cis-Diaminedichloroplatinum(II) complexes reversibly bound to water-soluble polyaspartamide carriers for chemotherapeutic applications. I. Platinum coordination to preformed, carrier-attached ethylenediamine ligands

Copolyaspartamides3–5, bearing the ethylenediamine (en) ligand as a repetitive side-chain component in addition to various hydrosolubilizing groups, are synthesized from polysuccinimide1 by a two-step aminolytic ring opening reaction. The completely water-soluble polyamides, possessing inherent viscosities of 5–20 ml g^–1, are used as polymeric carriers for the anchoring of the biomedically important diaminedichloroplatinum(II) coordination complex. Conjugate formation is brought about by treatment of the carriers with the tetrachloroplatinate(II) dianion in aqueous solution at pH 6.0 ± 0.5. The resulting, water-soluble conjugates3-Pt-5-Pt, purified by dialysis (12,000–14,000 molecular mass cutoff) and isolated in the solid state by freeze-drying from aqueous solution, possess platinum contents in the typical range of 15–25%. The metal is bound as acis-dichloro-en-Pt(II) complex to the polymer main chain via a short spacer segment incorporating a biofissionable amide link suitable forin vivo release of the complex. The conjugates are of interest as water-soluble macromolecular platinum coordination compounds for potential use in the chemotherapy of cancerous diseases.Presented in part at the XXVII International Conference on Coordination Chemistry, Broadbeach, Australia, 2–7 July 1989, abstract T6.     

Synthesis, Crystal Structures and Properties of Two Metal–Organic Frameworks Constructed from Pyridine Dicarboxylate and Flexible Bis(imidazole) Ligand

Two novel interesting metal–organic frameworks, [Zn(PDA)(bbi)] _n (1) and [Cd₂(PDA)₂(bbi)₂(H₂O)₂·10H₂O] _n (2) [H₂PDA = pyridine-2,6-dicarboxylic acid, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)] have been isolated under hydrothermal conditions and structurally characterized. X-ray single crystal structure analysis reveals that complex 1 crystallize in monoclinic P2₁/c space group, while complex 2 crystallize in triclinic P-1 space group. The PDA^2? anions act in two different coordination modes: terminal chelating for 1 and chelating and bis-monoatomic bridging for 2. Polymeric chains of 1 and 2 are composed of Zn(II) and Cd(II) ions bridged by bbi ligands. The fluorescent properties of 1 and 2 were also investigated.     

Synthesis and Structural Characterization of Two New Nano-Coordination Compounds Based on Mercury(II) NN Donor Schiff Base

Two new nano mercury(II) coordination compounds, [Hg₂(μ-L1)(μ-I)₂I₃]_n (1) and [Hg(L2)(I)₂] (2) {L1?=?(E)-N′-(pyridin-2-ylmethylene)isonicotinohydrazide and L2?=?(E)-N′-(1-(pyridin-2-yl)ethylidene)isonicotinohydrazide} have been synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, elemental analysis and IR spectroscopy. The compounds were also characterized by single crystal X-ray diffraction and the results indicate a 1D fishbone-like structure containing dinuclear units for 1 and a mononuclear structure for 2. In coordination polymer 1, the two Hg(II) centers are four coordinate into a chain-axis and also in the terminal linkages. In complex 2, the Hg(II) center is four coordinate. The chains of polymer 1 interact with each other through π–π stacking interactions which create a 3D framework.     

