A Solvent-Dependent and Electrochemically Controlled Self-Assembling/Disassembling System

2003 ◽  
Vol 68 (9) ◽  
pp. 1647-1662 ◽  
Author(s):  
Valeria Amendola ◽  
Massimo Boiocchi ◽  
Yuri Diaz Fernandez ◽  
Carlo Mangano ◽  
Piersandro Pallavicini
Keyword(s):  
Equilibrium Mixture ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
The Self ◽  
Molar Ratio ◽  
Crystal And Molecular Structures ◽  
Self Assembling ◽  
Irreversible Oxidation ◽  
Irreversible Reduction ◽  
Metal Ligand

The bis-bidentate ligand R,S-1,2-diphenyl-N,N'-bis(2-quinolinemethylidene)ethane-1,2-diamine (ligand 4), containing two (iminomethyl)quinoline moieties separated by a cis-1,2-diphenylethylene spacer, forms stable complexes with both CuI and CuII. With CuII, the monomeric 1:1 complex [CuII(4)]2+ is obtained both in CH3CN and CH2Cl2. With CuI and overall 1:1 metal/ligand molar ratio, an equilibrium mixture is obtained in CH3CN, consisting of [CuI(4)2]+, [CuI2(4)2]2+ and [CuI2(4)(CH3CN)4]2+. The preponderant species is the two-metal one-ligand "open" complex [CuI2(4)(CH3CN)4]2+, in which each Cu+ cation is coordinated in a tetrahedral fashion by one (iminomethyl)quinoline unit and by two CH3CN molecules. Precipitation from the equilibrium mixture yields only crystals of [CuI2(4)(CH3CN)4](ClO4)2·2CH3CN, whose crystal and molecular structures have been determined. On the other hand, in the poorly coordinating CH2Cl2 solvent, only the dimeric helical [CuI2(4)2]2+ complex is obtained, when the overall metal/ligand 1:1 molar ratio is chosen. Addition of large quantities of acetonitrile to solutions of [CuI2(4)2]2+ in dichlorometane results in the formation of [CuI2(4)(CH3CN)4]2+, i.e. in the solvent-driven disassembling of the CuI helicate. While electrochemistry in CH3CN is poorly defined due to the presence of more than one CuI species, cyclic voltammetry experiments carried out in CH2Cl2 revealed a well defined behavior, with irreversible oxidation of [CuI2(4)2]2+ and irreversible reduction of [CuII(4)]2+ taking place at separate potentials (∆E ≈ 700 mV). Irreversibility and separation of the redox events are due to the self-assembling and disassembling processes following the reduction and oxidation, respectively.

scholarly journals 2-Deoxyglucose-Modified Folate Derivative: Self-Assembling Nanoparticle Able to Load Cisplatin

Molecules ◽  
2019 ◽  
Vol 24 (6) ◽  
pp. 1084 ◽  
Author(s):  
Shaoming Jin ◽  
Zhongyao Du ◽  
Pengjie Wang ◽  
Huiyuan Guo ◽  
Hao Zhang ◽  
...  
Keyword(s):  
Folic Acid ◽  
Self Assembly ◽  
Water Solubility ◽  
Pure Water ◽  
The Self ◽  
Molar Ratio ◽  
Antineoplastic Drugs ◽  
Self Assembling ◽  
Bonding Interaction ◽  
Nano Drug Delivery

Folic acid has been widely introduced into nano-drug delivery systems to give nanoparticle-targeted characteristics. However, the poor water solubility of folic acid may hinder the exploitation of its ability to load antineoplastic drugs. In the present study, we designed a new folate derivative (FA-2-DG) synthesized from folic acid and 2-Deoxyglucose (2-DG). The aim of this study was to evaluate the self-assembly characteristics of FA-2-DG, and its ability of loading cisplatin. The critical micelle concentration was 7.94 × 10−6 mol L−1. Fourier transform infrared spectroscopy indicated that hydrogen bonding interaction is a main driving force for the self–assembly of FA-2-DG. The particle was stable in pure water or 0.5% bovine serum albumin dispersions. By forming a coordination bond, the particles assembled from FA-2-DG can load cisplatin. The loading efficiency was maximal when the molar ratio of FA-2-DG to cisplatin was 2:1.

