新型多吡啶铂(Ⅱ)络合物的设计、合成及性能研究

<正>由于特殊的分子构型及电子排布,具有平面四边形构型的多吡啶Pt(Ⅱ)络合物能够产生许多特殊的、具有潜在应用价值的激发态性质．本论文设计、合成了一系列以三联吡啶、6-苯基-2,2’-二联吡啶、菲啰啉为主配体,取代苯乙炔为辅助配体的多吡啶Pt(Ⅱ)络合物,系统地研究了它们的光物理性质,取得如下有意义的研究结果:     

Synthesis and Properties of Platinum(II) 2-(2-Pyridyl)thiophenide Complexes and Ruthenium(II) Bisbipyridyl Complexes with 1,2-Bis(diphenylphosphino)ethene

Russian Journal of General Chemistry -     

Spectroscopic and Electrochemical Properties of Palladium(II) and Platinum(II) 2-(2-Pyridyl)thiophenide Complexes with 4,4'-Bipyridyl

Russian Journal of General Chemistry -     

Crystal Structures and Luminescence Properties of Platinum(II) Complexes Containing 3,3'-Biisoquinoline

Three new platinum complexes containing 3,3'-biisoquinoline (i-biq), [Pt(CN)(2)(i-biq)] (1), [PtCl(2)(i-biq)] (2), and [Pt(i-biq)(2)](PF(6))(2) (3), have been synthesized as orange-red, yellow, and colorless crystals, respectively. Their crystal structures and luminescence properties are reported. Crystal data: for 1.0.5H(2)O, PtO(0.5)N(4)C(20)H(13), orthorhombic, Pbcm, a = 13.989(2) ?, b = 18.304(1) ?, c = 6.682(3) ?, V = 1710.9(6) ?(3), Z = 4, and final R = 0.039 (R(w) = 0.033) for 970 independent reflections; for 2.DMF.H(2)O, PtCl(2)O(2)N(3)C(21)H(21), triclinic, P&onemacr;, a = 11.047(1) ?, b = 12.397(3) ?, c = 8.000(2) ?, alpha = 106.56(1) degrees, beta = 100.15(1) degrees, gamma = 76.15(1) degrees, V = 1012.8(3) ?(3), Z = 2, and final R = 0.058 (R(w) = 0.077) for 4219 independent reflections; for 3.2DMF, PtP(2)F(12)O(2)N(6)C(42)H(38), triclinic, P&onemacr;, a = 10.795(2) ?, b = 13.511(2) ?, c = 8.281(1) ?, alpha = 105.22(1) degrees, beta = 112.17(1) degrees, gamma = 85.02(1) degrees, V = 1079.2(3) ?(3), Z = 1, and final R = 0.038 (R(w) = 0.042) for 3606 independent reflections. Square-planar complexes of 1 are stacked in the crystal to form a columnar structure with the Pt-Pt distance of 3.34 ?. The crystal emits strongly, even at room temperature, and the emission spectrum is similar to that for the [Pt(CN)(2)(bpy)] crystal (bpy = 2,2'-bipyridine), which is due to a (3)dpi[dsigma(Pt) --> pi(i-biq)] transition. The single crystal emission spectrum at 77 K is, however, observed as a superposition of broad (3)dpi and sharp (3)pipi(i-biq) emissions. The crystal structure of 2 has a completely different stacking structure from that of 1. The stacking occurs on the i-biq ligands, and the Pt atoms are separated more than 6 ?. The complex exhibits only a structured emission component assigned to the (3)pipi(i-biq) transition in the crystal at 77 K, in agreement with the crystal structure with no Pt-Pt interaction. In the crystal of 3, the [Pt(i-biq)(2)](2+) complexes are stacked but offset, being in close contact between parts of adjacent i-biq ligands. There is no Pt-Pt interaction also in this case. Two i-biq ligands in the complex are distorted to adopt the bowed conformation due to the steric crowding of the alpha-hydrogens on opposite ligands. Nevertheless, 3 provides almost the same (3)pipi emission spectrum as 1 and 2 in dilute glassy solution at 77 K. The (3)pipi emission spectra observed in the crystals of these Pt(II) complexes are red-shifted compared with those in dilute glassy solution. The fact is attributable to the pi-pi intermolecular interactions between the ligands in the crystals. The factors controlling the crystal structures for these complexes are also discussed.     

