In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactio...In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.展开更多
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 ...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.展开更多
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 c...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.展开更多
Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
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 cel...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.展开更多
To understand the fundamental mechanism of aggregation-induced phosphorescent emission(AIPE)and to improve the development of mechanochromic molecules,five new Pt(II)complexes Pt-1–Pt-5 bearing different terminal sub...To understand the fundamental mechanism of aggregation-induced phosphorescent emission(AIPE)and to improve the development of mechanochromic molecules,five new Pt(II)complexes Pt-1–Pt-5 bearing different terminal substituents on 1,3-di(2-pyridyl)benzene(N^C^N)ligands were designed and synthesized.Their photophysical properties have been investigated systematically via a series of spectroscopic methods.Upon excitation,the solid states of these Pt complexes exhibit tunable emissions from yellow to red,and complexes Pt-2 and Pt-3 with a large steric hindrance display remarkable AIPE properties in a tetrahydrofuran/H_(2)O mixture.All complexes,except Pt-5,show evident mechanochromic and vapochromic behaviors.Based on in-depth experimental studies,the reason for the mechanochromic behavior could be the change in the distance of the neighboring Pt complexes,which causes a switching of the emission state from^(3)π,π*/^(3)MLCT(metal-to-ligand charge transfer)to^(3)MLCT.The above results suggest an example of phosphorescence tuning by a switching of the triplet excited state in the solid state,and provide a mechanism of mechanochromic behavior.Furthermore,complex Pt-2 was used as an emission ink in the field of advanced anti-counterfeiting.展开更多
Bladder cancer is a common cancer globally that suffers from expensive treatment,drug and hypoxia resistance,and high recurrence rate.A series of six novel diazido Pt(Ⅳ)complexes with the general formula trans,trans,...Bladder cancer is a common cancer globally that suffers from expensive treatment,drug and hypoxia resistance,and high recurrence rate.A series of six novel diazido Pt(Ⅳ)complexes with the general formula trans,trans,trans-[Pt(N3)2(OH)2(L)2]and various equatorial N-heterocyclic amine ligands(L=pyridines:1 and 3-6;or imidazole:2)have been synthesised and characterised,including their X-ray crystal structures,and their photoactivation investigated.展开更多
Supramolecular architectures such as helical fibers,tubular structures,and nanotoroids(nanorings)have attracted significant interest over the past few decades because of their special physical properties.In this study...Supramolecular architectures such as helical fibers,tubular structures,and nanotoroids(nanorings)have attracted significant interest over the past few decades because of their special physical properties.In this study,we synthesized bis[terpyridine-based Pt(Ⅱ)]complexes with different terminal ligands such as Cl^(-),phenyl acetylene,or pyridine units.Interestingly,the binuclear terpyridine-based Pt(Ⅱ)complex(Ch-1),consisting of Cl^(-)as one ligand at both ends.展开更多
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 muc...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.展开更多
In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)comp...In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)complexes are slightly emissive at ambient conditions,the trans-Pt_(2)Ag_(2)complexes exhibit moderate photoluminescence in dichloromethane and have strong emission in the solid state,originating from aromatic acetylide to(Ph_(2)P)_(2)py ligand-to-ligand charge transfer(^(3)LLCT)and Pt_(2)Ag_(2)cluster metal-centered(^(3)MC)triplet states.Remarkably,the trans-Pt_(2)Ag_(2)complex[Pt_(2)Ag_(2){(Ph_(2)P)_(2)py}_(2)(CuCC_(6)H_(5))_(4)](SO_(3)CF_(3))_(2)exhibit remarkable luminescent vapochromism with emission red-shifts of 100 nm in response to MeCN vapor,arising from intramolecular structural conversion from staggered to parallel arrangements of two face-to-face Pt(CuCC_(6)H_(5))_(2)moieties,which results in the alteration of the excited-state energy in the solid state as supported by TD-DFT studies.展开更多
Two Pd(II)and Pt(II)complexes with two pyrrol-2-carbaldehyde N-p-chlorophenylthiosemicarbazone ligands are designed and characterized showing mononuclear structures.An important pharmacological property for both compo...Two Pd(II)and Pt(II)complexes with two pyrrol-2-carbaldehyde N-p-chlorophenylthiosemicarbazone ligands are designed and characterized showing mononuclear structures.An important pharmacological property for both compounds is the high selectivity for tumor cells and a lack of activity in healthy cells.The Pd(II)compound shows a higher antitumor activity and selectivity than the Pt(II)compound.Both complexes present a variety of biological interactions:with DNA models(pBR322 and CT DNA),proteins(lysozyme and RNase)and other biological targets like proteosome.Our results show that the Pd(II)complex is a more interesting candidate for potential anticancer therapies than the Pt(II)complex,and we provide new insight into the design and synthesis of palladium compounds as potential antitumor agents.展开更多
