A New Acentric Heterometallic Inorganic-organic Hybrid Framework [ZnK_2(m-BDC)_2(H_2O)_2]n: Fluorescent, NLO and Ferroelectric Properties

Solvothermal reactions of Zn（NO3）2·6H20 with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional （3D） hereto-metallic inorganic-organic hybrid framework [ZnK2（m-BDC）ffH20）2]n （1, m-H2BDC = benzene-l,3-dicarboxylic acid）. The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc2j with a = 19.764（6）, b = 19.948（6）, c = 12.039（4） A, V = 4746（3） A3, Z = 4, C32H20019KaZn2, Mr = 995.66, Dc= 1.393 g/cm3, F（000） = 2000 andp = 1.426 mm-1. The final R = 0.0761 and wR = 0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate （KDP） powder. In addition, it also exhibits potential ferroelectric property.

Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

Synthesis and Crystal Structure of a Novel Heterometallic Complex with 1,2,4,5-Benzenetetracarboxylic Acid and 1,3,5-Tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene

A novel heterometallic complex,[Zn4Ni（OH）2（btec）2（titb）2（H2O）2]·2H2O（1）（H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris（imidazol-1-ylmethyl）-2,4,6-trime-thylbenzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817（10）,b=11.878（11）,c=14.569（14）,α=71.762（12）,β=76.122（13）,γ=71.493（13）°,V=1665（3）3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F（000）=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections（Ⅰ 2σ（Ⅰ））.In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.

Hydrothermal Synthesis and Crystal Structure of a Heterometallic Cu/Cd Complex with H_2dipic(Pyridine-2,6-dicarboxylic Acid)

A new heterometallic complex {[Cu（pic）2（H2O）2][Cd2（Hdipic）2（H2O）2Cl2]}n （Mr = 1007.73） has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group PI^- with a = 5.8397（4）, b = 9.8664（7）, c = 14.1739（10） °A, α= 82.0150（10）, β = 80.4540（10）, γ= 82.3570（10）°, Z= 1, V= 792.47（10）°A^3, Dc = 2.112 g/cm^3,μ（MoKα） = 2.247 mm^-1, F（000） = 495, the final R = 0.0232 and wR = 0.0644 for 2748 observed reflections （I〉 2σ（I））. In the complex, seven-coordinated·Cd ions form a zigzag chain based on the alternated dinuclear Cd units. The neutral [Cu（pic）2（H2O）2] units are located at the centers of the inter space and fasten to the 1-D chain by hydrogen bonds.

A Heterometallic Cu(Ⅰ)-Sr(Ⅱ) Coordination Polymer Based on Isonicotinic Acid Ligand: Synthesis, Crystal Structure, Luminescence and Photocatalytic Performance for Methylene Blue Degradation

Presented here is a new heterometallic Cu(I)-Sr(Ⅱ) coordination polymer, [Cu(3)Sr_2(isonic)_5 Br_2(H_2O)_3]n·n(H_2O)(1, Hisonic = isonicotinic acid), has been synthesized via the hydrothermal reactions of CuBr, Sr(NO_3)_2 and isonicotinic acid. The crystal structure is of triclinic system, space group P1 with a = 7.111(2), b = 14.934(4), c = 18.0255(11) ?, α = 83.137(15), β = 87.155(15), γ = 79.75(2)°, V = 1869.4(8) ?~3, C_(30)H_(29)Br_2Cu(3)N_5O_(14)Sr_2, Mr = 1209.27, Z = 2, Dc = 2.148 g/cm^3, F(000) = 1178, μ = 6.725 mm^(-1), R = 0.0500 and wR = 0.1008 for 4688 observed reflections(I > 2s(I)). Single-crystal X-ray diffraction analysis revealed that compound 1 features a 3 D heterometallic framework stabilized by bifunctional isonic ligands. In addition, the luminescent and photocatalytic properties of compound 1 were also investigated at room temperature.

Three Two-dimensional Heterometallic Chalcogenides[TM(tren)][InSbSe_3S](TM = Fe, Co, Mn): Syntheses,Crystal Structures, and Properties

