Interactions Between Anticancer Pt(II) complexes and Human Erythrocyte Spectrin *

The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are 4.7×10 2 binding sites of cisplatin(CDDP) in a spectrin tetramer(SPT). Among them, about 70 sites with apparent binding constant K 1】3.47×10 6 were of highest affinity, 1.8×10 2 sites with K 2 = 3.47×10 6 were of high affinity, and other 2.2×10 2 sites with K 3 = 8.77×10 5 were of low affinity. The conformation change of spectrin, depending on the concentration of Pt(II) complex and molar ratio(R) of Pt(II) complex to spectrin, was induced by the binding of Pt(II) complexes. It indicated that the interaction of both CDDP and cis diaquodiamine platinum(DADP) with SP followed a two step first order kinetic process in the first stage (1 h), and the kinetic constants were determined. In the second stage, the induced conformation change, polymerization and depolymerization of SP were probably involved. It was noticed that in the reaction of SP and Pt(II) complexes with 1,2 cyclohexanediammine isomers as chiral carrier ligand, stereo matching played a more important role than the affinity of Pt(II) to thiol groups of SP.

One-dimensional Chain Crown Ether Complexes Synthesis and Crystal Structure of ([K(DB18-crown-6)]_(2)(CH_(3)CN))[Pt(SCN)_(4)]

The complexe{[K(DB18-crown-6)]_(2)(CH_(3)CN)}[Pt(SCN)_(4)]was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complexe belongs to monoclinic,space group c2/c with cell dimensions,a=2.5904(8),6=1.3653(4),c-1.84706(6)nm,β=123.811(4)°,V=5-339(3)nm^(3),Z=4,.Dcalcd=l.577 g/cm^(3),F(000)=2552,R_(1)=0.051 l,wR_(2)=0.1411.The complexe shows one-dimensional chain of{[K(DB18-crown-6)]+complex cation and[Pt(SCN),i]2-complex anion bridged by N atom of CHaCN moleculer between two[K(DB18-crown-6)]_(2)[Pt(SCN)_(4)]groups respectively.

The First Three-dimensional Crown Ether Complex:{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)]}[Pt(SCN)_(6)](SCN)_(2)with Covalent Bond

The novel benzo-18-crown-6(B18-C-6)complex;{[Na(Bl8-C-6)]_(6)[Pt(SCN)_(6)]}[Pt(SCN)_(6)](SCN)_(2)(1)was synthesized and characterized by elemental analysis,IR spectrum and x-ray diffraction analysis.Thr crystal structure belongs to rhomobohedral,space group R-3 with cell dimesions:a=6=1.9933(3),c=2.9760(6)nm,α=β=90,γ=120°,V=10.240(3)nm^(3),Z=3,A,aclcd=1.564 g/cm^(3),F(000)=4908.1 is composed of one{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)]}4+complex cation,one[Pt(SCN)_(6)]^(2-)complex anion and two SCN~anions.{[Na(B18-C-6)]_(6)[Pt(SCN)_(6)3}4+complex cation shows a three-dimensional network structure bridged by Na-O interactions between adjacent[Na(B18-C-6)]+units.The function of[Pt(SCN)_(6)]^(2-)complex anion and two SCN'anions are balancing charge in crystal.

Multiresponsive,easy-reversible,and dual-visual Pt(Ⅱ)salt nanostructures for advanced anti-counterfeiting application

Smart materials that integrate multi-stimuli response,full reversibility,and dual-visual read-out channel are highly desired for anticounterfeiting and information encryption applications.Herein,we developed a multiresponsive perchlorate terpyridyl Pt(Ⅱ)nano complex which could undergo fully reversible conversion between three forms stimulated by water or formaldehyde molecule due to the extent of Pt–Pt interaction.Meanwhile,a dual-visual channel,i.e.,the colorimetric channel changed from yellow to orange or red and the corresponding luminescent channel from orange to orange-red or red,has also been found.The weak and equivalent strength of ion-dipole interaction and hydrogen bond that generated between formaldehyde/water and Pt(II)salt result in the easy-control reversibility between the three forms.Furthermore,by introducing different polymer matrices,1Cl·ClO_(4)@PMMA(1Cl·ClO_(4):[Pt(tpy)Cl]·ClO4,tpy:2,2':6',2''-terpyridine),PMMA:poly(methyl methacrylate))and 1Cl·ClO4@PVA(PVA:polyvinyl alcohol)are successfully constructed,which exhibit different reversible behaviors since the PMMA and PVA matrix exert different influences on the strength of hydrogen-bond.Those smart Pt(II)salt nanostructures present great potential for high-security-level anticounterfeiting application.