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 struct...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.展开更多
Luminescent Single-Molecule Magnets(SMMs)have gained broad scientific attention due to their potential applications in the dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring ...Luminescent Single-Molecule Magnets(SMMs)have gained broad scientific attention due to their potential applications in the dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring of temperature in SMM-based devices.We present a route toward thermoresponsive emissive SMMs based on linking two molecular components separately providing luminescent thermometry and SMM features.展开更多
In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as a...In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as an excellent strategy to promote the luminescence efficiency.A series of new materials show over 82%phosphorescence quantum yield and good stability,but they are still not fully elucidated.In this work,several different stable o-carborane cages are introduced into the traditional C,N,C-cyclometalated Pt(Ⅱ)complexes in order to explore their influence completely in contrast to the original phenyl ligand from the view of theoretical investigation.Comprehensive analyses of the geometric structure,molecular orbital and configuration information,spin-orbit coupling elements,vibrational modes,etc.have been carried out.More importantly,our theoretical model highlights that the embedded o-carborane ligands will have an impact on the photophysical properties and quantum efficiency of these Pt(Ⅱ)complexes significantly,which can provide a valuable guideline for designing and regulating several aspects of highly efficient blue phosphorescent materials.展开更多
A new series of mono-cyclometalated square planar platinum(Ⅱ)complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyP...A new series of mono-cyclometalated square planar platinum(Ⅱ)complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O isβ-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ)complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction ofπ-πinteractions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs)and even for nondoped PhOLEDs.展开更多
DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO)respond of platinum(Ⅱ)complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phena...DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO)respond of platinum(Ⅱ)complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,theβvec value of complex 1b-5b is larger than one of complex a,while theβvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,theβvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.展开更多
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 t...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.展开更多
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 nob...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.展开更多
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...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.展开更多
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 t...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.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22201057 and 22472044)Zhejiang Provincial Natural Science Foundation of China(Nos.LR22B010001 and LQ23B010001)。
文摘In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.
文摘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.
基金supported by the National Natural Science Foundation of China(No.21601043,21961009,21663011)Natural Science Foundation of Hainan Province(ZDYF2019140,219MS041)。
文摘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.
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
文摘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.
基金support pro-vided in part by the Natural Science Foundation of Jiangsu Province-Outstanding Youth Foundation(BK20170104)the National Natural Science Foundation of China(21602106)+2 种基金the Six Talent Peaks Project in Jiangsu Province(XCL-037)the Strategic Pioneer Program on Space Science,Chinese Academy of Sciences(XDA15013100 and XDA15013101)the Undergraduate Innovation and Entrepreneurship Training Program(201910291053Z).
文摘To understand the fundamental mechanism of aggregation-induced phosphorescent emission(AIPE)and to improve the development of mechanochromic molecules,five new Pt(II)complexes Pt-1–Pt-5 bearing different terminal substituents on 1,3-di(2-pyridyl)benzene(N^C^N)ligands were designed and synthesized.Their photophysical properties have been investigated systematically via a series of spectroscopic methods.Upon excitation,the solid states of these Pt complexes exhibit tunable emissions from yellow to red,and complexes Pt-2 and Pt-3 with a large steric hindrance display remarkable AIPE properties in a tetrahydrofuran/H_(2)O mixture.All complexes,except Pt-5,show evident mechanochromic and vapochromic behaviors.Based on in-depth experimental studies,the reason for the mechanochromic behavior could be the change in the distance of the neighboring Pt complexes,which causes a switching of the emission state from^(3)π,π*/^(3)MLCT(metal-to-ligand charge transfer)to^(3)MLCT.The above results suggest an example of phosphorescence tuning by a switching of the triplet excited state in the solid state,and provide a mechanism of mechanochromic behavior.Furthermore,complex Pt-2 was used as an emission ink in the field of advanced anti-counterfeiting.
