Synthesis,Crystal Structure,and Characterization of a Novel Metallo‐Organically‐Templated Pentaborate with Mixed Ligands

A novel metallo‐organically templated pentaborate with layered framework, [Cd(TETA)(C₂H₃O₂)][B₅O₆(OH)₄] ( 1 ) (TETA = triethylenetramine), was synthesized under mild solvothermal conditions. The structure was determined by single‐crystal X‐ray diffraction and further characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, and photoluminescence spectroscopy. The structure consists of an isolated polyborate anion [B₅O₆(OH)₄]^– and the cadmium complex cation of [Cd(TETA)(C₂H₃O₂)]⁺, which contains both organic amine and organic acid ligands. The [B₅O₆(OH)₄]^– units are connected together by hydrogen bonds, and a 2D sheet‐like framework with rectangle‐like 12‐membered boron rings are formed. The [Cd(TETA)(C₂H₃O₂)]⁺ complex cations are located in the free space between the layers and connect the adjacent borate layers through hydrogen bonds to form a three‐dimensional supramolecular network. The luminescent properties of the compound were studied for the first time in the series of metallo‐organically‐templated pentaborates, and a blue luminescence occurs with an emission maximum at 468 nm upon excitation at 397 nm.     

Two New Piperazine Templated Lanthanide Sulfates with 2D Corrugated Layered Crystal Structures

Two new piperazine templated lanthanide sulfates (C₄N₂H₁₂)_1.5[Ln(SO₄)₃(H₂O)]·H₂O[Ln=Gd(1), Tb(2)] have been synthesized solvothermally and structurally characterized by single crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Single crystal X-ray diffraction reveals that both compounds 1 and 2 crystallized in the monoclinic crystal system, with space group P2₁/c and cell dimensions: a=0.64468(19) nm, b=2.9979(9) nm, c=0.9818(3) nm, β=101.271(4)°, V=1.8608(10) nm³, Z=4 for compound 1; a=0.64259(19) nm, b=3.0010(9) nm, c=0.9812(3) nm, β=101.229(4)°, V=1.8560(10) nm³, Z=4 for compound 2. Compounds 1 and 2 are isomorphous and have similar 2D corrugated inorganic frameworks fabricated via the connection of single chains and S2O₄ groups, while fully protonated piperazine cations and water molecules are located between the inorganic layers. The solid state luminescent properties of compound 2 were investigated and it displayed a typical luminescent property of Tb³⁺ with excitation wavelength at 371 nm.     

以二亚乙基三胺为模板的链状结构硫酸钬配合物的合成、晶体结构及性质

通过溶剂热技术合成了一种以二亚乙基三胺(dien)为模板的链状结构硫酸钬(H₃dien)[Ho(SO₄)₃(H₂O)₂] (1),并通过X射线分析、红外光谱、元素分析和粉末衍射进行了表征。X射线晶体结构分析,化合物1结晶于单斜晶系,P2₁/c空间群,a=0.660 20(13) nm,b=1.476 7(3) nm,c=1.655 6(3)nm,β=93.313(2)°,V=1.611 4(5) nm³,Z=4。化合物1是由HoO₈多面体和SO₄四面体为建筑单元构建成新颖的单一链状结构。在a轴方向上,配位水分子通过氢键连接相邻的链形成三维超分子结构。有机胺分子镶嵌于链间,在合成化合物1合成过程中,pH值(pH=1.5)起了关键作用。     

Syntheses and Crystal Structures of Three Organically Templated Gallium Phosphates

Three open‐framework gallium phosphates [C₆H₁₆N₂][Ga(HPO₄)(PO₄)] ( 1 ), {H[C₆H₁₆N₂]₂[Ga₇(OH)₂(PO₄)₈]} ( 2 ), and {H[C₄H₁₂N₂]₂[Ga₇(OH)₂(PO₄)₈] · 2H₂O} ( 3 ) were solvothermally synthesized in the presence of 2,6‐dimethylpyrazine, N‐ethylpiperazine, and piperazine as templates, respectively. Compound 1 possesses an infinite one‐dimensional chain structure connected by hydrogen‐bond interactions to generate a 3D supramolecular framework. Compounds 2 and 3 show similar inorganic framework structures, which may be viewed as the assembly of a secondary building unit (SBU), Ga₆P₈ containing two GaO₄, two GaO₅, two GaO₆ as well as eight PO₄ groups. The SBUs are linked with each other by vertex‐sharing oxygen atoms to form 2D sheets, which are further connected by GaO₄ tetrahedra to result in the final 3D open‐framework with left‐ and right‐handed helical chains. In these materials, the well‐ordered organic species reside in the voids of structures and interact with the framework by way of hydrogen bonds.     

