Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,...Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.展开更多
Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen...Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.展开更多
The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5...The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.展开更多
An azo-based ligand of azotetrazolyl-2,7-dihydroxynaphthalene(H3ATD)was used to synthesize three unprecedented Fe^(Ⅲ)-M^(Ⅱ)-Fe^(Ⅲ)(M=Fe,Cd)linear trinuclear complexes with different high temperature spin crossover(...An azo-based ligand of azotetrazolyl-2,7-dihydroxynaphthalene(H3ATD)was used to synthesize three unprecedented Fe^(Ⅲ)-M^(Ⅱ)-Fe^(Ⅲ)(M=Fe,Cd)linear trinuclear complexes with different high temperature spin crossover(SCO)behaviours for the terminal Fe^(Ⅲ)ions.展开更多
Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and thei...Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and their structures determined.Both complexes have linear trinuclear structures composed of two ligands and three metal ions.Cryomagnetic studies reveal that both complexes show intramolecular antiferromagnetic interactions between the metal ions.展开更多
Spin-crossover(SCO)complexes have been extensively studied in the past few decades owing to their bistable nature which find application in a myriad of areas.In order to enhance and optimize the SCO behavior,considera...Spin-crossover(SCO)complexes have been extensively studied in the past few decades owing to their bistable nature which find application in a myriad of areas.In order to enhance and optimize the SCO behavior,considerable attention is being paid towards the synthesis of discrete multinuclear spin-crossover complex systems.Here,two mixed-valence Fe_(2)^(Ⅲ)Fe^(Ⅱ)trinuclear complexes of the formula{[Fe^(Ⅱ)(TPMA)][Fe^(Ⅲ)(TpR)(CN)_(3)]_(2)}·MeOH·2H_(2)O(1)and{[Fe^(Ⅱ)(TPMA)][Fe^(Ⅲ)(TpR)(CN)_(3)]_(2)}·H_(2)O(2)[where TPMA=tris(2-pyridylmethyl)amine,Tp=tris(pyrazol-1-yl)borate,R=3,5-dimethyl for 1 and H for 2]were synthesized and characterized.Magnetic measurements confirmed that complex 1 undergoes SCO at a high temperature(T_(1/2)=410 K for the fresh sample and T_(1/2)=406 K for the dried sample),while complex 2 displays near room temperature SCO(T_(1/2)=283 K for the fresh sample and T_(1/2)(↑)=283 K and T_(1/2)(↓)=257 K for the dried sample).To the best of our knowledge,complex 1 has the highest transition temperature reported among trinuclear SCO complexes so far,which is a remarkable feature of multinuclear materials.Slight structural modifications tend to upend the SCO behavior which paves the way for fine tuning SCO.展开更多
3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the ...3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the first example of silver pyrazolate adducts emissive in solution at room temperature.The electronic coupling was observed for pyrazole with a structurally flexible triphenylamine substituent,determining the intraligand charge-transfer(ILCT)nature of the excited states.The association-dissociation of the trinuclear complex core with the heavy atom effect leads to the intense phosphorescence of the triphenylamine-containing complex.The structural rigidity of the N-ethyl carbazole substituent allows only twisting via the bond to the pyrazolate core leading to typical carbazole-centered(LC)fluorescence in solution.In the solid-state,aggregation plays the primary role in emission properties.The observed behavior is in good agreement with the theoretical calculations.展开更多
A novel double-stranded trinuclear bis(tridipyrrin)zinc(Ⅱ)complex,constructed from a linearπ-conjugated tridipyrrin ligand,was synthesized and characterized.The complex featuring six directly linked dipyrrin units e...A novel double-stranded trinuclear bis(tridipyrrin)zinc(Ⅱ)complex,constructed from a linearπ-conjugated tridipyrrin ligand,was synthesized and characterized.The complex featuring six directly linked dipyrrin units exhibits a stable double-helical structure with two non-superimposable P and M enantiomers,as confirmed by X-ray crystallography.Chirality was further demonstrated through HPLC separation and mirror-image circular dichroism(CD)spectra.The complex shows strong near-infrared(NIR)absorption and excellent solubility in various solvents,attributed to its sterically hindered structure.Spectroscopic,electrochemical,and theoretical studies revealed its unique electronic properties and redox behavior.This work advances the design of chiral NIR-active metallo-supramolecular systems and highlights potential applications in chiroptical mateials.展开更多
Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this a...Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.展开更多
Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was ...Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was characterized with variable temperature magnetic susceptibility (4-300 K). The exchange integrals J (Cu-Gd) and J'(Cu-Cu) were found to be 0.83 cm^(-1) and -1.62 cm^(-1), indi- cating that very weakly ferromagnetic spin-exchange interaction operates between Cu(II) and Gd (III) ions.展开更多
A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized...A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.展开更多
A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） c...A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） crystallizes in tetragonal,space group P4 2 /n,a=2.08581（12）,b=2.08581（12）,c=0.72331（4） nm,M r=761.73,V=3.1468（3） nm 3,Dc=1.608 g/cm 3,Z=4,F（000）=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.展开更多
A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray s...A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P2 1/c with a = 7.706（7）, b = 14.882（6）, c = 18.639（6） A, β = 108.08（2）°, V= 2032（1） A3, Dc = 1.525 g/cm3, Mr = 932.95, Z= 2, F（000） = 972,μ = 1.442 mm-1, the final R = 0.0359 and wR = 0.0771. The three nickel（II） atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3＋/Ni2＋ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.展开更多
Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and full...Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.展开更多
A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and wat...A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.展开更多
Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000)...Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.展开更多
The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1...The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1. 637 g/cm-3 p=12. 680 cm-1, F(000)=1404. The final refinement is convergedwith R=0. 052 and Rw=0. 055. In the molecule [Cd3(py8(Oac)4] (CIO4)2, the aver-age values of Cd-N and Cd-O bonds are 2. 306 and 2. 288 A, respectively. In thecanon of the title complex. each Cd atom is coordinated by N and O atoms, which arefrom pyridine molecules and acetatoes, respectively, to form a distorted octahedron.And three Cd atoms are linked by two u2-O atoms of two acetatoes and other two u-ac-etato side bridges.展开更多
Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperatur...Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperature magnetic susceptibility has been set up to produce coupling constants and spin states of the magnetic centers.Calculation has been carried out on a series of Co(Ⅱ)complexes containing mixed thiolato and phosphine ligands:Co3(mp)2(mpH)2(PR3)3(R=Et,R=Bu) and Co3(bdt)3 (PBu3)3.It has been found that all these studied complexes are anti-ferromagnetically coupled.Coupling constant shows the strength of the exchange interaction,which is determined by many factors.Relation between the spin state and the coordination circumstance of Co(Ⅱ) was discussed too.展开更多
Four new heterotrinuclear complexes have been synthesized and characterized, namely [(CoL 2) 2Cu(pbaOH)](ClO 4) 2, where pbaOH denotes 2 hydroxy 1,3 propylenebis(oxamato) and L stands for 1,10 phenanthroline(p...Four new heterotrinuclear complexes have been synthesized and characterized, namely [(CoL 2) 2Cu(pbaOH)](ClO 4) 2, where pbaOH denotes 2 hydroxy 1,3 propylenebis(oxamato) and L stands for 1,10 phenanthroline(phen), 5 nitro 1,10 phenanthroline(NO 2 phen), 2,2 bipyridyl(bpy) and 4,4 dimethyl 2,2 bipyridyl(Me 2bpy). The temperature dependence of the magnetic susceptibility of [(Cophen 2) 2Cu(pbaOH)](ClO 4) 2·H 2O has been studied in the range of 4—300 K, the plot of χ M T vs. T exhibits a minimum at about 120 K, but abnormal magnetic behavior below 78 K.展开更多
基金Supported by the 973 Program (2007CB815301 and 2006CB932904)the National Natural Science Foundation of China (20333070, 20871114 and 20673118)+1 种基金the Science Foundation of CAS (KJCX2-YW-M05)Fujian Province (2006F3132 and 2007J0171)
文摘Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.
文摘Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.
文摘The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.
基金supported by the National Natural Science Foundation of China(No.21271052 and 21905062)the Science and Technology Program Foundation of Guangdong Province(No.2015A030313502).