基金the Engineering and Physical Sciences Research Council(EPSRC grant no.EP/P030572/1)Anglo-American Platinum for fundingWe thank Dr Richard T.Bryan(University of Birmingham)for providing SW-780 and VMCUB-1 bladder cancer cells,Professor Elizabeth Wellington(University of Warwick)for access to the hypoxic chamber and BSU team at University of Warwick for providing rat bladders.Single-crystal X-ray diffraction measurements were made using equipment housed within the X-ray Diffraction Research Technology Platform at Warwick with funding from EPSRC grant EP/X034836/1.
文摘Bladder cancer is a common cancer globally that suffers from expensive treatment,drug and hypoxia resistance,and high recurrence rate.A series of six novel diazido Pt(Ⅳ)complexes with the general formula trans,trans,trans-[Pt(N3)2(OH)2(L)2]and various equatorial N-heterocyclic amine ligands(L=pyridines:1 and 3-6;or imidazole:2)have been synthesised and characterised,including their X-ray crystal structures,and their photoactivation investigated.
基金supported by a National Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2020R1A4A2002831,2019R1A6C1010042,2021R1A2C2007664 and 2022R1A4A1022252).
文摘Supramolecular architectures such as helical fibers,tubular structures,and nanotoroids(nanorings)have attracted significant interest over the past few decades because of their special physical properties.In this study,we synthesized bis[terpyridine-based Pt(Ⅱ)]complexes with different terminal ligands such as Cl^(-),phenyl acetylene,or pyridine units.Interestingly,the binuclear terpyridine-based Pt(Ⅱ)complex(Ch-1),consisting of Cl^(-)as one ligand at both ends.
基金financial support from the National Natural Science Foundation of China(No.21978042)the Fundamental Research Funds for the Central Universities(No.DUT22LAB610).
文摘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.
基金National Natural Science Foundation of China(Grants 92061202,21531008 and 21801242)Fujian Science and Technology Project(Grant 2020L3022)Strategic Priority Research Program of Chinese Academy of Sciences(Grant XDB20000000)。
文摘In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)complexes are slightly emissive at ambient conditions,the trans-Pt_(2)Ag_(2)complexes exhibit moderate photoluminescence in dichloromethane and have strong emission in the solid state,originating from aromatic acetylide to(Ph_(2)P)_(2)py ligand-to-ligand charge transfer(^(3)LLCT)and Pt_(2)Ag_(2)cluster metal-centered(^(3)MC)triplet states.Remarkably,the trans-Pt_(2)Ag_(2)complex[Pt_(2)Ag_(2){(Ph_(2)P)_(2)py}_(2)(CuCC_(6)H_(5))_(4)](SO_(3)CF_(3))_(2)exhibit remarkable luminescent vapochromism with emission red-shifts of 100 nm in response to MeCN vapor,arising from intramolecular structural conversion from staggered to parallel arrangements of two face-to-face Pt(CuCC_(6)H_(5))_(2)moieties,which results in the alteration of the excited-state energy in the solid state as supported by TD-DFT studies.
基金supported by the following grants for the Spanish MINECO:SAF-2012-34424,CTQ2015-68779R and CTQ2015-70371-REDT。
文摘Two Pd(II)and Pt(II)complexes with two pyrrol-2-carbaldehyde N-p-chlorophenylthiosemicarbazone ligands are designed and characterized showing mononuclear structures.An important pharmacological property for both compounds is the high selectivity for tumor cells and a lack of activity in healthy cells.The Pd(II)compound shows a higher antitumor activity and selectivity than the Pt(II)compound.Both complexes present a variety of biological interactions:with DNA models(pBR322 and CT DNA),proteins(lysozyme and RNase)and other biological targets like proteosome.Our results show that the Pd(II)complex is a more interesting candidate for potential anticancer therapies than the Pt(II)complex,and we provide new insight into the design and synthesis of palladium compounds as potential antitumor agents.
文摘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.