Solvothermal Synthesis, Structural Characterization and Properties of Two New Layered Lanthanide Sulfates

Two new layered lanthanide sulfates,[C₁₀H₁₀N₂][Pr₂(SO₄)₄(H₂O)₂](1)and[H₅O₂][Sm(SO₄)₂(H₂O)₃](2)were synthesized via solvothermal reaction and structurally characterized by single-crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Crystal data for compound 1, triclinic, P space group, a=0.8052(4) nm, b=0.9438(4) nm, c=1.4990(7) nm, α=79.450(5)°, β= 83.703(5)°, γ=74.048(5)°, V=1.0746(9) nm³, Z=2; for compound 2, monoclinic, P2₁/c space group, a=0.6599(11) nm, b=1.8940(3) nm, c=0.8765(14) nm, β=96.596(2)°, V=1.0883(3) nm³, Z=4. Structure analysis indicates that both the compounds exhibit a 2D corrugated layer structure, with protonated 4,4'-bipyridine cations and water dimmers (H₅O₂)⁺ located between the inorganic layers of compounds 1 and 2, respectively. Luminescent properties of compounds 1 and 2 were further investigated.     

Syntheses,Crystal Structures,and Thermal Behaviors of Two New Metallo‐Organically Templated Pentaborates

Two new cadmium borates, [Cd(en)₃][B₅O₆(OH)₄]₂ · 2H₂O (en = ethylenediamine) ( 1 ) and [Cd(DETA)₂][B₅O₆(OH)₄]₂ (DETA = diethylenetriamine) ( 2 ) were synthesized in a novel procedure under mild solvothermal conditions and characterized by single‐crystal X‐ray diffraction, IR spectroscopy, elemental analysis, and TG–DTA. The compound 1 crystallizes in monoclinic system, space group P2₁/c (No. 14) with a = 8.526(2) Å, b = 23.127(6) Å, c = 15.438(4) Å, β = 94.320(3) °, V = 3035.5(13) Å³, Z = 4. Compound 2 is triclinic, space group P$\bar{1}$ (No. 2), a = 8.632(5) Å, b = 9.418(6) Å, c = 27.856(18) Å, α = 95.415(8) °, β = 91.891(7) °, γ = 93.563 (7) °, V = 2248(2) Å³, Z = 3. The anionic units of the both structures, [B₅O₆(OH)₄]^– are linked by hydrogen bonds to form a three‐dimensional framework with large channels, in which the templating cadmium complex cations are located. The thermal decomposition performance of compound 1 requires three steps, whereas only two steps are needed for compound 2 , which all lead to amorphous phases. These processes are well explained considering the structure and the change in the Cd²⁺ coordination during heating.     

Solvothermal Synthesis and Structural Characterization of an Organic‐Templated New Aluminogermanate with the GIS Topology

A new organic‐templated aluminogermanate [C₄H₁₂N][AlGe₃O₈] ( 1 ) has been prepared under solvothermal conditions by using 2‐propanol as solvent. The structure of the title compound was characterized by IR spectroscopic, elemental analysis, TG, single‐crystal X‐ray diffraction and powder X‐ray diffraction. Compound 1 crystallizes in the tetragonal space group I4₁/a, a = b = 10.7754(8) Å, c = 9.9116(14) Å, V = 1150.8(2) Å³, Z = 4. The structure of the title compound shows eight‐membered ring channels along a and b axes with a typical GIS topology, and – most importantly – the structure of the inorganic framework is retained when the organic amine is removed by calcination.     

