparticles. The nanoparticles were heated to 500 °C in an electric furnace to synthesize phase‐pure silver nanoparticles.