Structural Variations in Coordination Polymers of Sodium and Cesium Dicarboxylates

The coordination polymer {[Na₂L(μ-H₂O)(H₂O)₃]·H₂O} _n (1) derived from 2,2′-(phenylmethylidene-bis(3,5-methyl-2-phenyleneoxy)] diacetic acid (H₂ L) has repeat units comprising of hexa-coordinate diaqua-bridged dinuclear sodium complex ions. These units are connected through intervening mononuclear complex parts having penta-coordinated sodium ions. The sodium ions adopt repeated hexameric chair-like arrangement in the polymer. The cesium salt of H₂ L namely [Cs(HL)(μ-H₂O)(H₂O)] _n (2) is a coordination polymer. In this case one acid group of the ligand is deprotonated and 2 form self-assembly by intermolecular hydrogen bonds between the free carboxylic acid groups. The fluoro-substituted ligand 2,2′-(2-fluorophenylmethyledene-bis(3,5-methyl-2-phenyleneoxy)] diacetic acid (H ₂ L _f ) forms disodium salt with a composition [{Na₂L_f(μ-H₂O)(H₂O)₃}·H₂O] _n (3); which is a two dimensional coordination polymer. On the other hand the corresponding cesium salt of H ₂ L _f has a composition [{(H₂O)Cs(μ-H₂O)(μ-L_f)Cs(H₂O)₂}] (4); which is also a 2-D coordination polymer. The cesium ions are six or nine coordinate in the polymer and the coordination polymer possesses unusual Cs···F–C coordination bond.     

Synthesis, Crystal Structures and Fluorescence Properties of Two One-Dimensional Cadmium(II) Coordination Polymers Containing Flexible Bis(benzimidazole) Ligands

Two one-dimensional Cd(II) coordination polymers constructed by ribbon-like molecules, {[Cd(L₁)₂(NO₃)]·NO₃} _n (1) (L₁ = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)benzene) and [Cd(L₂)₂(NO₃)₂] _n (2) (L₂ = 1,3-bis(benzimidazol-1-yl)benzene) have been obtained through assembly of the two structurally similar flexible bis(benzimidazole)-based ligands and cadmium nitrate tetrahydrate. The cadmium(II) centers display different coordination environments with trigonal-bipyramidal geometry in 1, and a octahedral geometry in 2. Weak C–H···O interactions in 1 result in a two-dimensional supramolecular layer; two π–π interactions are present in 2 forming a three-dimensional supramolecular network structure. The solid state fluorescence properties of 1 and 2 were investigated.     

Fluorescence Properties Change of Lanthanide Coordination Polymers Dispersed in Mesoporous SBA-15 by Energy Transition Process

Four lanthanide coordination polymers, {[Ln(HPDA)(PDA)(H₂O)₂]·4H₂O} _n (Ln?=?Sm (1), Eu (2), Tb (3)) and {[Sm₃(H₂PDA)₂(HPDA)₂(PDA) (OH)₅(H₂O)₃]·2dta·4H₂O} _n (4) (H₂PDA?=?pyridine-2,6-dicarboxylic acid, dta?=?diethyl amine), have been synthesized under hydrothermal conditions and were characterized by elemental analysis, IR spectrometer, and single-crystal X-ray crystallography. In the complexes 1–3, the 1D chains are assembled into 2D layer by hydrogen bonds formed between the carboxyl groups, and were further assembled into 3D framework by hydrogen bonds and π–π stacking interactions. In complex 4, each Sm³⁺ ion connected to the neighboring Sm³⁺ ion through bridging carboxyl oxygen atoms, and then give rise to a new 2D layered open-framework structure. The 3D supramolecular structure of 4 is constructed through hydrogen-bonding and π–π stacking interactions between adjacent metal–organic polymeric coordination chains. Complexes 1–3 were dispersed in mesoporous materials SBA-15 in DMF solution (denoted as ML-SBA-15, ML?=?1, 2, 3), which were characterized by XRD, IR, and fluorescence spectra. Compared to the complexes 1–3, the photoluminescence efficiency of hybrid material was improved by the energy transition between mesoporous materials and the complexes. The complexes encapsulated in mesoporous materials SBA-15 exhibited stronger luminescence intensity and longer fluorescence lifetime.     