Organically‐Templated Zinc and Thorium Sulfates with Chain and Layered Structures

Amine‐templated zinc sulfates of the formulae, [Zn(SO₄)(H₂O)₂(C₁₀N₂H₈)] ( I ) and [C₃N₂H₁₂][Zn(SO₄)] ( II ) both with linear structures have been prepared under hydro/solvothermal conditions. Of these, I has the chain structure formed by ZnO₄N₂octahedra and SO₄ tetrahedra, while II comprises ladders formed by corner‐sharing four‐membered rings. Amine‐templated thorium sulfates of the formula [HN(CH₂)₆NH]₂[Th₂(SO₄)₆(H₂O)₂]·2H₂O, ( III ) and [H₂N(CH₂)₄NH₂][Th₃(SO₄)₇(H₂O)₄]·5H₂O ( IV ) are also obtained under hydrothermal conditions. III has a sheet structure consisting of cages whereas IV has a two‐dimensional structure derived from the connectivity of ladders.     

Metal Ion Induced Assembly of Two Coordination Polymers with Different Topological Nets: Syntheses,Crystal Structures,and Luminescent Properties

The coordination polymers [Zn₂(NDA)(HNDA)₂(IPT)₂]_n ( 1 ) and [Mn(NDA)(IPT)]_n ( 2 ) [H₂NDA = naphthalene‐1,4‐dicarboxylic acid and IPT = 4′‐(4‐(1H‐imidazol‐1‐yl)phenyl)‐4,2′:6′,4′′‐terpyridine] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Complex 1 features a one‐dimensional ladder‐like chain, whereas complex 2 shows a three‐dimensional CdS topology. The different coordination modes for organic ligands and topological nets for complexes 1 and 2 are mainly related with the metal ions.     

Syntheses,Characterizations, and Crystal Structures of Two New Organically Templated Borates

Two new organically templated borates, [H₂DAB][B₇O₉(OH)₅]·2H₂O ( 1 ) and [H₂DAB][B₇O₁₀(OH)₃] ( 2 ), have been synthesized under mild conditions in the presence of DAB acting as structure‐directing agent (DAB = 1,4‐diaminobutane). The structures were determined by single crystal X‐ray diffraction and further characterized by FTIR, elemental analysis, and thermogravimetric analysis. Both 1 and 2 crystallize in the same triclinic system, space group (No. 2); 1: a = 8.238(4) Å, b = 8.348 (5) Å, c = 14.574(8) Å, a = 101.050(3)°, β = 92.313(7)°, γ = 112.694(5)°, V = 900.3(8) ų, Z = 2; 2: a = 8.8769(3) Å, b = 9.3204(2) Å, c = 10.2204(5) Å, α = 74.474(2)°, β = 85.292(5)°, γ = 72.730(2)°, V = 778.01(5) ų, Z = 2. The structure of 1 consists of [B₇O₉(OH)₅]^2? groups, which represents the first example of organically templated heptaborate. The structure exhibits interesting hydrogen‐bonded network formed by borate polyanion [B₁₄O₂₀(OH)₆]^4?, which can be regarded as being constructed from the dehydration of the FBBs in 1 . The diprotonated organic amines are filled in the free space of the hydrogen‐bonded network and interact with the inorganic framework by extensive hydrogen bonds.     

Hydrothermal Syntheses,Crystal Structures and Thermal Properties of Two New Organically Templated Open-framework Gallium Phosphites

Two new open-framework gallium phosphites formulated as (C₂N₂H₁₀)_0.5Ga₂(OH)(H₂O)(HPO₃)₃(1) and (C₃N₂H₅)₂(C₃N₂H₆)Ga₈(H₂O)₆(HPO₃)₁₄(2) were hydrothermally synthesized in the presence of ethylenediamine(en) and imidazole as structure directing agents(SDA), respectively. Structural analyses reveal that the 3D structures of compounds 1 and 2 are both built up from the linkage of GaO₆, GaO₅(H₂O) and HPO₃^2? units by sharing vertices. The structure of compound 2 is constructed from well-known 4.6.12-net connecting layers in the AAAA stacking sequence, which are penetrated by the 1D Ga-O-P chains to form a 3D pillared-layered structure.     