Sulfobridged Polynuclear Complexes of Platinum(II) and Palladium(II)

When the platinum(II) and palladium(II) salts interact with ligands such as cystamine-(mercamine) HSCH₂CH₂NH₂ and 2-mercaptoethanol HSCH₂CH₂OH under certain conditions, polynuclear complexes of the compositions are obtained: [Pt₆(SCH₂CH₂NH₂)₈]Cl₄. 5H₂O and [Pd₆(SCH₂CH₂OH)₈]Cl₄. In a comparative study of the IR and X-ray spectra of synthesized complexes and ligands, as well as the results of X-ray diffraction studies, it was established that sulfur atoms of 2-mercaptoethanol occupy a bridge position with a mixed coordination of ligands in the palladium complex. In the platinum(II) complex bidentate coordination of ligands is realized through sulfur and nitrogen atoms.     

Photophysical Properties and OLED Applications of Phosphorescent Platinum(II) Schiff Base Complexes

The syntheses, crystal structures, and detailed investigations of the photophysical properties of phosphorescent platinum(II) Schiff base complexes are presented. All of these complexes exhibit intense absorption bands with λ_max in the range 417–546 nm, which are assigned to states of metal‐to‐ligand charge‐transfer (¹MLCT) ¹[Pt(5d)→π*(Schiff base)] character mixed with ¹[lone pair(phenoxide)→π*(imine)] charge‐transfer character. The platinum(II) Schiff base complexes are thermally stable, with decomposition temperatures up to 495 °C, and show emission λ_max at 541–649 nm in acetonitrile, with emission quantum yields up to 0.27. Measurements of the emission decay times in the temperature range from 130 to 1.5 K give total zero‐field splitting parameters of the emitting triplet state of 14–28 cm^?1. High‐performance yellow to red organic light‐emitting devices (OLEDs) using these platinum(II) Schiff base complexes have been fabricated with the best efficiency up to 31 cd A^?1 and a device lifetime up to 77 000 h at 500 cd m^?2.     

The Anticancer Activity and HSA Binding Properties of the Structurally Related Platinum (II) Complexes

The development of resistance and unwanted harmful interaction with other biomolecules instead of DNA are the major drawbacks for application of platinum (Pt) complexes in cancer chemotherapy. To conquer these problems, much works have been done so far to discover innovative Pt complexes. The objective of the current study was to evaluate the anti cancer activities of a series of four and five-coordinated Pt(II) complexes, having deprotonated 2-phenyl pyridine (abbreviated as C^N), biphosphine moieties, i.e., dppm?=?bis(diphenylphosphino) methane (Ph₂PCH₂PPh₂) and dppa?=?bis(diphenylphosphino)amine (Ph₂PNHPPh₂), as the non-leaving carrier groups. The growth inhibitory effect of the Pt complexes [Pt(C^N)(dppm)]PF₆: C ₁ , [Pt(C^N)(dppa)]PF₆: C ₂ , and [Pt(C^N)I(dppa)]: C ₃ , toward the cancer cell lines was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. In addition, the florescence quenching experiments of the interaction between human serum albumin (HSA) and the Pt complexes were performed in order to obtain the binding parameters and to evaluate the denaturing properties of these complexes upon binding to the general carrier protein of blood stream. The structure?Cactivity relationship studies reveal that four-coordinated Pt complexes C ₁ and C ₂ with both significant hydrophobic and charge characteristics, not only exhibit strong antiproliferation activity toward the cancer cell lines, but also they display lower denaturing effect against carrier protein HSA. On the other hand, five-coordinated C ₃ complex with the unusual intermolecular NH??Pt hydrogen binding and the intrinsic ability for oligomerization, exhibits poor anticancer activity and strong denaturing property. The current study reveals that the balance between charge and hydrophobicity of the Pt complexes, also their hydrogen binding abilities and coordination mode are important for their anticancer activities. Moreover, this study may suggest C ₁ and C ₂ as the potential template structures for synthesis of new generation of four-coordinated Pt complexes with strong anticancer activities and weak denaturing effects against proteins.     