The Reaction of (PPri3)2H2Cl2Ir With Phosphines: Crystal and Molecular Structures of mer-cis-(PMe2Ph)2(PPri3)-cis-Cl2HIrIII and mer-cis-(PMe2Ph)2(PPri3)-trans-Cl2HIrIII

1993 ◽  
Vol 46 (4) ◽  
pp. 529 ◽  
Author(s):  
EJ Ditzel ◽  
GB Robertson
Keyword(s):  
Phosphine Ligands ◽  
Molecular Structures ◽  
Iridium Complex ◽  
Steric Strain ◽  
Distorted Octahedral Coordination ◽  
Crystal And Molecular Structures ◽  
Distorted Octahedral ◽  
Spontaneous Reaction ◽  
Summary Data ◽  
Metal Ligand

Ambient temperature reactions of the complex (PPri3)2H2Cl2IrIV (1) with ethyl-substituted monodentate phosphine ligands are shown to yield different product types to those obtained both with methyl-substituted analogues and with phosphine itself. With the phosphines PH3 and PMe3-nPhn (n = 0, 1) there is spontaneous reaction to give the complexes mer-trans-(Ppri3)2(PR3)H-trans-Cl2IrIII, whereas with PEt3-nPhn (n = 0-2) the reaction yields mer-cis-(PR3)2(PPri3)H-trans-Cl2IrIII complexes. Under reflux the phosphines PMe3 and PMe2Ph also yield mer-cis-(PR3)2(PPri3)H-trans-Cl2IrIII complexes [PR3 = PMe3 (2), Pme2Ph (3)]. The differing course of the reactions of (1) with PMe3 and with PEt3 has permitted the synthesis of mer-(Pme3)-trans-(PPri3)(PEt3)H-trans-Cl2IrIII, the first example of an octahedral iridium complex containing three different monodentate phosphine ligands. All of the products obtained have been fully characterized by 31P and 1H n.m.r. spectroscopy. Crystal structure analyses of (3) and of its photoisomer mer-cis-(PMe2Ph)2(PPri3)H-cis-Cl2IrIII (4) have been carried out to permit comparison of the metal-ligand bonding in these complexes with that in their previously characterized, sterically less crowded, tris-PMe2Ph analogues. Summary data are as follows: (3), triclinic, Pī, a 13.414(1), b 12.062(1), c 9.077(1) Ǻ, α 79.53(1), β 88.05(1), γ 79.47(1)° [T 158�3 K], Z 2, R 0.022, Rw 0.032 (4822 reflections); (4), monoclinic, P21/n, a 19.694(1), b 15.972(1), c 9.548(1) Ǻ, β 101.45(1)° (T 293�2 K), Z 4, R 0.026, Rw 0.032 (5476 reflections). Both molecules exhibit distorted octahedral coordination of the metal atom and appreciably greater steric strain than in their (Pme2Ph)3HCl2IrIII analogues. Metal-ligand distances to the mutually trans Pme2Ph and PPri3 ligands are 2.322(1) and 2.372(1)Ǻ, respectively, for (3), and 2.359(1) and 2.406(1)Ǻ for (4), and suggest that the thermodynamically favoured cis-dichloro isomer (4) is the more strained. The preparations of the complexes (PCy3)2H2Cl2IrIV (1a) and (PCy3)2H2Br2IrIV (1b) (Cy = cyclohexyl), and their reactions with the same phosphines as used with (1), are also reported.

Group 12 Metal Complexes of 2-Formylpyrrole-(4PL1) and 2-Acetylpyrrole-N(4)-phenylthiosemicarbazone (4Pl2), as Examples form Different Donor Modes. Crystal and Molecular Structures of [Hg(4PL1- H)Br]2 and [Zn(4PL2)2Br2] · 2 EtOH

2001 ◽  
Vol 56 (9) ◽  
pp. 881-888 ◽  
Author(s):  
Rosa Carballo ◽  
Alfonso Castiñeiras ◽  
Teresa Pérez
Keyword(s):  
Mass Spectrometry ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Fab Mass Spectrometry ◽  
Nmr Spectrometry ◽  
Group 12 ◽  
Monodentate Ligands ◽  
New Compounds

Abstract The reactions of 4N-phenyl-2-[ 1 -(pyrrol-2-yl)methylidene]-hydrazine carbothioamide (4PL1) and 4N-phenyl-2-[l-(pyrrol-2-yl)ethylidene]-hydrazine carbothioamide (4PL2) with Group 12 metal halides afford complexes of types [M(L)2X2] [M = Zn, L = 4PL1 or 4PL2, X = Cl, Br or I; M = Cd, L = 4PL1, and X = Cl, or L = 4PL2 and X = Cl, Br or I] and [M(L)X2] [M = Cd, L = 4PL1, X = Br or I; M = Hg, L = 4PL1 or 4PL2, X = Cl, Br or I]. The new compounds were characterized by elemental analysis, FAB mass spectrometry, IR spectroscopy, and, in the case of sufficiently soluble compounds, 1H, 13C and, when appropriate, 113Cd or 199Hg NMR spectrometry. The structures of [Hg(4PL1-H)Br] and [Zn(4PL2)2Br2] · 2 EtOH were also studied by single-crystal X-ray diffractometry. In [Hg(4PL1-H)Br] crystallized from the mother liquor of its synthesis, 4PL1 behaves as a monodeprotonated S,N-bidentate ligand. Otherwise, with Hg(II), Zn(II) and Cd(II), 4PL1 and 4PL2 both behave as neutral S-monodentate ligands.