Three two-dimensional(2-D) heterometallic chalcogenides [TM(tren)][InSbSe_3S](TM = Fe(1), Co(2), Mn(3); tren = tris(2-aminoethyl)-amine) have been solvothermally synthesized in this paper. Single-crystal X-ray analysis indicates that they are isostructural to each other except the different transition metal ions. These compounds contain an unsaturated complex cation [TM(tren)]^(2+), which can be further coordinated by the 2-D [InSbSSe_3]_n^(2n-) anion, resulting in a new neutral organic-decorated heterometallic chalcogenide. These compounds crystallize in monoclinic space group P21/c, with a = 11.768(12), b = 13.884(14), c = 11.095(11) ?, Z = 4, D_c =2.910 Mg·m^(-3), F(000) = 1304, M_r = 707.60 for 1; a = 11.843(9), b = 14.064(10), c = 10.979(8) ?, Z= 4, Dc = 2.875 Mg·m^(-3), F(000) = 1308, M_r = 710.68 for 2; a = 11.969(10), b = 14.191(11), c =11.112(9) ?, Z = 4, D_c = 2.779 Mg·m^(-3), F(000) = 1300, Mr = 706.69 for 3. The maximum and minimum peaks of compounds 1～3 are 6.996 and –2.880 e·?^(-3), 2.242 and –3.066 e·?^(-3), 3.655 and –3.569 e·?^(-3), respectively. These compounds were structurally characterized by powder X-ray diffraction measurement, thermal analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy. A solid-state UV/Vis reflectance spectroscopy measurement on 1, 2 and 3 confirmed that these compounds are semiconductor materials.

Synthesis and Crystal Structure of a Heterometallic Trinuclear Ni/Ag/S Compound

A new tri-nuclear mixed metal thiolate complex [Ag（PPh3）2]2[Ni（edtO2）2] 1 has been synthesized and structurally characterized by single-crystal diffraction.The molecule has a crystallographic inversion centre occupied in the central Ni（II） atom and the two silver（I） atoms are related by the inversion centre.The unique structural feature is that one of thiolates of each edt ligand has been oxidized to sulfinate from the precursor [Ni（edt）2]2-to the neutral linear trinuclear complex.The crystal structure belongs to the monoclinic system,space group P21/n with a = 13.581（11）,b = 12.239（9）,c = 22.316（17） ,β = 103.08（2）o,V = 3613（5） 3,Z = 2,Mr = 1571.87,Dc = 1.445 g/cm3,μ = 1.046 mm-1,F（000） = 1604,T = 293（2） K,the final R = 0.0652 and wR = 0.1499 for 6776 observed reflections with I 2σ（I）.

Synthesis and Characterization of a Silver(Ⅰ)-indium(Ⅲ) Heterometallic Metalorganic Framework Based on Nicotinate

A heterometallic metal-organic framework, Agln（nicotinate）4.1.5DMF, was obtained from the reaction of nicotinic acid, AgNO3 and In（NO3）3 in DMF. The complex was characterized by elemental analysis, infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are： C28.5H26.5N55O9.5Agln, orthorhombic space group/222, a = 10.775（15）, b = 11.939（18）, c = 13.93（2） A, V= 1792（5） A3, Z = 2, Dc = 1.521 mg/m3,μ = 1.244 mm1, F（000） = 816, the final R = 0.0672 and wR= 0.1812 for 1912 observed reflections with I 〉 2σ（I）. Single-crystal X-ray structure analysis reveals that nicotinate bridges In（III） and Ag（I） through carboxylate chelating with In（III） and pyridyl nitrogen atom coordinating to Ag（I）, generating a new 2D network consisting of tetrahedral building units of [AgN4]＋ and [In（COO）4]-.

Synthesis and Characterization of a Tetranuclear [Sm_2Co_2] Heterometallic Compound

A new tetranuclear square compound （H3O）[Sm2Co2（CDTA）2（DMF）2 （μ4-O） （H2O）6]ClO4 was synthesized through the assembly reaction of Co2＋ , Sm3＋ and trans-1,2-cclohexylenedinitrilotetraacetic acid （H4CDTA） in aqueous solution. X-ray crystal structural analysis shows that the compound belongs to the monoclinic C2/c space group, with a=27.213（2）, b=10.5574（9）, c=19.4923（17）,β=98.799（1）°, V=5534.1（8）3 , C34H65ClCo2N6O30Sm2 , Mr=1491.93, Dc=1.791g/cm-3 , F（000）=2984,=2.820 mm-1 and Z=4. In the compound, Co2＋ is 7-coordianted while Sm3＋ is 9-coordinated. With the help of a central O2- and 8 carboxylate oxygen atoms, two Co2＋ and two Sm3＋ ions are linked into a square with the side length of 3.45 . Magnetic property was investigated.

Syntheses and Crystal Structures of Five Sr^(Ⅱ)-Ln^(Ⅲ)(Ln=Nd,Pr,Er) Heterometallic Coordination Polymers

Five novel SrⅡ-LnⅢ heterometallic coordination polymers based on pyridine-2,6- dicarboxylic acid （H2pda） and imidazole （im）, namely, [LnSr（pda）3（H2O）5]-Him·C2H5OH·3H2O （Ln = Nd （1）; Pr （2））, [Ln2Sr（pda）6（H2O）5]-4Him·C2H5OH·5H2O （Ln = Nd （3）; Pr （4））, and [ErSr（pda）3（H2O）4].Him-3.5H2O （5）, have been prepared and structurally characterized. X-ray crystallographic analyses revealed that these complexes display three varieties of l-D chain structures. Several types of hydrogen bonding interactions are found for 1-5, which connect the 1 -D chain structures to form 2-D suoramolecular networks.