Synthesis,Crystal Structures,Optical Properties,and Photocurrent Response of Heteroacene Derivatives

Six 5,9,14,18‐tetrathiaheptacene derivatives ( 1 a – 1 f ) were synthesized by using a simple ether–ether exchange reaction and fully characterized. In contrast to the planar conformation usually observed in thiophene‐fused benzene systems, single‐crystal analysis indicates that 7,16‐dipropyl‐5,9,14,18‐tetrathiaheptacene ( 1 a ), 7,16‐diphenyl‐5,9,14,18‐tetrathiaheptacene ( 1 b ), and 7,16‐di(4′‐chlorophenyl)‐5,9,14,18‐tetrathiaheptacene ( 1 c ) adopt chair conformations. The as‐formed dihedral angle between anthracene and the terminal benzene units are 137.258, 137.855, and 134.912° for 1 a , 1 b , and 1 c , respectively, which is close to the theoretical optimization results (128° for 1 b ). Interestingly, the oxidized product of 7,16‐di(trifluoromethylphenyl)‐5,9,14,18‐tetrathiaheptacene ( 1 e ) has a saddle shape, which results in the formation of column‐shaped units in the single crystal. The substituents on the side phenyl group have less effect on their UV/Vis absorption spectra, but a distinct redshift that accounts for the intramolecular charge transfer can be observed in the emission spectra. The electrochemical measurements show that all compounds present two oxidation waves. The photoswitching behavior based on 1 a–1 f was further measured and the experimental results suggest that these heteroacene derivatives are promising semiconductor materials for organic electronics.     

Synthesis and Crystal Structures of Two Cadmium Coordination Chain Polymers

Hydrothermal reactions of cadmium precursors with 2, 2′‐bipyridine, fumaric acid or NaN₃ in basified aqueous solutions gave rise to two cadmium complexes [Cd(bipy)(fum)(H₂O)]_n ( 1 ), and [Cd(bipy)(μ_{1, 1}‐N₃)₂]_n ( 2 ) (fum = fumarate dianion), which were characterized by X‐ray crystallography. Complex [Cd(bipy)(fum)(H₂O)]_n ( 1 ) crystallizes in the orthorhombic system, space group Pbca, with a = 9.0488(8), b = 16.246(3), c = 19.810(4) Å, and Z = 8 while complex [Cd(bipy)(μ_{1, 1}‐N₃)₂]_n ( 2 ) in the monoclinic system, space group C2/c, with a = 12.378(3), b = 14.788(3), c = 6.6139(13) Å, β = 91.49(3)°, and Z = 4. The photoluminescence spectra for compounds 1 and 2 have also been studied.     

Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties

The use of the [Fe^III(AA)(CN)₄]^? complex anion as metalloligand towards the preformed [Cu^II(valpn)Ln^III]³⁺ or [Ni^II(valpn)Ln^III]³⁺ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H₂valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu^II(valpn)Ln^III(H₂O)₃(μ‐NC)₂Fe^III(phen)(CN)₂ {(μ‐NC)Fe^III(phen)(CN)₃}]NO₃ ? 7 H₂O}_n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃] ? NO₃ ? H₂O ? CH₃CN ( 4 ) were obtained with the [Cu^II(valpn)Ln^III]³⁺ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni^II(valpn)Ln^III(ONO₂)₂(H₂O)(μ‐NC)₃Fe^III(bipy)(CN)] ? 2 H₂O ? 2 CH₃CN}_n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [Ni^II(valpn)Ln^III]³⁺ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃]⁺, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {Fe^III(bipy)(CN)₄} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {Ni^II(valpn)Ln^III} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu^II?Ln^III ( 1 – 3 ) and Ni^II?Ln^III ( 5 – 7 ) units, as well as through the single cyanide bridge between the Fe^III and either Ni^II ( 5 – 7 ) or Cu^II ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τ_o) and energy barrier (E_a) through the Arrhenius equation being 2.0×10^?12 s and 29.1 cm^?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (Ni^II–Dy^III) and single cyanide (Fe^III–Ni^II) pathways are masked by the depopulation of the Stark levels of the Dy^III ion, this feature most likely accounting for the continuous decrease of χ_M T upon cooling observed for this last compound.     