An AIPE-active fluorinated cationic Pt(Ⅱ)complex for efficient detection of picric acid in aqueous media

A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits much higher aggregation-induced phosphorescent emission activity than that of a nonfluorinated complex 1 in CH_(3)CN/H_(2)O.The complex 2 demonstrates efficient detection on picric acid(PA)in CH_(3)CN/H_(2)O,providing a high quenching constant(K_(SV)=2.3×10^(4) L/mol)and a low limit of detection(LOD=0.26μmol/L).In addition,complex 2 shows high selectivity for detection of PA in real water samples.Density functional theory calculations and proton nuclear magnetic resonance spectra suggest that the detection mechanism is attributed to the photo-induced electron transfer.

Multicolor circularly polarized phosphorescence of axially chiral binuclear platinum(Ⅱ) complexes

D-A charge transfer, including through-bond charge transfer and through-space charge transfer between two different electron donors(D) and electron acceptors(A), is a fundamental and powerful tool to tune the optical properties of organic dyes. Herein,we demonstrate a unique strategy to tune phosphorescence and circularly polarized luminescence properties of axially chiral binuclear Pt(Ⅱ) complexes through long-range charge transfer, even though these molecules have two totally identical segments on either side of the chiral core. The presence of axial chirality would break not only the symmetry of molecular structure and π-conjugation system but also the symmetry of charge distribution for long-range charge transfer. These binaphthyl-based Pt(Ⅱ)complexes bearing coordinated atoms far away from chiral axis exhibit no Pt-Pt interactions but colorful concentrationdependent phosphorescence with quantum yield up to 86.4% and could be applied as emitters in highly efficient solutionprocessed organic light-emitting diodes to achieve luminance, luminance efficiency, power efficiency, external quantum efficiency, and asymmetry factor up to 8.94 × 10^(3)cd m^(-2), 41.9 cd A-1, 18.8 lm W^(-1), 12.6% and 2.98 × 10^(-3), respectively. Therefore,the present work affords a new and simple way to utilize the inherently asymmetric advantage of chirality for the design of D-Abased organic dyes.

A STUDY OF SILICA-SUPPORTED CROSS-LINKED POLY (MALEIC ACID-CO-STYRENE)-PLATINUM COMPLEX IN THE HYDROGENATION OF p-CRESOL

A silica-supported cross-linked poly(maleic acid -co- styrene)-platinum complex (PMS-Pt) has been prepared and found to be active in the hydrogenation of p-cresol under mild conditions (303-323K, 1.01 x 10(5)Pa). In this hydrogenation system water serves as a solvent and p-cresol can be converted to 4-methylcyclohexanol quantitatively via 4-methylcyclohexanone as intermediate.

Synthesis,Characterization and Catalytic Hydrosilylation Activity of [60] Fullerene n-Propylamine Platinum,Rhodium Complex

Fullerene n propylamine platinum,rhodium complex have been prepared from C 60 via amination with n propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two noble metal complexes can effectively catalyze hydrosilylation of olefins with triethoxysilane. The Pt complex exhibits high regioselectivty for styrene, nearly 100% branched product is obtained.

Synthesis and Structure of bc-Dichloro-af-dihydroxo-de-bis(N-3-pyridinylmethanesulfonamide)platinum(Ⅳ) Diydrate

The Pt（IV） complex cis,cis,trans-[Pt（PMSA）2Cl2（OH）2]·2H2O（1）, where PMSA = N-3-pyridinylmethanesulfonamide, has been synthesized and characterized by elemental analysis, molar electric conductivity and IR spectrum. X-ray crystallography revealed that the title compound crystallizes in the monoclinic C2/c space group with unit cell dimensions a = 16.5424（7）, b = 8.6973（3）, c = 16.6079（6） A, β = 117.185（5）° and Z = 4. Pt（IV） has an octahedral coordination geometry and the PMSA ligands are coordinated via the pyridine N atom. They are in a transoid orientation between each other and are inclined in the same direction with respect to the Pt-C1-Cli-N-Ni plane at an angle of 64.6（1）° （symmetry operation： （i） 1- x, y, 3/2-z）. The structure is stabilized by a system of hydrogen bonds involving the complex and water molecules.

Molecular design and theoretical investigation into one-and two-photon absorption properties of two series of cyclometalated platinum(Ⅱ) complexes

We have theoretically investigated two series of cyclometalated Pt（II） complexes, a series [Pt （C, N, N） Cl] and b series [Pt （C, N, Npyrazolyl） Cl]. The geometrical and electronic structures are calculated at the ECP60MWB//6-31G＊（H, C, Cl, N, S） basis set level using DFT method; one-photon absorption （OPA） properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption （TPA） properties are obtained with the ZINDO/SOS method. The resonance integrals parameters （βsp and βd） for Pt are adjusted to -1 and -28.5 eV, respectively, to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results. The calculated results indicate the molecule 2b （[Pt （Cnaphthyl, N, Npyrazolyl） Cl]） has the biggest potential as outstanding TPA materials because （i） the TPA properties of b series are more outstanding in IR wavelength range, the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination （e.g., dimerization） and chemical interactions; （ii） when C is CnaphthyI in the C, N, N ligand of cyclometalated Pt（II） complexes, the molecules have the best conjugation effect and the best TPA properties.

