Effect of Metal Ions on the Structures of Coordination Polymers Based on Biphenyl‐2,2′,4,4′‐Tetracarboxylate

Two new coordination polymers, {[Cd₂(btc)(2,2′‐bpy)₂] · H₂O}_n ( 1 ) and [Zn₂(btc)(2,2′‐bpy)(H₂O)]_n ( 2 ) (H₄btc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine), were synthesized hydrothermally under similar conditions and characterized by elemental analysis, IR spectra, TGA, and single‐crystal X‐ray diffraction analysis. In complexes 1 and 2 , the (btc)^4– ligand acts as connectors to link metal ions to give a 2D bilayer network of 1 and a 3D metal‐organic framework of 2 , respectively. The differences in the structures are induced by diverging coordination modes of the (btc)^4– ligand, which can be attributed to the difference metal ions in sizes. The results indicate that metal ions have significant effects on the formation and structures of the final complexes. Additionally, the fluorescent properties of the two complexes were also studied in the solid state at room temperature.     

Influence of the Size of Aromatic Chelate Ligands on the Structures of Cadmium(II) Tetracarboxylates Polymers: From 2D Layered Network to 3D Metal‐Organic Framework

To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)_0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)_0.5(phen)]·H₂O ( 2 ) (H₄btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd₂ units are linked by bridging btc^4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd₂ units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature.     

Two Keggin Templated Supramolecular Compounds by Exerting the Chelate and Linking Dual Roles of the Ligand 2, 2′‐Biimidazole

Two new Keggin templated supramolecular compounds, [Zn₂(H₂biim)₅(SiM₁₂O₄₀)] · 4H₂O [M = W ( 1 ), Mo ( 2 )] (H₂biim = 2, 2′‐biimidazole), were synthesized under hydrothermal conditions by using the ligand 2, 2′‐biimidazole. They were characterized by single‐crystal X‐ray diffraction, elemental analyses, IR and photoluminescence spectroscopy as well as cyclic voltammetry. The two isostructural compounds are constructed by two discrete supramolecular moieties: the inorganic chains consist of Keggin anions and metal‐organic chains constructed by [Zn₂(H₂biim)₅]⁴⁺ subunits. In the dinuclear [Zn₂(H₂biim)₅]⁴⁺ subunit, the H₂biim ligands exhibit a dual role, chelating and linking. The metal‐organic chains further construct a 3D supramolecular framework with channels, in which the Keggin‐based inorganic chains are accommodated. The electrochemical behaviors of compounds 1 and 2 bulk‐modified carbon paste electrodes ( 1 ‐CPE, 2 ‐CPE) were studied.     

A Bifunctional Luminescent Metal–Organic Framework for the Sensing of Paraquat and Fe3+ Ions in Water

The hydrothermal reaction of Zn²⁺ ions with a mixture of two ligands, Hcptpy and H₃btc (Hcptpy=4‐(4‐carboxyphenyl)‐2,2′:4′,4′′‐terpyridine; H₃btc=1,3,5‐benzenetricarboxylic acid), led to the formation of a 3D metal–organic framework (MOF) with 1D channels, [Zn₂(cptpy)(btc)(H₂O)]_n ( 1 ), which was structurally characterized by using single‐crystal X‐ray diffraction (SXRD). In MOF 1 , two independent Zn²⁺ ions were interconnected by btc^3? ligands to form a 1D chain, whilst adjacent Zn²⁺ ions were alternately bridged by cptpy^? ligands to generate a 2D sheet, which was further linked by 1D chains to form a 3D framework with a new (3,3,4,4)‐connected topology. Furthermore, compound 1 also exhibited excellent stability towards air and water and, more importantly, luminescence experiments indicated that it could serve as a probe for the sensitive detection of paraquat (PAQ) and Fe³⁺ ions in aqueous solution.     

A d10 Metal Coordination Polymer Containing a Thiodiphthalic Ligand: Crystal Structure and Luminescent Property

A new two‐dimensional metal‐organic coordination polymer [Cd₂(2,3,2′,3′‐sdpa)(H₂O)₃] · 2H₂O ( 1 ) were hydro(solvo)thermally synthesized by the reaction of 2,3,2′,3′‐sulfonyldiphthalic acid (2,3,2′,3′‐H₄sdpa) with Cd(NO₃)₂ · 4H₂O and characterized by elemental analysis, thermogravimetry, IR and luminescence spectroscopy, and X‐ray diffraction. In complex 1 , two kinds of cadmium atoms are linked together by anionic sdpa^4– ligands to form a 2D metal‐organic network. The adjacent 2D layers further interact with each other through hydrogen bonds and π ··· π interactions to form a 3D supramolecular structure. The luminescence spectra and thermal properties of 1 were also investigated.     