文摘An azo-based ligand of azotetrazolyl-2,7-dihydroxynaphthalene(H3ATD)was used to synthesize three unprecedented Fe^(Ⅲ)-M^(Ⅱ)-Fe^(Ⅲ)(M=Fe,Cd)linear trinuclear complexes with different high temperature spin crossover(SCO)behaviours for the terminal Fe^(Ⅲ)ions.
基金supported by a Grant-in-Aid for Scientific Research on Innovative Areas(“Coordination Programming”Area 2107,no.21108006)the Ministry of Education,Culture,Sports,Science and Technology,Japan,and by a Grant-in-Aid for Scientific Research(no.25248014)from the Japan Society for the Promotion of Science(JSPS).
文摘Two trinuclear complexes,[Cu^(II)_(3)(L)_(2)](BF_(4))_(2)(1)and[Ni~(II)_(3)(L)_(2)(MeOH)_(4)](BF_(4))_(2)(2),supported by the multidentate ligand L^(2-)(H_(2)L=5,5’-pyridyl-3,3’-bi-1H-pyrazole)were obtained and their structures determined.Both complexes have linear trinuclear structures composed of two ligands and three metal ions.Cryomagnetic studies reveal that both complexes show intramolecular antiferromagnetic interactions between the metal ions.
基金supported by the National Natural Science Foundation of China(NSFC,21971124 and 22035003).
文摘Spin-crossover(SCO)complexes have been extensively studied in the past few decades owing to their bistable nature which find application in a myriad of areas.In order to enhance and optimize the SCO behavior,considerable attention is being paid towards the synthesis of discrete multinuclear spin-crossover complex systems.Here,two mixed-valence Fe_(2)^(Ⅲ)Fe^(Ⅱ)trinuclear complexes of the formula{[Fe^(Ⅱ)(TPMA)][Fe^(Ⅲ)(TpR)(CN)_(3)]_(2)}·MeOH·2H_(2)O(1)and{[Fe^(Ⅱ)(TPMA)][Fe^(Ⅲ)(TpR)(CN)_(3)]_(2)}·H_(2)O(2)[where TPMA=tris(2-pyridylmethyl)amine,Tp=tris(pyrazol-1-yl)borate,R=3,5-dimethyl for 1 and H for 2]were synthesized and characterized.Magnetic measurements confirmed that complex 1 undergoes SCO at a high temperature(T_(1/2)=410 K for the fresh sample and T_(1/2)=406 K for the dried sample),while complex 2 displays near room temperature SCO(T_(1/2)=283 K for the fresh sample and T_(1/2)(↑)=283 K and T_(1/2)(↓)=257 K for the dried sample).To the best of our knowledge,complex 1 has the highest transition temperature reported among trinuclear SCO complexes so far,which is a remarkable feature of multinuclear materials.Slight structural modifications tend to upend the SCO behavior which paves the way for fine tuning SCO.
基金financially supported by the Russian Science Foundation(project no.19-73-20262).
文摘3-Trifluoromethyl-pyrazoles containing strong fluorophore groups:triphenylamine(TPAPz)and carbazole(CarbPz),and their trinuclear silver(Ⅰ)complexes are found to be emissive in solution and the solid state,giving the first example of silver pyrazolate adducts emissive in solution at room temperature.The electronic coupling was observed for pyrazole with a structurally flexible triphenylamine substituent,determining the intraligand charge-transfer(ILCT)nature of the excited states.The association-dissociation of the trinuclear complex core with the heavy atom effect leads to the intense phosphorescence of the triphenylamine-containing complex.The structural rigidity of the N-ethyl carbazole substituent allows only twisting via the bond to the pyrazolate core leading to typical carbazole-centered(LC)fluorescence in solution.In the solid-state,aggregation plays the primary role in emission properties.The observed behavior is in good agreement with the theoretical calculations.
基金supported by the National Natural Science Foundation of China(22478005,22578006 and 22271002)the Natural Science Foundation of Anhui Province(2308085J14)the Scientific Research Foundation of the Higher Education Institutions of Anhui Province(2022AH051142).