Complexes of Platinum(II) Chloride with Cyanophosphines

Platinum(II) cyanophosphine complexes PtL₂Cl₂, where L = P(CN)₃, PhP(CN)₂, or Ph₂PCN, were synthesized. Their properties and mode of coordination were examined.     

Synthesis and Characterization of Novel Trans-Mixed Diamine Platinum(II) and Platinum(IV) Complexes

A series of novel trans-mixed diamine platinum(II) and platinum(IV) complexes of type trans-[Pt^II(R-NH₂)(R'-NH₂)Cl₂] and trans -[Pt^IV(R-NH₂)(R'-NH₂)Cl₄] (where R-NH₂ = ethylamine or butylamine and R'-NH₂ = methylamine, propylamine, isopropylamine, pentylamine, or hexylamine) was synthesized and characterized using elemental analysis and infrared and ¹⁹⁵Pt nuclear magnetic resonance spectroscopic techniques.     

Resolution of 5- and 6-Membered P-Heterocycles: Racemic and Optically Active Platinum(II)-3-Phospholene Complexes

Abstract

Methods were developed for the resolution of several five- and six-membered phosphorus heterocycles (1c-e, 2, 4). It was investigated if the optical activity is preserved during the 1a→2→3→4 reaction sequence. Racemic and optically active 1b-e 3-phospholene 1-oxides were converted to the corresponding platinum-complexes (10b-e), which are potential catalysts.     

Platinum(II) Mono-N1-(2"-Tetrahydrofuranyl)-5-Fluorouracilate Complexes with Ammonia

The reaction between cis-[Pt(NH₃)₂Cl₂], N¹-(2"-tetrahydrofuranyl)-5-fluorouracil (HL), and NaOH (taken in a molar ratio of 1 : 1 : 1) or between cis-[Pt(NH₃)₂Cl₂], HL, and Ag₂O (taken in the molar ratio of 1 : 1 : 0.5) was used to synthesize complexes Ia (in the case of NaOH) or Ib (in the case of Ag₂O) with composition Pt(NH₃)₂LCl. The model complex [Pt(NH₃)₃L]NO₃ (II) was synthesized by the reaction between [Pt(NH₃)₃Cl]Cl, HL, AgNO₃, and Ag₂O (1 : 1 : 1 : 0.5). The obtained compounds were characterized by chemical analysis, chromatography, thermogravimetry, conductometry, potentiometry, IR, electronic, and NMR spectroscopies. Complexes Ia and Ib were found to have both similar and different properties. The structures of the compounds and the type of L^– coordination to platinum(II) were suggested. Cytotoxic properties of Iaand Ib were studied.     

The synthesis and structural characterisation of [Ru(eta-Cp)(dppf)SnBr3

The reaction of [Ru(eta-Cp)(dppf)N(3)] (1) with equimolar amount of SnBr(2) yielded an interesting heterotrimetallic compound [Ru(eta-Cp)(dppf)SnBr(3)] (2) (dppf: 1,1'-bis-diphenylphosphinoferrocene). Compounds 1 and 2 were characterised by IR, NMR (1H, 13C, 31P and 119Sn), and 2, additionally, by 57Fe and 119Sn M?ssbauer spectroscopy and X-ray crystallography. The latter results were as follows: monoclinic, C2/c, a = 32.8879(4)A, b = 11.9888(2)A, c = 20.8986(3)A, beta = 92.545(1)degrees, V = 8231.9(2)A(3), Z =8.     