2, 4‐Dimethylpenta‐1, 3‐dien‐ und 2, 4‐Dimethylpentadienyl‐Komplexe des Rhodiums und Iridiums

2, 4‐Dimethylpenta‐1, 3‐diene and 2, 4‐Dimethylpentadienyl Complexes of Rhodium and Iridium The complexes [(η⁴‐C₇H₁₂)RhCl]₂ ( 1 ) (C₇H₁₂ = 2, 4‐dimethylpenta‐1, 3‐diene) and [(η⁴‐C₇H₁₂)₂IrCl] ( 2 ) were obtained by interaction of C₇H₁₂ with [(η²‐C₂H₄)₂RhCl]₂ and [(η²‐cyclooctene)₂IrCl]₂, respectively. The reaction of 1 or 2 with CpTl (Cp = η⁵‐C₅H₅) yields the compounds [CpM(η⁴‐C₇H₁₂)] ( 3a : M = Rh; 3b : M = Ir). The hydride abstraction at the pentadiene ligand of 3a , b with Ph₃CBF₄ proceeds differently depending on the solvent. In acetone or THF the “half‐open” metallocenium complexes [CpM(η⁵‐C₇H₁₁)]BF₄ ( 4a : M = Rh; 4b : M = Ir) are obtained exclusively. In dichloromethane mixtures are produced which additionally contain the species [(η⁵‐C₇H₁₁)M(η⁵‐C₅H₄CPh₃)]BF₄ ( 5a : M = Rh; 5b : M = Ir) formed by electrophilic substitution at the Cp ring, as well as the η³‐2, 4‐dimethylpentenyl compound [(η³‐C₇H₁₃)Rh{η⁵‐C₅H₃(CPh₃)₂}]BF₄ ( 6 ). By interaction of 2, 4‐dimethylpentadienyl potassium with 1 or 2 the complexes [(η⁴‐C₇H₁₂)M(η⁵‐C₇H₁₁)] ( 7a : M = Rh; 7b : M = Ir) are generated which show dynamic behaviour in solution; however, attempts to synthesize the “open” metallocenium cations [(η⁵‐C₇H₁₁)₂M]⁺ by hydride abstraction from 7a , b failed. The new compounds were characterized by elemental analysis and spectroscopically, 4b and 5a also by X‐ray structure analysis.     

Syntheses,Structures, and Magnetic Properties of Two Cobalt(II) Metal‐Organic Frameworks Based on Y‐shaped 3,5,4′‐Azobenzenetricarboxylic Acid and Different N‐donor Ligands

Two metal‐organic frameworks, [Co₂(ABTC)(bimh)(OH)] · 2H₂O ( 1 ) and [Co₃(ABTC)₂(dimb)₄]_n ( 2 ) [H₃ABTC = 3,4′,5‐azobenzenetricarboxylic acid, bimh = 1,1′‐(1,4‐hexanediy)bis(imidazole), dimb = 1,4‐bis(1H‐imidazol‐1‐yl)benzene], were prepared under solvothermal conditions and structurally characterized. Complex 1 demonstrates a complicated 3D (3,8)‐connected tfz‐d net with (4³)₂(4⁶.6¹⁷.8⁵) topology. The framework of 2 can be classified as a rare 3D (3,6,6)‐connected net with the Schäfli symbol of (4.6²)₂(4².6¹⁰.8³)(4⁴.6¹⁰.8), and exhibits an intriguing self‐penetrating motif. Meanwhile, the thermal stabilities and magnetic properties for 1 and 2 were also probed.     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

Syntheses,Structures and Characterization of Four Metal‐Organic Frameworks constructed by 2,2′,6,6′‐Tetramethoxy‐4,4′‐biphenyldicarboxylic Acid