A Copper(Ⅱ)-cadmium(Ⅱ) Heterometallic Hexanuclear Complex:[Cd_4Cu_2(pdc)_4(H_2O)_(14)](H_3pdc=3,5-Pyrazoledicarboxylic Acid)

The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.

Synthesis and Crystal Structure of a New Pr(Ⅲ)–K(Ⅰ) Heterometallic Oxalate Coordination Polymer

A new 3D heterometallic coordination polymer, namely [K2Pr2（C2O4）4·H2O]n（1）, has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a = 12.060（4）, b = 8.493（3）, c = 15.776（5）（A）, β = 93.235（3）°, V = 1613.4（9） A3, Z = 4, Mr = 730.12, Dc = 3.006 Mg/m^3, μ = 6.581 mm-1, F（000） = 1368, the final R = 0.0283 and wR = 0.0866 for 2939 observed reflections with I 〉 2σ（I）. Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.

Heterometallic Mg-Ni-Mg Complex Promoted Hydrosilylation of Alkenes: Catalytic Performance and Intermediates Characterization

Background and Originality Content The catalytic hydrosilylation of unsaturated hydrocarbons,facilitated by transition metal(TM),is widely recognized as a proficient technique for the synthesis of high-value organosilicon compounds'ti-4l over the past few decades,the most dominant cata.lysts in hydrosilylation processes have been constituted by pre-Ccious metar complexesroceinerecent vears omore sustainabile earth-abundant metal catalysts have received increased attentionj2-14l The classcal mechanism of transition metal-catalyzed hydrosilylation is generally accomplished through a series of fundamental processes(Scheme 1a),including(i)coordination and oxidative addition of Si-H bond to a low-valent metal center to form e.g.,o-complex or silyl metal hydride;(ii)insertion of.C-C multipe bonds intometal-hdridelsior metal-silicon bond;jiol and(ii)reductive elimination that forwards the hydrosilylated product with Markovnikov or anti-Markovnikov selectivity.

Heterometallic Ti-Zr oxo nanocluster photoresists for advanced lithography

Extreme ultraviolet lithography(EUVL)and electron beam lithography(EBL)are considered to be crucial lithography techniques utilized in the fabrication of nanoscale semiconductor devices.However,the industry currently faces a scarcity of EUV photoresists that meet the increasingly challenging standards in terms of resolution,sensitivity and roughness.Metal oxo nanoclusters have garnered significant interest in the field of EUV photoresist due to their relatively stronger absorption cross-section for extreme ultraviolet light and lower dimensions.In this study,we utilize a heterometallic nanocluster strategy by a combination of titanium and zirconium metals to investigate their solubility,assess the suitability of various developers,and evaluate their performance in electron-beam and EUVL,as well as study their etch resistance for pattern transfer.We demonstrate that R-4 is able to get a critical dimension(CD)of 25 nm at low doses under EBL,as well as 50 nm resolution at EUVL with a remarkable sensitivity of 19.7 mJ cm−2.This study offers an efficient heterometallic method for optimizing the lithographic performance of metal oxo nanocluster photoresists,which can benefit the development of commercially viable next-generation EUV photoresists.

Parallelogram 3d-4f-5d heterometallic clusters based on trilacunary tungstoantimonates with excellent proton conductivity

Two 3d-4f-5d heterometallic cluster-containing polyoxometalates,formulated as Na_(22){(SbW_(9)O_(33))_(4)[La_(3)W_(6)MO_(18)(H_(2)O)_(8)(CH_(3)COO)_(4)]_(2)}·nH_(2)O(abbreviated as La_(6)M_(2),M=Co/Mn)were synthesized and structurally characterized.Single-crystal X-ray diffraction analyses reveal that the polyanions of La_(6)Co_(2)and La_(6)Mn_(2)consist of the uncommon 3d-4f-5d clusters{La_(6)W_(12)Co_(2)}and{La_(6)W_(12)Mn_(2)},which are encapsulated by four trilacunary Keggin tungstoantimonates to form the parallelogram-shaped title compounds.Additionally,the polyanions can be extended into a two-dimensional(2D)frame by the linkage of peripheral Na+ions.The inner space of the 2D layer was filled with water molecules and thus an H-bonded network was formed,which is expected to exhibit a fascinating proton conductivity.The study of water-assisted proton conduction demonstrated that La_(6)Co_(2)and La_(6)Mn_(2)were temperature-and humiditydependent proton conductors,respectively,and the proton conductivities could reach 1.3×10^(-2)and 2.3×10^(-2)S/cm at 65℃and 90%RH conditions.