Cyanoalkyl Complexes of Platinum (II). I. Preparation and Spectroscopic Properties

The oxidative addition of XRCN to PtL₄ yields cis-and/or trans-PtX(RCN)L₂ (X = Cl, Br; R = (CH₂)_n, n = 1, 2, 3; L = PPh₃, PPh₂CH₃, AsPh₃). L is readily displaced by more basic phosphines or by a diphosphine. In each case the trans complex is the thermodynamically more stable isomer and cis-trans isomerization catalyzed by free L occurs in dichloromethane. Insertion of CO in the σ Pt? C bond takes place quantitatively in the case of cyanoethyl and cyanopropyl. Abstraction of X by AgBF₄ gives cis or trans cationic complexes with N-bonded CN group.     

Chemistry of N,N-Dimethylaminoalkylchalcogenolate Complexes of Palladium(II) and Platinum(II)

Abstract

Four different series of N,N-dimethylaminoalkylchalcogenolates, viz. Me₂NCH₂ CH₂E^?, Me₂NCH(Me)CH₂E^?, Me₂NCH₂CH(Me)E^?, and Me₂NCH₂CH₂CH₂E^? (E = S, Se, Te), (referred as E^∩N) have been synthesized and characterized. Their reactions with palladium(II) and platinum(II) precursors have been explored. Complexes of the general formula, [MCl(E^∩N)]_n, [MCl(E^∩N)₂]_n, [MCl(E^∩N)(PR₃)], [M₂Cl₂(μ-E^∩N)₂(PR₃)₂], [M₂(μ-E^∩N)₂(P^∩P)₂]²⁺, etc. have been isolated. All the complexes have been characterized by elemental analysis, IR, NMR (¹H, ¹³C, ³¹P, ⁷⁷Se, ¹²⁵Te, ¹⁹⁵Pt), UV-vis, and FAB mass spectral data. A weak absorption in the electronic spectra of [MCl(E^∩N)(PR₃)] has been attributed to metal mediated ligand-to-ligand charge transfer and showed pronounced chalcogen dependence being red shifted on moving from S → Se → Te. Structures of several complexes have been established by X-ray diffraction analyses. Thermal behavior of some of these complexes has been investigated by TGA.     

Preparation of Platinum(II) Cyclooctadiene Complexes by Photoirradiation

Preparation of platinum cyclooctadiene complexes under photoirradiation was studied, and the reaction mechanism was suggested.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 353–356.Original Russian Text Copyright © 2005 by de Vekki, Uvarov, Skvortsov.     

Carbonyl Complexes of Platinum (II) and Palladium(II) with Heterocyclic Cyclometalating Ligands

Russian Journal of General Chemistry -     

Mixed Platinum(II) Halide Complexes with Sulfur Donors

Abstract

The reaction of platinum(II) halides with stoichiometric amounts of either dimethyl sulfoxide (DMSO) or thiocarbamic ester (L) in acetone yields the complexes cis-[Pt(L)(DMSO)X₂], where L α MTC (EtOSCNHMe), ETC (EtOSCNHEt) or TC (EtOSCNH₂) and X α Cl or Br. The compounds have been isolated and characterized by elemental analysis and by infrared and nmr (¹H and ¹³C) spectroscopy. Either dimethyl sulfoxide or thiocarbamic ester coordinate through the sulphur atom. In the MTC and ETC adducts the planar ligand molecule is present in the isomeric form bearing the N-alkyl group in an anti position with respect to the thiocarbonyl group.     

Preparation of Palladium(II) and Platinum(II) Phosphine Complexes Promoted by Phase-Transfer Catalysts

The synthesis of M(PR₃)₂Cl₂ (M = Pd and Pt, R = alkyl or aryl) front K₂MCl₄ (in H₂O) and PR₃ (in CH₂Cl₂) was promoted by the addition of phase-transfer catalysts (PTC). The greater the amount of PTC used, the more quickly the reaction completed. ³¹P NMR spectra of some M(PR₃)₂Cl₂ in the presence of free PR₃ were measured; these NMR resulls were used to explain problems encountered during the preparations.