Four metal‐organic frameworks (MOFs), {[Mn_3.5L(OH)(HCOO)₄(DMF)] · H₂O} ( 1 ), {[In_2.5L₂O(OH)_1.5(H₂O)₂] · DMF · CH₃CN · 2H₂O} ( 2 ), {[Pb₄L₃O(DMA)] · CH₃CN} ( 3 ), and {[LaL(NO₃)(DMF)₂] · 2H₂O} ( 4 ) were synthesized by utilizing the ligand 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H₂L) via solvothermal methods. All MOFs were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction, thermogravimetric analysis, and infrared spectroscopy. In 1 , the Mn²⁺ ions are interconnected by formic groups in situ produced via DMF decomposition to form a rare 2D macrocyclic plane, which is further linked by L^2– to construct the final 3D network. In 2 , 1D zip‐like infinite chain is formed and then interconnected to build the 3D framework. In 3 , a [Pb₆(μ₄‐O)₂(O₂C)₁₀(DMA)₂] cluster with a centrosymmetric [Pb₆(μ₄‐O)₂]⁸⁺ octahedral core is formed in the 3D structure. In 4 , the La³⁺ ions are connected with each other through carboxylate groups of L^2– to generate 1D zigzag chain, which is further linked by L^2– to construct a 3D network with sra topology. Solid photoluminescence properties of 3 and 4 were also investigated.     

A Three‐dimensional DyIII‐based Metal‐organic Framework: Smart Drug Carrier and Anti‐lung Cancer Activity

A 3D lanthanide metal‐organic framework (MOF) with the formula [Dy₂(L)₂(H₂O)₂]_n ( 1 ) (H₃L = biphenyl‐3,4′,5‐tricarboxylic acid) was synthesized under solvothermal conditions and structurally characterized by elemental analysis, powder X‐ray diffraction analysis, infrared spectroscopy, and single‐crystal X‐ray diffraction analysis. Compound 1 features a 3D porous framework based on 1D rod‐shaped Dy^III‐carboxylate chains. The efficient encapsulation and controllable release of an anticancer drug (5‐Fu) make it a promising drug delivery host. Furthermore, the GCMC simulation was used to probe the drug‐framework interaction at the atomic lever. The in vitro anti‐lung cancer activity of 1 and 5‐Fu loaded 1a were also evaluated using MTT assay.     

Two Bulky Conjugated 4′‐(4‐Hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine‐based Layered Complexes: Synthesis,Structure, and Photocatalytic Hydrogen Evolution Activity

Two new layered complexes with the formulas of {[Cu(H₂O)(HL)₂Cl](NO₃)}_n ( 1 ) and {[Cu(H₂O)₂(HL)₂](NO₃)₂}_n ( 2 ) were solvothermally synthesized by the reactions of the bulky conjugated 4′‐(4‐hydroxyphenyl)‐4,2′:6′,4′′‐terpyridine ligand (HL) with different Cu^II salts, which were further used as photocatalysts to achieve hydrogen production from water splitting. Single‐crystal structural analyses reveal that both complexes feature coplanar (4 4) layers with different connection manners between the HL extended Z‐shaped chains. More interestingly, 1 possessing more negative conduction band potential and higher structural stability exhibits a large hydrogen production rate of 2.43 mmol · g^–1 · h^–1, which is four times higher than that of 2 . Thus, the Cu^II‐based coordination polymers modified by the bulky conjugated organic ligand can become potentially promising non‐Pt photocatalysts for hydrogen production from water splitting.     

Syntheses,Crystal Structures,and Fluorescence Properties of Two Transition Metal‐Organic Coordination Polymers Based on 4,4′‐Dimethyl‐2,2′‐bipyridine

Two transition metal‐organic coordination polymers, [Mn₂(1,3‐bdc)₂(Me₂bpy)₂] · Me₂bpy ( 1 ) and [Co(4,4′‐oba)(Me₂bpy)] ( 2 ) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray diffraction [1,3‐H₂bdc = benzene‐1,3‐dicarboxylic acid, H₂oba = 4,4′‐oxybis(benzoic acid) Me₂bpy = 4,4′‐dimethyl‐2,2′‐bipyridine]. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁, with a = 23.371(5), b = 14.419(3), and c = 14.251(3) Å. Compound 2 crystallizes in the monoclinic system, space group P2₁/c, with a = 7.4863(15), b = 18.272(4), c = 16.953(5) Å, and β = 107.44(3)°. The crystal structure of complex 1 is a wave‐like layer with central Mn²⁺ atoms bridged by 1,3‐bdc ligands, whereas the structure of compound 2 presents a ladder chain of hexacoordinate Co²⁺ atoms, in which the metal atoms are bridged by 4,4′‐oba ligands and decorated by Me₂bpy ligands. The two compounds are further extended into 3D supramolecular structures through π–π stacking interactions. Additionally, the compounds show intense fluorescence in solid state at room temperature.     