Cu(II) and Zn(II)-Pyridine-2,3-Dicarboxylate Complexes with 2-Methylimidazole: Syntheses, Crystal Structures, Spectroscopic and Thermal Analyses

Two new Cu(II) and Zn(II)-pyridine-2,3-dicarboxylate (pydc) complexes with 2-methylimidazole (2-Meim), [Cu(pydc)(2-Meim)₃]·H₂O (1) and {[Zn(μ-pydc)(H₂O)(2-Meim)]·H₂O}_n (2) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of mononuclear (1) and polynuclear (2) complexes have been determined by the single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic P ? 1 space group, while compound 2 crystallizes in the monoclinic P2₁/c space group. The pyridine-2,3-dicarboxylate ligand acts in two different coordination modes; namely, bidentate-(N,O) for 1 and μ-tridentate-(N,O,O) for 2, the latter displaying a 1D polynuclear structure. The crystal packing of the complexes exhibit 3D supramolecular frameworks including channels by C–H···π, π···π, and N–H···O interactions. Water molecules occupy the channels by O–H···O hydrogen bonds.     

Syntheses, Structures and Magnetic Properties of Two Novel Cu(II) Diphosphonate Coordination Polymers with N-Heterocyclic Auxiliary Ligand

By introducing the second organic N-heterocyclic ligand 2,2′-bipyridine (2,2′-bipy), two binuclear examples of Cu(II)-diphosphonate coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H₅L=CH₃C(OH)(PO₃H₂)₂), [Cu₂(H₄L)₂(H₃L)(2,2′-bipy)₂] 1 and [Cu(H₃L)(2,2′-bipy)] 2, have been hydrothermally obtained and characterized by powder X-ray diffraction, elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions show that both the two compounds possess zero-dimensional binuclear structures built through a single O–P–O bridge for 1 and a double O–P–O bridge for 2 in syn–anti fashion. Then H-bond and π–π interactions further expand the two zero-dimensional binuclear structures into three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks of 1–2 centered at 423.5 nm for 1 and 423 nm for 2, respectively, are mainly caused by intraligand π*–π emission state of N-heterocyclic ligand 2,2′-bipy (λ _ex = 233 nm). The further magnetic study shows the two coordination polymers exhibit ferromagnetic behaviors derived from O–P–O bridges in syn–anti mode between the metal centers.     

Syntheses and Structural Analytical Studies of Two Co(II) Complexes Based on 1,4-Di(benzimidazole-1-yl)benzene

Two new Co(II) complexes of 1,4-di(benzimidazole-1-yl)benzene ligand (L) with the formulas [(CoLCl₂)(CHCl₃)(DMF)]_∞ (1) and [CoL(NO₃)₂]_∞ (2) have been synthesized by anion-directed self-assembly. Both complexes have been characterized by elemental analyses, IR, and X-ray single crystal diffraction. Complexes 1 and 2 exhibit 1D chain structures. In 1, Co(II) ions possess a distorted tetrahedral coordination environment composed of N₂Cl₂ donors from two L ligands and two chloride ions, while the Co(II) ions in 2 reveal a distorted octahedral structure defined by the N₂O₄ donors from two L ligands and two nitrate anions. These results illustrate that the anions play an important role in the self-assembly of metal–organic materials.     

A New 3D Coordination Polymer Based on Pentanuclear Cd(II) Rod-Shaped Secondary Building Unit: Synthesis,Crystal Structure and Luminescent Property

A new coordination polymer [Cd_2.5(μ₃-OH)(L)₂(bipy)]_n (1). (L = 1,2-naphthalene dicarboxylate, bipy = 4,4′-bipyridine), was obtained under hydrothermal condition. The structure of 1 has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectrum. Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in triclinic system, Pī space group. Complex 1 possesses a 3D pcu net based on a pentanuclear Cd(II) cluster. Each pentanuclear Cd(II) cluster links with neighboring ones and generates a rod-shaped secondary building unit, which is further extended by bipy ligands to forms a three-dimensional network. Furthermore, the luminescent properties of this complex and the free ligand have been investigated. Complex 1 can be excited directly and emit strong soild-state fluorescence at room temperature, which may make them excellent candidates for fluorescent materials.     