Variance of Solid-state Pt…Pt Interactions in Luminescent Cyclometalated Cationic Pt(Ⅱ)-isocyanide Complexes

Polymorphic structures of cyclometalated cationic Pt(Ⅱ)-isocyanide complexes(-)-1[Pt((−)-NNC)(Dmpi)]Cl with different packing modes can be isolated before.In this paper,a series of solid-state powders with variable colors(yellow,orange and red)have been obtained from the evaporation of complex(-)-1 in different solvents.The crystallinity,thermogravimetric properties,absorption,luminescence and excited state lifetimes have been studied.In addition,intermolecular Pt…Pt interactions in the optimized configurations of different aggregates have been explored,and calculations of frontier molecular orbitals of monomer,dimer,trimer and tetramer have been carried out.

Synthesis and Crystal Structure of cis-[meso-1, 3-Bis(propylsulfinyl)propane]dichloroplatinum(Ⅱ)

A mononuclear complex, cis-[meso-1, 3-bis(propylsulfinyl)propane]- dichloroplatinum(Ⅱ) (Pt(C9H20O2S2)Cl2) 1, has been prepared and structurally characterizated by single-crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group Pna21 with a = 22.800(3), b = 11.7662(13), c = 5.8115(6) ? V = 1559.0(3) ?, Mr = 490.36, Dc = 2.089 g/cm3, Z = 4, F(000) = 936, m (MoKa) = 9.596 mm-1 and l = 0.71073 ? The structure was refined to R = 0.0204 and wR = 0.0473 for 2703 reflections with I > 2(I). It is revealed that the central Pt(Ⅱ) ion in the title complex is bonded to two Cl atoms in a cis-configuration and two S atoms of the ligand to form the coordination geometry deviating slightly from the square planar.

Synthesis,Crystal Structure and Luminescent Mechanochromism of a Square-planar Pt(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative

A new square-planar platinum(Ⅱ) complex, [Pt(Me3SiC≡Cphen)(C≡CC6H4Cl-3)2](1), was synthesized by using 3-trimethylsilylethynyl-1,10-phenanthroline(Me3SiC≡Cphen) and 3-chlorophenylacetylene ligands, and its structure was characterized by single-crystal X-ray crystallography. 1 crystallizes in triclinic, space group P1 with a = 6.9524(5), b = 12.7796(11), c = 17.5846(10) ?, α = 78.484(5), β = 88.700(5), γ = 75.600(6)°, V = 1482.23(19) ?3, Z = 2, C33H24Cl2N2 PtSi, Mr = 742.62, Dc = 1.664 g/cm3, F(000) = 724, μ(Mo Ka) = 4.979 mm-1, R = 0.0369 and wR = 0.0786. In 1, adjacent molecules along the a axis are stacked in a columnar structure through π···π interactions, and such neighboring columnar structures are connected with each other by C–H···π hydrogen bonds to form a 2D supramolecular network. 1 exhibits reversible luminescence mechanochromic property with the luminescence red shift in a range of ca. 146~182 nm. Extremely large red-shifts of luminescence spectra suggest that luminescent mechanochromic property of 1 is due to the formation of aggregate via Pt–Pt interaction during the mechanical grinding. Based on this property, a simple device was developed and used for rewritable data storage.

TD-DFT Studies on Electronic and Spectral Properties of Platinum（II） Complexes with Phenol and Pyridine Groups

The molecular structures of the ground and the lowest triplet states for a series of Pt（ll） complexes PtLCl（l）[L=6-（2-hydroxyphenyl）-2,2＇-bipyridine], Pt（pp）2[pp=2-（2-hydroxyphenyl）pyridine]（2）, PtbpyClz（bpy=2,2＇- bipyridine）（3）, and the free tridentate L ligand（4） were optimized by the density functional theory B3LYP and UB3LYP methods, respectively. On the basis of optimized geometries, the spectral properties were investigated with time-dependent density functional theory（TD-DFT）. In comparison with those of complexes 2 and 3, the more rigid structure of complex 1 together with its low rate of the radiationless decay via nonemissive d-d state leads to higher photoluminescence quantum efficiency. And the phosphorescence quantum efficiency of complex 1 can be easily controlled by modifying auxiliary ligands. The introduction of fluorine ligand into complexes can effectively increase the radiation transition rate and decrease the radiationless d-d transition rate, and as a result, a novel complex PtLF（5） might be a good phosphorescent material suitable for organic electronic devices.

Controlling Molecular Packing in Aqueous Metallosupramolecular Self-assembly by Ligand Geometry

The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.