文摘A novel double-stranded trinuclear bis(tridipyrrin)zinc(Ⅱ)complex,constructed from a linearπ-conjugated tridipyrrin ligand,was synthesized and characterized.The complex featuring six directly linked dipyrrin units exhibits a stable double-helical structure with two non-superimposable P and M enantiomers,as confirmed by X-ray crystallography.Chirality was further demonstrated through HPLC separation and mirror-image circular dichroism(CD)spectra.The complex shows strong near-infrared(NIR)absorption and excellent solubility in various solvents,attributed to its sterically hindered structure.Spectroscopic,electrochemical,and theoretical studies revealed its unique electronic properties and redox behavior.This work advances the design of chiral NIR-active metallo-supramolecular systems and highlights potential applications in chiroptical mateials.
基金Guo-Hong Ning is thankful for the support from the Guangdong Basic and Applied Basic Research Foundation (2019B151502024)the Guangzhou Science and Technology Project (202201020038)+1 种基金supported by the National Natural Science Foundation of China (22371091, 21975104, 22150004, 22101099)the Guangdong Major Project of Basic and Applied Research (2019B030302009)。
文摘Development of transition metal-based photocatalysts with low cost, strong visible light absorption, and high efficiency is a longstand pursuit for advanced organic synthesis, yet remains highly challenging. In this article, an anthraquinone-based copper(I)cyclic trinuclear complex(1) was designed and it featured strong visible light absorption, high charge separation efficiency and photochemical properties. Complex 1 as a heterogeneous photocatalyst can efficiently catalyze homo-coupling of terminal alkynes and denitrification-oxidative coupling reaction between hydrazinopyridine and terminal alkynes with excellent yield(up to 99%), broad substrate tolerance(27 examples) and superior reusability(up to 10 cycles without loss of performance) under mild conditions.
基金Project supported by the National Natural Science Foundation or China.
文摘Six novel μ-oxamido trinuclear complexes, namely Cu_2(oxap)_2Ln(ClO_4)_3 (Ln: La, Pr, Nd, Gd, Yb, Ho), where oxap is N,N'-bis(2-aminopropyl)oxamido, have been synthesized. The complex Cu_2(oxap)_2Gd(ClO_4)_3 was characterized with variable temperature magnetic susceptibility (4-300 K). The exchange integrals J (Cu-Gd) and J'(Cu-Cu) were found to be 0.83 cm^(-1) and -1.62 cm^(-1), indi- cating that very weakly ferromagnetic spin-exchange interaction operates between Cu(II) and Gd (III) ions.
文摘A Schiff base ligand（H2CSF,C13H11NO4,1） derived from 3-carboxylsalicylaldehyde and furfurylamine,and its trinuclear complex [Ni3（CSF）2（CH3COO）2（DMF）2（H2O）2]（2） were synthesized.Compound 1 was characterized by elemental analysis,1H NMR,IR,MS and X-ray diffraction analysis.The crystal of 1 belongs to the monoclinic system,space group P21/c with a = 8.472（2）,b = 19.743（5）,c = 7.2300（18） ,β = 110.278（4）°,V = 1134.4（5） 3,Z = 4,Mr = 245.23,Dc = 1.436 g·cm-3,μ = 0.108 mm-1,F（000） = 512,λ = 0.71073 ,the final R = 0.0440 and wR = 0.1199 for 1426 observed reflections（I 2σ（I））.In the crystal of 1,there exist intramolecular hydrogen bonds and weak intermolecular C-H···O hydrogen bonds.Compound 2 was characterized by elemental analysis,IR,TG and X-ray diffraction analysis.The crystal of 2 is of triclinic system,space group P1 with a = 10.1237（17）,b = 10.4086（18）,c = 10.4884（18） ,α = 82.528（2）,β = 67.339（2）,γ = 83.010（2）°,V = 1008.1（3） 3,Z = 1,Mr = 962.87,Dc = 1.586 g·cm-3,μ = 1.463 mm-1,F（000） = 498,λ = 0.71073 ,the final R = 0.0517 and wR = 0.0805 for 2065 observed reflections（I 2σ（I））.The geometry of the trinuclear molecule is centrosymmetric,in which every Ni（Ⅱ） ion is coordinated in a slightly distorted octahedron.The three Ni（Ⅱ） ions are arranged in a straight line.The two CSF2-ions act as NOO tridentate ligands with the phenolate and carboxylate oxygen as bridging atoms.The coordination atoms of CSF2-anions and water molecules are coordinated on the equatorial plane,while the two bridging acetate ions and two DMF are trans-coordinated on the apical sites.