Three New Metal–Organic Polymers Based on Flexible 3-(4-(Carboxymethoxy) Phenyl) Propanoic Acid: Crystal Structures, Luminescent and Magnetic Properties

Three new metal–organic coordination complexes, [Zn₂L(bpp)₂Cl₂] _n (1), [ZnL(bipy)] _n (2), [NiL(bipy)(H₂O)] _n (3), have been synthesized through hydrothermal reactions of flexible 3-(4-(carboxymethoxy)phenyl) propanoic acid(H₂L) with different pyridyl-containing 1,3-bis(4-pyridyl)propane(bpp) or 4,4′-bipyridine(bipy) ligand, and they are characterized by elemetal analysis and single-crystal X-ray diffraction techniques. Complex 1 has a 2-D layer supramolecular network composed of 1-D distorted trapezoidal chains via C–H···π stacking interactions. Complex 2 displays a 2-D lattice-shaped layer structure. Complex 3 has three kinds of O–H···O intermolecular hydrogen bonds, exhibiting a 3-D supramolecular framework. The luminescent properties of complex 1 and 2 have indicated the mixture characteristic of intraligand and ligand-to-ligand charge transition. The magnetic property of 3 has shown the ferromagnetic coupling between Ni²⁺ ions.     

Synthesis, Crystal Structures and Luminescent Properties of pH-Dependent Zn (II) Coordination Polymers

Two new coordination polymers [Zn(L)(bib)] _n (1) and [Zn(L)(bib)_0.5] _n (2) [L = 5-hydroxyisophthalic acid and bib = 1,4-bis(2-methyl-imidazol-1-yl)butane] have been synthesized and characterized. X-ray single crystal diffractions show that complex 1 is a 2D layered structure and complex 2 is a 3D 6-connected topological net. Complex 1 are further assembled into a 3D supramolecular structure by intermolecular hydrogen bonding. Complex 2 features a two-fold interpenetrated pcu topology. Moreover, the fluorescent properties of complexes 1 and 2 were studied in the solid state at room temperature.     

Simultaneous Growing of Two New Cd(II) Metal–Organic Frameworks with 2,6-Naphthalendicarboxylic Acid as New Precursors for Cadmium(II) Oxide Nanoparticles: Thermal, Topology and Structural Studies

Crystal structure and thermal stability of two new 3D Cd(II) metal–organic frameworks (MOF) containing 2,6-naphthalenedicarboxylate, [Cd(NDC)(DMF)], 1, and [Cd₃(NDC)₄], 2 (H₂NDC = 2,6-naphthalenedicarboxylic acid; DMF = N,N-dimethylformamide) have been studied. These two MOFs grow simultaneously within the same solution to give multiple crystals that are due to the general lability of Cd(II) complexes. Structure 1 shows a 3D neutral metal–organic framework with PtS topology and crystallizes in the triclinic system, space group P-1 (No. 2), whilst 2 crystallizes in the orthorhombic system, space group Fdd2 (No. 43) with body-centered cubic bcu-(4²⁴.6⁴) topology. The elongated nature of NDC results in large cavities in both compounds; however, the pores are filled by coordinated DMF molecules in 1. The thermal stability of 1 and 2 were studied by thermogravimetry and show stability to 400 °C for 1 and continuous weight loss for 2. CdO nanoparticles were prepared by direct calcination of 1 and 2 at 600 °C. The CdO nanoparticles were characterized by X-ray powder diffraction and its morphology were studied by scanning electron microscopy. The results show that the CdO is pure and has a uniform morphology.     