Two Zinc(II) Coordination Polymers Based on Terphenyl‐2,2′,4,4′‐tetracarboxylate and Dipyridyl Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two coordination polymers, {[Zn₂(L)(bpy)] · 2H₂O}_n ( 1 ) and [Zn₂(L)(bpe)]_n ( 2 ) [H₄L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.     

Crystallographic report: A three‐dimensional coordination polymer: [Zn6(btc)4(4,4′‐bipy)5]n (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine)

The three‐dimensional (3D) coordination polymer [Zn₆(btc)₄(4,4′‐bipy)₅]_n ( 1 ) (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine) has been prepared hydrothermally. The zinc(II) centers in 1 are bridged by btc ligands to form a trinuclear subunit, which is further linked by 4,4′‐bipy and btc ligands to construct the 3D coordination architecture. Copyright © 2003 John Wiley & Sons, Ltd.     

Metal Ion‐tuned Complexes based on Benzene‐1, 2, 4, 5‐tetracarboxylic Acid and the Semirigid Ligand 1, 4‐Bis(2‐methylbenzimidazol‐1‐ylmethyl) Benzene

Abstract. Two metal‐organic coordination polymers [Co(bmb)(btc)_0.5]_n( 1 ) and {[Zn(bmb)_0.5(btc)_0.5(H₂O)] · 0.5bmb · H₂O}_n ( 2 ) [H₄btc = benzene‐1, 2, 4, 5‐tetracarboxylic acid, bmb = 1, 4‐bis(2‐methylbenzimidazol‐1‐ylmethyl) benzene] were prepared under hydrothermal conditions. Single‐crystal X‐ray diffraction indicates that both complexes have a 2D framework structure with (4 · 6²) (4² · 6² · 8²) topology. Interestingly, the hydrogen bonds in 2 form a fascinating meso‐helix. The catalytic activity of 1 for oxidative coupling of 2, 6‐dimethylphenol (DMP) and the photoluminescence properties of 2 were investigated. Furthermore, the complexes were investigated by IR spectroscopy and thermogravimetric analysis.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

Synthesis,Structures, Fluorescence Properties,and Natural Bond Orbital (NBO) Analysis of Two Metal [EuIII,CoII] Coordination Polymers Containing 1, 3‐Benzenedicarboxylate and 2‐(4‐methoxyphenyl)‐1H‐imidazo[4, 5‐f][1, 10]phenanthroline Ligands

Two new metal‐organic coordination polymers[Eu(m‐BDC)_1.5(MOPIP) · 1/2H₂O]_n ( 1 ) and [Co(m‐BDC)(MOPIP)₂ · 2H₂O]_n ( 2 ) [m‐H₂BDC = benzene‐1, 3‐dicarboxylic acid, MOPIP = 2‐(4‐methoxyphenyl)‐1H‐imidazo[4, 5‐f] 1 , 10 phenanthroline] were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. The coordination polymers crystallize in monoclinic space group P2₁/m for 1 ( 2 : P2₁/n), with a = 9.779(2), b = 18.242(4), c = 17.146(3) Å, β = 106.41(3)° for 1 , and with a = 8.2153(16), b = 27.974(6), c = 17.974(4) Å, β = 100.40(3)° for 2 . The crystal structure of complex 1 is a zipper‐like chain of octacoordinate Eu³⁺ ions, in which Eu³⁺ ions are bridged in two coordination modes by m‐BDC²⁺ ligands and decorated by MOPIP ligands. The molecular structure of complex 2 consists of a hexacoordinte Co²⁺ atom, which generates a slightly distorted octahedral arrangement, and assembles into three‐dimensional supramolecular nets by π ··· π stacking interactions. Additionally, these two compounds show strong fluorescence in the solid state at room temperature. Natural bond orbital (NBO) analysis is performed by using the NBO method built in Gaussian 03 Program. The calculation results show a weak covalent interaction between the coordinated atoms and metal ions.     