基金financed by the National Science Centre of Poland,the OPUS-21 project,no.2021/41/B/ST5/02544The research has been supported by an infrastructure grant from the Faculty of Chemistry under the Strategic Programme Excellence Initiative at Jagiellonian Univ.The study was carried out using the research infrastructure co-funded by the EU in the framework of the Smart Growth Operational Program,Measure 4.2+1 种基金Grant No.POIR.04.02.00-00-D001/20,“ATOMIN 2.0-ATOMic scale science for the INnovative economy”We also gratefully acknowledge Polish high-performance computing infrastructure PLGrid(HPC Center:ACK Cyfronet AGH)for providing computer facilities and support within computational grant no.PLG/2019/013095.
文摘Luminescent Single-Molecule Magnets(SMMs)have gained broad scientific attention due to their potential applications in the dual sensing of temperature and magnetic field or optical thermometry for the self-monitoring of temperature in SMM-based devices.We present a route toward thermoresponsive emissive SMMs based on linking two molecular components separately providing luminescent thermometry and SMM features.
基金supported by the State Key Development Program for Basic Research of China(Grant No.2013CB834801)the Natural Science Foundation of China(Grant No.21573088)+1 种基金the Young Scholar Training Program of Jilin Universitythe Open Project Funding of Beijing National Laboratory for Molecular Sciences(BNLMS).
文摘In recent years,cyclometalated Pt(Ⅱ)complexes with a terdentate ligand have been used as prospective blue phosphorescent materials.For improving these materials further,the introduction of o-carborane is treated as an excellent strategy to promote the luminescence efficiency.A series of new materials show over 82%phosphorescence quantum yield and good stability,but they are still not fully elucidated.In this work,several different stable o-carborane cages are introduced into the traditional C,N,C-cyclometalated Pt(Ⅱ)complexes in order to explore their influence completely in contrast to the original phenyl ligand from the view of theoretical investigation.Comprehensive analyses of the geometric structure,molecular orbital and configuration information,spin-orbit coupling elements,vibrational modes,etc.have been carried out.More importantly,our theoretical model highlights that the embedded o-carborane ligands will have an impact on the photophysical properties and quantum efficiency of these Pt(Ⅱ)complexes significantly,which can provide a valuable guideline for designing and regulating several aspects of highly efficient blue phosphorescent materials.
基金support from the National Natural Science Foundation of China(Grant No.20472060)the Basic Research Foundation of Sichuan Province,China(Grant No.07JY029-015)
文摘A new series of mono-cyclometalated square planar platinum(Ⅱ)complexes have been synthesized and the single-crystal X-ray structures of complex 1 and 2 have been determined.The complexes have the general formula ppyPt(O^O),where ppy is 2-phenylpyridyl,and O^O isβ-diketonate ancillary ligands with the acyl substituent group in position 3 of(D)-(+)-camphor.Although,like the many Pt(Ⅱ)complexes with square-planar geometry,these complexes have plane stacking modes in crystal structure,the sterically bulky camphor-derived groups compel extensive slipping of the molecular stacking planes,resulting in the negligible overlapping of the aromatic ring fragments between molecules and the considerable Pt-Pt distance.The resolved spectra and a little shifted emission in solid state of complexes show that there is significant reduction ofπ-πinteractions and Pt-Pt interactions,and suggest these complexes may be good candidates for doped phosphorescent organic light emitting diodes(PhOLEDs)and even for nondoped PhOLEDs.
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University,the Foundation of Jilin Provincial Excellent Youth(Grant No.20050107)Youth Science Foundation of Northeast Normal University(Grant No.111494117)
文摘DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO)respond of platinum(Ⅱ)complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,theβvec value of complex 1b-5b is larger than one of complex a,while theβvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,theβvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.
文摘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.
文摘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.
基金support of the Bulgarian National Science Fund under contract DRNF 02/1
文摘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.
基金supported by the Youth Scholar Backbone Supporting Plan Project for General Universities of Heilongjiang Province (1155G22)China Postdoctoral Science Foundation (20100481018)+2 种基金Heilongjiang Postdoctoral Financial Assistance (LBH-Z09096)Youth Science Foundation of Harbin University of Science and Technology (2009YF020)National Natural Science Foundation of China (20973078)
文摘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.