基金Supported by the Natural Science Foundation of Hunan Province (No. 11JJ9006)Science and Technology Committee of Hengyang (2011kj25)
文摘A three-dimensional framework copper（Ⅱ） coordination polymer with copper carbonate basic and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） has been hydrothemally synthesized.The complex （2,C14 H10 CuN8 ·3H2 O） crystallizes in tetragonal,space group P4 2 /n,a=2.08581（12）,b=2.08581（12）,c=0.72331（4） nm,M r=761.73,V=3.1468（3） nm 3,Dc=1.608 g/cm 3,Z=4,F（000）=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.
基金Supported by the Foundation of Fujian Educational Committee, China (No. JB10007 and JB10004)
文摘A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P2 1/c with a = 7.706（7）, b = 14.882（6）, c = 18.639（6） A, β = 108.08（2）°, V= 2032（1） A3, Dc = 1.525 g/cm3, Mr = 932.95, Z= 2, F（000） = 972,μ = 1.442 mm-1, the final R = 0.0359 and wR = 0.0771. The three nickel（II） atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3＋/Ni2＋ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.
基金Supported by the National Natural Science Foundation of China(Nos.20371028and20671052).
文摘Two multidentate ligands 2,9-di[6＇-（2″-hydroxyl-3″-methoxyphenyl）-n-2＇,5＇-diazahexyl]-1,10-phenanthroline（LA）and 2,9-di（6＇-α-phenol-n-2＇,5＇-diazahexyl）-1,10-phenanthroline（LB）were synthesized and fully characterized.Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated.The trinuclear metal complexes [Cu（Ⅱ）and Zn（Ⅱ）] of the ligands were studied,as catalysts,for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate（HPNP）.The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained,which indicated that Zn3LBH-1 was the most efficient catalyst among them.The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.
文摘Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.
文摘The crystal of the title complex with formula C48H52N8O16CI2Cd3(Mr=1405. 10) was crystallized in monoclinic, space group P21/n, with a=12. 666 (3), b=18. 306(6), c=13. 231 (4) A, p=111. 68(3), V=2851 (2) A3, Z=2, Dr=1. 637 g/cm-3 p=12. 680 cm-1, F(000)=1404. The final refinement is convergedwith R=0. 052 and Rw=0. 055. In the molecule [Cd3(py8(Oac)4] (CIO4)2, the aver-age values of Cd-N and Cd-O bonds are 2. 306 and 2. 288 A, respectively. In thecanon of the title complex. each Cd atom is coordinated by N and O atoms, which arefrom pyridine molecules and acetatoes, respectively, to form a distorted octahedron.And three Cd atoms are linked by two u2-O atoms of two acetatoes and other two u-ac-etato side bridges.
文摘Theories based on the isotropic Heisenberg model have been adjusted to the study of magnetic properties in exchange coupled unsymmetrical trinuclear complexes.Program for theoretical fitting of the variable-temperature magnetic susceptibility has been set up to produce coupling constants and spin states of the magnetic centers.Calculation has been carried out on a series of Co(Ⅱ)complexes containing mixed thiolato and phosphine ligands:Co3(mp)2(mpH)2(PR3)3(R=Et,R=Bu) and Co3(bdt)3 (PBu3)3.It has been found that all these studied complexes are anti-ferromagnetically coupled.Coupling constant shows the strength of the exchange interaction,which is determined by many factors.Relation between the spin state and the coordination circumstance of Co(Ⅱ) was discussed too.
文摘Four new heterotrinuclear complexes have been synthesized and characterized, namely [(CoL 2) 2Cu(pbaOH)](ClO 4) 2, where pbaOH denotes 2 hydroxy 1,3 propylenebis(oxamato) and L stands for 1,10 phenanthroline(phen), 5 nitro 1,10 phenanthroline(NO 2 phen), 2,2 bipyridyl(bpy) and 4,4 dimethyl 2,2 bipyridyl(Me 2bpy). The temperature dependence of the magnetic susceptibility of [(Cophen 2) 2Cu(pbaOH)](ClO 4) 2·H 2O has been studied in the range of 4—300 K, the plot of χ M T vs. T exhibits a minimum at about 120 K, but abnormal magnetic behavior below 78 K.