Synthesis,characterization,properties and crystal structure of heterometallic 1D coordination polymers {[CuLZn·CuLZn(H_2O)]·H_2O}_n

Copper-zinc heterometallic 1D chain coordination polymer has been synthesized and characterized by elemental analysis, and IR spectra etc. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is 1D chain coordination polymer with the chemical formula {[CuLZn·CuLZn(H2O)]·H2O}n, where H4L=N-(2-hydroxybenzamido)-N’-(3-carboxy- lsalicylidene)ethylenediamine. Its structural unit is comprosed of two tetranuclear cycles formed by two dissymmetrical tetranuclear units. These units polymerized each other to form 1D chain coordi- nation polymer.

Fe_(2)Mn(μ_(3)-O)(COO)_(6) Cluster Based Stable MOF for Oxidative Coupling of Amines via Heterometallic Synergy

The direct catalytic oxidative coupling of amines is one of the attracting methods for the synthesis of a variety of pharmaceutical or industrial needed imines.Numerous earth-abundant manganese based salts,oxides,and complexes have been applied in this reaction.However,these compounds suffered from difficult separation,large catalyst loading,complicated reactivation or indeterminate activity.Considering the facts that metal-organic frameworks(MOFs)with crystalline structure,precise composition,and enormous surface area have superior performance in heterogeneous catalytic reactions,herein,we introduced Mn into[Fe_(3)(μ_(3)-O)(CH_(3)COO)_(6)],one of the precursors for the preparation of stable MOFs,and got[Fe_(2)Mn(μ_(3)-O)(CH_(3)COO)_(6)]cluster.After ligand replacement with biphenyl-3,4’,5-tricarboxylic acid(BPTC),heterometallic cluster-based[Fe_(2)Mn(μ_(3)-O)(BPTC)2(DMF)2(H_(2)O)](1)was obtained.As expected,1 is stable and able to catalyze the homo-or cross-coupling of amines effectively and selectively with 0.9 mol%catalyst loading at room temperature.Control experiments indicated that the catalytic activity of 1 mainly stems from Mn sites and that Fe synergistically contributes to the stability.Additionally,1 is recyclable and can be reused easily for at least 8 runs without obvious decrease in catalytic ability.To our knowledge,1 should be the first heterometallic cluster-based MOF with defined structure suitable for the synthesis of diverse imines from oxidative coupling of amines under mild conditions,which may shed light on the easy preparation of effective heterogeneous catalysts for organic synthesis.

Synthesis and Structural Determination of a Novel Heterometallic Complex [Sb2（edta）2-μ4- Co（H2O）2]·5.15H2O

The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.

Control of Heterometallic Three-Dimensional Macrocycles with Aromatic Stacks in Tunable Host Cavities

Using coinage metal （Cu（Ⅱ）, Ag（Ⅰ）） hinges, two sets of heterometallic molecular capsules with analogous open-ended cavities were prepared based on the half-sandwich rhodium fragments. In the case of [Rh4Cu4] cages, up to six-fold-stacked host-guest structures were formed by varying the cavity＇s dimensions. Moreover, the series of capsules were demonstrated to self-fine-tune to form multi-heteroguest arrays via favourable donor-acceptor interactions and Ag-π interactions, as evidenced from single-crystal X-ray analysis.

Sm（Ⅲ）-Bi（Ⅲ） Heterometallic Complexes with Aminopolycarboxylate Ligand： Structure, Thermal Stability and Spectral Property

Samnium（Ⅲ）-bismuth（Ⅲ） heterobimetallic complexes, SmBi（edta）（NO3）2·7H2O （1） and SmBi（dtpa）（NO3）·3.5H2O（2） （edta=ethylenediaminetetraacetate, dtpa=diethylenetriaminepentaacetate）, were synthesized and characterized by means of X-ray single crystal diffraction, X-ray powder diffraction, elemental analysis, ICP, FT-IR spectra and thermal analysis. The structure analysis revealed that 1 is in crystalline and 2 is in non-crystal state. Complex 1 crystallizes in monoclinic, space group P2（1）/n with a= 1.2622（2） nm, b=0.81157（15） nm, c=2.3634（5） nm, β= 105.340（2）°, V=2.3347（8） nm3, Z=4, Dc=2.563 gocm^-3,μ=10.125 mm-1. Bridging edta4 anions between Bi（Ⅲ） atoms and Sm（Ⅲ） atoms result into infinite 3D network structure. Thermal decomposition of the two complexes proceeds in similar stages, i.e., dehydration, pyrolysis of ligand, and decomposition of salt, and the final residue is oxide. In addition, the spectral properties have been studied through FL spectra and UV-Vis DRS. The two complexes exhibit one broad band Bi 6s6p-6s2 emission under UV excitation and the characteristic Sm3＋ ion 4G5/2→6Hj/2 （J= 5, 7, 9, 11） transitions under visible light excitation, respectively.