A Robust Microfluidic Device for the Synthesis and Crystal Growth of Organometallic Polymers with Highly Organized Structures

A simple and robust microfluidic device was developed to synthesize organometallic polymers with highly organized structures. The device is compatible with organic solvents. Reactants are loaded into pairs of reservoirs connected by a 15 cm long microchannel prefilled with solvents, thus allowing long‐term counter diffusion for self‐assembly of organometallic polymers. The process can be monitored, and the resulting crystalline polymers are harvested without damage. The device was used to synthesize three insoluble silver acetylides as single crystals of X‐ray diffraction quality. Importantly, for the first time, the single‐crystal structure of silver phenylacetylide was determined. The reported approach may have wide applications, such as crystallization of membrane proteins, synthesis and crystal growth of organic, inorganic, and polymeric coordination compounds, whose single crystals cannot be obtained using traditional methods.     

Solvothermal Synthesis,Crystal Structure,and Properties of a New Organic‐Templated Holmium Sulfate with 1D Single Ladder Chains

A new organic amine templated 1D holmium sulfate (C₂H₈N)[Ho(SO₄)₂ · H₂O] ( 1 ) has been synthesized and solvothermally and structurally characterized by single‐crystal X‐ray diffraction, IR spectroscopy, thermogravimetric and X‐ray diffraction analyses as well as scanning electron microscopy (SEM). The structure of framework 1 is constructed from HoO₈ polyhedra and SO₄ tetrahedra. S(1) and S(2) connects Ho(1) and its crystallographic partners by using three S–O–Ho linkages to generate double chains, whereas the adjacent double chain are connected by μ₃‐O (O₅) atoms to form a novel single ladder chains.     

Solvothermal Synthesis,Crystal Structure and Properties of a 3D Organically Amine Templated Lanthanide Sulfate

A new sulfate inorganic framework, {(C2H8N)9[Nd5(SO4)12]·2H2O}n(1) templated by organic amine, has been solvothermally synthesized and characterized by TGA, PXRD and single-crystal X-ray diffraction. Compound 1 crystalizes in monoclinic, space group C2/c with a = 20.570(5), b = 35.815(8), c = 10.106(2) , C318H72N9Nd5O50S12, Mr = 2315.73, V = 6765(3) , Z = 4, Dc = 2.274 g·cm-3, μ = 4.253 mm-1, F(000) = 4520, 2.52θ25°, λ(MoKα) = 0.71073 , T = 273(2) K, the final R = 0.0401, wR = 0.1022 and S = 1.042. X-ray diffraction analysis reveals that complex 1 possesses a 3D inorganic sulfate framework with large 20-membered ring(20 MR) and 10-membered ring(10 MR) channels constructed by two kinds of SBUs. Moreover, the UV-vis and luminescent properties of complex 1 were also investigated.     

Oxamido‐bridged N4 Macrocyclic Complexes CuII/MII/CuII (M = Mn,Co): Synthesis,Crystal Structures and Magnetic Properties

Two new oxamido‐bridged N₄ macrocyclic complexes [(CuL)₂Mn(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 1 ) and [(CuL)₂Co‐(C₂H₅OH)₂](ClO₄)₂ · 2C₂H₅OH ( 2 ) (H₂L = 2,3‐dioxo‐5,6:14,15‐di‐benzo‐7,13‐diphenyl‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐diene) have been synthesized and structurally characterized by X‐ray crystallographic investigations. In the two complexes, all copper(II) ions adopt a slightly distorted square‐planar configuration and the central manganese(II) and cobalt(II) ions are set in a distorted octahedral coordination sphere, connected to the other CuL fragments through exo‐cis oxamido bridges. The analyses of the magnetic properties were carried out by means of the theoretical expression of the magnetic susceptibility deduced from the spin Hamiltonian ? = –2J?₁?₂, leading to J = –14.58 cm^–1 for complex 1 and J = –26.95 cm^–1 for complex 2 , respectively.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.