Two New Zn(II) Coordination Polymers Constructed from Asymmetric Biphenyl-Dicarboxylate and Imidazole-Containing Ligands: Structures and Photoluminescent Properties

Two new coordination polymers, [Zn(2,4′-bpdc) (L₁)_0.5·(H₂O)] _n (1) and {[Zn(3,4′-bpdc) (L₁)]·(H₂O)} _n (2), have been obtained from hydrothermal reactions of zinc (II) nitrate with the ligands 1,4-bis(imidazol-1-yl)benzene (L) and two asymmetric biphenyl-dicarboxylate [biphenyl-2,4′-dicarboxylate (2,4′-bpdc) and biphenyl-3,4′-dicarboxylate (3,4′-bpdc)]. Single-crystal X-ray diffraction analysis the two coordination polymer show different structures due to the different dicarboxylate ligands. Complex 1 features a 3D mab topological net. Complex 2 is unusual case that has 3D frameworks constructed from 2D 4⁴-sql layers by parallel polycatenation. The photoluminescent properties of 1 and 2 have also been investigated.     

Cadmium(II)-N-Ethylimidazole Coordination Polymer via Different Coordination Environment and Chloro Bridges: Synthesis, X-ray Structure, Spectroscopic and Thermal Analysis

A novel coordination polymer [Cd₂(μ-Cl)₄(Neim)₃]_n (1) (Neim = N-ethylimidazole) was synthesized and structurally characterized by means of elemental analysis, thermal analysis, FT-IR spectrum and single-crystal X-ray diffraction. There are two different cadmium centers in 1. One of these metal centers has octahedral geometry, while the other has square pyramidal geometry. Two Neim ligands are coordinated to the Cd(II) ion in octahedral geometry while one Neim ligand is coordinated to the Cd(II) ion in square pyramidal geometry. Relatively weak C–H···Cl interactions between N-ethylimidazole molecules and chloro ions in the complex play an important role in the construction of a three-dimensional supramolecular framework. Complex 1 exhibits photoluminescence emission in solid state at room temperature.     

Positions and Stereochemistry of Methyl Branches in the Novel Sex Pheromone Components Produced by a Lichen Moth, Lyclene dharma dharma

Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce three sex pheromone components (I–III), for which we assigned the following novel chemical structures; 6-methyl-2-octadecanone (1) for I, 14-methyl-2-octadecanone (2) for II, and 6,14-dimethyl-2-octadecanone (3) for III. In the Iriomote Islands where the insects were collected, a lure including racemic 1 and 2 attracted the male moths without mixing 3. In this study for further confirmation of the plane structures, the positional isomers with a methyl branch at the 4-, 5-, 7-, 13-, or 15-position (4–8, respectively) were synthesized. The GC-MS analyses revealed that natural components I and II were best fitted with those of 1 and 2, respectively, among the methyl-2-octadecanones examined, indicating the usefulness of this analytical instrument and authentic standards for the determination of the positions of methyl branches. In field trapping tests, 4–8 could not substitute for 1 or 2, nor did these compounds inhibit the active binary lure of 1 and 2, indicating that the males strictly recognized the 2-ketones with a methyl branch at the 6- or 14-positions. Next, the absolute configurations of I and II were determined by HPLC with a normal-phased chiral column (Chiralpak AD-H), which could separate the enantiomers of both 1 and 2. The chiral HPLC analysis of a crude pheromone extract indicated that the females exclusively produced (S)-1 and (S)-2. Furthermore, a field evaluation of each enantiomer revealed that (S)-1 and (S)-2 were bioactive but (R)-1 and (R)-2 were not.     

Synthesis,Crystal Structures,Luminescence, Biological and Catalytic Properties of Two d10 Metal-Organic Coordination Polymers Constructed from Mixed Ligands