Crystallographic Study on Metal(II) Complexes with N-(2-Nitrophenylsulfonyl)glycine

1999 ◽  
Vol 52 (8) ◽  
pp. 741 ◽  
Author(s):  
Daniela Iacopino ◽  
Ledi Menabue ◽  
Monica Saladini
Keyword(s):  
Metal Ion ◽  
Chelating Agent ◽  
Ternary Systems ◽  
Molecular Structures ◽  
Molar Ratio ◽  
Acidic Ph ◽  
Crystal And Molecular Structures ◽  
Crystallographic Study ◽  
Deprotonation Reaction ◽  
Solid Compounds

The interaction of MII ions (MII =Mn II, CoII, NiII, CuII, ZnII, CdII, PbII) with N-(2-nitrophenylsulfonyl)- glycine (NO2psglyH2) leads to the formation at acidic pH of the complex carboxylate-type M(NO2psgly- O)2.x H2O species. At higher pH the deprotonation reaction of the sulfonamide nitrogen takes place, leading to the formation of the M(NO2psgly-N,O).x H2O species where the ligand acts as a chelating agent toward the metal ion through the carboxylic oxygen and the deprotonated sulfonamide nitrogen. In ternary systems the addition of 2,2′-bipyridine (bpy) allows the deprotonation of the sulfonamide nitrogen also in presence of metal ions such as ZnII, CoII and NiII, which were inactive in the binary system, and the solid compounds isolated are in the M/bpy/L molar ratio 1 : 1 : 1 (MII = CuII , ZnII ) or 1 : 2 : 1(MII = CoII , NiII, CdII). Here we describe the crystal and molecular structures of NO2psglyH2 (1), [Pb(NO2psgly-N,O)]n (2), [Cd(bpy)2(NO2psgly-N,O)].H2O (3) and [Cu(bpy)(NO2psgly-N,O)(H2O)] (4).

Thermodynamics of metal-ligand bond formation. XI. Adducts of heterocyclic bases with copper(II) complexes of fluorinated β-diketones

1974 ◽  
Vol 27 (4) ◽  
pp. 741 ◽  
Author(s):  
DP Graddon ◽  
WK Ong
Keyword(s):  
Enthalpy Of Formation ◽  
Benzene Solution ◽  
Bidentate Ligand ◽  
Molecular Structures ◽  
Enthalpies Of Formation ◽  
Complex Forms ◽  
Heterocyclic Bases ◽  
The Enthalpy Of Formation ◽  
Metal Ligand ◽  
Ligand Bond

Thermodynamic data have been obtained for the reaction in benzene solution of copper(11) complexes of hexafluoropentanedione and three trifluorinated α-diketones with several unidentate and bidentate heterocyclic bases and terpyridine. With pyridine the hexafluoro� complex forms very stable 1 : 1 and 1 : 2 adducts. The enthalpy of adduct formation (-ΔH) is about 39 kJ mol-1 for the addition of each molecule of pyridine, about 10 kJ mol-1 more than for the formation of the 1 : 1 adduct with the acetylacetone complex. The trifluoro complexes form only 1 : 1 adducts with enthalpy of formation about 31 kJ mol-1 ; these are much more stable than Cu(acac)2(py), but the extra stability is mainly due to entropy factors. With bipyridine and phenanthroline all four fluoro complexes form very stable 1 : 1 adducts with enthalpies of formation about twice those for addition of one molecule of pyridine; this shows that two Cu-N bonds are formed. 2,9-Dimethyl-1,l0-phenanthroline forms a similar adduct, but the enthalpy of formation is much less, due to steric interference. Terpyridine forms a 1 : 1 adduct of much lower stability, probably behaving as an ortho-substituted bidentate ligand. Infrared spectra of the adducts of Cu(tfaa)2 and Cu(hfaa)2 support molecular structures in which one of the Cu-O bonds linking each β-diketone is lengthened to allow the formation of a strong pair of Cu-N bonds.

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