Syntheses,Structures, Electrochemistry,and Electrocatalysis of Three Copper(II) Coordination Polymers constructed from 5‐[4‐(1H‐Imidazol‐1‐yl)phenyl]‐1H‐tetrazole

Three coordination polymers (CPs) based on the 5‐[4‐(1H‐imidazol‐1‐yl)phenyl]‐1H‐tetrazole ( HL ) ligand, namely, [Cu(μ₂‐ L )(μ₄‐pbda)(H₂O)] ( 1 ), [Cu₂(μ‐Hbtc)(H₂btc)(μ₃‐OH)(μ₄‐ HL )] ( 2 ) and [Cu₅(μ₃‐ L )(μ₄‐ L )(μ₃‐ip)(μ₃‐OH)(H₂O)₂] · 2H₂O ( 3 ) (H₂pbda = 1,4‐benzenedicarboxylic acid, H₃btc = 1,3,5‐benzenetricarboxylic acid, H₂ip = isophthalic acid) were hydrothermally synthesized and structurally characterized. Complex 1 represents “weave”‐type 2D layers consisting of wave‐like 1D chains and 1D straight chains, which are further connected by hydrogen bonds to form a 3D supramolecular structure. Complex 2 exhibits a uninodal (4)‐connected 2D layer with a point symbol of {4⁴ · 6²}, in which the L ligand can be described as μ₅‐bridging and the H₂btc^– ions display multiple kinds of coordination modes to connect Cu^II ions into 1D “H”‐type Cu‐H₂btc chains. In complex 3 , 2D Cu‐ L layers with two kinds of grids and 1D “stair”‐type Cu‐ip chains link each other to construct a 3D {4¹² · 6³} framework, which contains the pentanuclear subunits. Deprotonated degree and coordination modes of carboxylate ligands may consequentially influence the coordination patterns of main ligands and the final structures of complexes 1 – 3 . Furthermore, electrochemical behaviors and electrocatalytic activities of the title complexes were analyzed at room temperature, suggesting practical applications in areas of electrocatalytic reduction toward nitrite and hydrogen dioxide in aqueous solutions, respectively.     

Two New Cadmium(II) Compounds based on Distinct Second Building Subunits: Solvothermal Syntheses,Crystal Structures,and Luminescent Properties

Two cadmium(II) coordination polymers, namely [Cd₃(bpt)₂(DMA)₂]_n ( 1 ) and [Cd₂(bpt)(btz)(DMF)]_n ( 2 ) (H₃bpt = biphenyl‐3,4′,5‐tricarboxylic acid, Hbtz = 1H‐benzotriazole, DMA = N,N‐dimethylacetamide; DMF = N,N‐dimethylformamide), were solvothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 displays a 3D framework based on trinuclear {Cd₃(COO)₄} subunits and can be simplified into a (4,8)‐connected topological network by viewing bpt^3– ligands and trinuclear {Cd₃(COO)₄} units as 4‐, 8‐connected nodes, respectively. Compound 2 also displays a 3D framework but based on 1D chain subunits controlled by carboxylate groups and btz^– ligands. In addition, the thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated.     

Porous GdIII‐Organic Framework as a Dual‐Functional Material for Cyanosilylation of Aldehydes and Ablation of Human Liver Cancer Cells

Metal‐organic frameworks (MOFs) have gained great attention in recent years because they could behave as multifunctional materials which combine the advances of porous solids and coordination complexes. With the aim of constructing multifunctional MOFs, in this study, we choose a Y‐shaped tricarboxylic ligand biphenyl‐3,4′,5‐tricarboxylic acid (H₃bpt) to react with Gd^III ions to afford a new dual‐functional lanthanide‐organic framework with the chemical formula of [Gd₂(bpt)₂(H₂O)₂] · (DMF)₂(H₂O)₆ ( 1 ) (DMF = N,N‐dimethylformamide) under solvothermal condition. The title complex was characterized by means of elemental analysis, FT‐IR spectroscopy, thermogravimetric and X‐ray diffraction analyses. Crystal structure analysis reveals that compound 1 is composed of 1D helical chain secondary building units that connect by the bpt^3– ligands into a 3D framework with 1D nanosized channels running along the b axis. In view of its high porosity and accessible open metal sites, the activated 1 ( 1a ) was studied for the cyanosilylation of aldehydes under solvent‐free conditions. The catalytic activity of 1a is much higher than that of compound 1 , indicating that the exposed open metal sites of 1a is beneficial to the cyanosilylation reaction. In connection to these, the different cytotoxicities of 1 and 1a were also evaluated on four human liver cancer cells (SMMC‐7721, Bel‐7402, MHCC97 and Hep3B) by the MTT assay.