Two d¹⁰ metal-organic coordination polymers, [Cd₂(4-cpa)₄(bmip)₂]_n (1) and [Zn(4-cpa)₂(4,4′-bpy)]_n (2), [4-cpa = 4-chlorophenylacetate, bmip = 1,3-bis(2-methylimidazoly)propane, 4,4′-bpy = 4,4′-bipyridine], were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicated that both 1 and 2 display analogous wave-like infinite chain structures. The two coordination polymers are further extended into 3D supramolecular structures through π···π stacking interactions and C–H···O hydrogen bonds for 1 and π···π stacking interactions, C–H···π stacking interactions and C–H···O hydrogen bonds for 2. Both 1 and 2 emit the intense blue luminescence at room temperature. The 4-Hcpa ligand and complexes 1 and 2 have been screened for their herbicidal activities against Brassica napus L. and Echinochloa crusgalli L. The results are compared with the activity of quizalofop-P-ethyl. Both compounds exhibit high catalytic properties on degradation of methyl orange in Fenton-like process.     

A Facile Access to New Polymethylmethacrylate-Anchored Ferrocene Substituted Nickel(II) Unsymmetrical Schiff Base Complexes: Synthesis and Characterization

This paper discloses two new side-chain metallopolymers containing an unsymmetrical organometallic Schiff base complex of Ni(II) linked to a polymethylmethacrylate (PMMA) matrix. The neutral ferrocene substituted Schiff base complex 1, Ni{CpFe(η⁵-C₅H₄)-C(O)CH=C(CH₃)N–o-C₆H₄N=CH-(2-O,5-OH-C₆H₃)} where (Cp = η⁵-C₅H₅), was synthesized via template reaction by condensation of the tridentate half-unit metalloligand Fc-C(O)CH=C(CH₃)-N(H)-o-C₆H₄NH₂ (Fc = ferrocenyl = CpFe(η⁵-C₅H₄)) with 2,5-dihydroxybenzaldehyde in the presence of nickel(II) acetate tetrahydrate. The binuclear Schiff base complex of Ni(II) containing an aromatic free hydroxyl group was reacted under basic conditions with PMMA to afford, upon trans-esterification reaction, metallopolymers 2 (complex 1 monomeric unit/PMMA = 1/5) and 3 (complex 1 monomeric unit/PMMA = 1/3). Elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopies, and cyclic voltammetry were utilized to characterize the newly synthetized compounds. Surface morphology of the metallopolymer film of 2 was studied using atomic force microscopy.     

Sonochemical Synthesis and Characterization of A Nano-Rod Lead(II) Supramolecular, Three Dimensional Coordination Compound: New Precursor to Produce Pure Phase Nano-Sized Lead(II) Oxide

Nanorods of a lead(II) supramolecular three-dimensional (3D) coordination compound, [Pb(tfpb)₂]_n (1) (Htfpb?=?4,4,4-trifluoro-1-phenyl-1,3-butanedione), was prepared by the sonochemical method. The new nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. A single-crystal structure of the compound showed that the coordination number of Pb(II) is eight with six O-donor atoms from the tfpb ligand and two F-donors from anionic ligands. The 3D supramolecular structure of 1 is realized by weak directional C–F···F–C and π–π stacking interactions. After calcination of nano-sized 1 at 500?°C, pure phase nano-sized lead(II) oxide is produced.     

Hydrothermal Syntheses and Crystal Structures of Three Complexes Constructed with Dipyrido[3,2-a:2′,3′-c]phenazine and 2,4′-Biphenyldicarboxylic Acid

Three new metal complexes, [Pb(dppz)(2,4′-bpdc)] _n ·n(H₂O) (1), [Fe(dppz)(2,4′-bpdc)(H₂O)] _n (2) and [Cu(dppz)(2,4′-bpdc)(H₂O)] _n (3) (2,4′-H₂bpdc = 2,4′-biphenyldicarboxylic acid and dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, IR, X-ray single-crystal diffraction and powder X-ray diffraction. The complexes 1, 2 and 3 have 1D chains formed via coordination bonds, and unique three-dimensional or two-dimensional supramolecular structures are further formed due to π–π stacking interactions. The results reveal that the coordination preferences of metal ions play a critical role in the framework construction of these complexes. Meanwhile, the thermogravimetric analysis and photoluminescent property of compounds 1–3 have also been investigated.