Synthesis,Structure, and Magnetic Properties of a Copper(II) Metal‐Organic Framework with Biphenyl‐2,2′,4,4′‐tetracarboxylic Acid

The 2D Cu^II metal‐organic framework [Cu₂(bptc)(H₂O)₄]_n · 4nH₂O ( 1 ) (H₄bptc = biphenyl‐2,2′,4,4′‐tetracarboxylic acid) was hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and magnetic measurements. In the structure, bptc^4– serves as a twisted Π‐shaped organic building block to connect paddlewheel [Cu₂(COO)₄] dinuclear units and mononuclear units through 2‐/2′‐carboxylate and 4‐/4′‐carboxylate, respectively. According to the magnetic analysis using a dimer‐plus‐monomer model, strong antiferromagnetic coupling is operative within the dinuclear unit (J = –311 cm^–1 based on H = –J S ₁ S ₂), and the compound behaves like a mononuclear molecule at low temperature.     

Supramolecular Open‐Framework of a Bipyridinium‐Carboxylate Based Copper Complex with High and Reversible Water Uptake

The rigid zwitterionic ligand 1,1′‐bis(4‐carboxylatphenyl)‐(4,4′‐bipyridinium) (pc1) and copper(II) ions give rise to a linear complex [Cu(pc1)₂(H₂O)₄]²⁺, which self assembles in a pseudo tetragonal supramolecular arrangement leading to the supramolecular open‐framework [Cu(pc1)₂(H₂O)₄](Cl)₂ · 8H₂O exhibiting an open structure including water molecules and chlorides in pores. The dehydration of this material occurs at relatively low temperature (70 °C) and results in structure modification accompanied by shrinking of the crystals. Characterization of the obtained material by FT‐IR spectroscopy reveals appearance of coordinated carboxylates groups, which may indicate the formation of coordination polymer after dehydration. Water adsorption (maximum uptake 0.23 g H₂O per g) on dehydrated material allows to restore the initial structure. A large hysteresis in water adsorption‐desorption isotherm is characteristic of a significant modification of the structure during the hydration‐dehydration cycle which is in line with the structural transition determined from thermodiffractometry and FT‐IR spectroscopy.     

Encapsulation of 5‐Fluorouracil in a Copper(II)‐based Porous Metal‐organic Framework: Drug Delivery and Inhibiting Human Spinal Cord Tumor Cells

Solvothermal reaction of a semirigid tricarboxylic acid with Cu(NO₃)₂ · 3H₂O gives rise to a robust microporous metal‐organic framework with the formula {[Cu₂(OH)bcb](DMF)₂(H₂O)₃}_n ( 1 ) [H₃bcb = 3,5‐bis((4′‐carboxylbenzyl)‐oxy)benzoic acid, DMF = N,N‐dimethylformamide]. Its structure was determined by single‐crystal X‐ray diffraction analysis and further characterized by elemental analysis, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. The efficient encapsulation of an anticancer drug 5‐fluorouracil (5‐Fu) on the desolvated 1 ( 1a ) was studied by both grand canonical Monte Carlo (GCMC) simulation and drug release experiments. In addition, in vitro anticancer activity of compounds 1 and 5‐Fu loaded 1a were also evaluated using MTT assay.     

A Polyhedron‐based Metal‐Organic Framework showing high CO2 Adsorption Capacity

A novel porous copper‐based metal‐organic framework {[Cu₂(TTDA)₂]*(DMA)₇}_n ( 1 ) (DMA = N,N‐dimethylacetamide) was designed and synthesized via the combination of a dual‐functional organic linker 5′‐(4‐(4H‐1,2,4‐triazol‐4‐yl)phenyl)‐[1,1′:3′,1′′‐terphenyl]‐4,4′′‐dicarboxylic acid (H₂TTDA) and a dinuclear Cu^II paddle‐wheel cluster. This MOF is characterized by elemental analysis, powder X‐ray diffraction (PXRD), thermo gravimetric analysis (TGA), and single‐crystal X‐ray diffraction. The framework is constructed from two types of cages (octahedral and cuboctahedral cages) and exhibits two types of circular‐shaped channels of approximate size of 5.8 and 11.4 Å along the crystallographic c axis. The gas sorption experiments indicate that it possesses a large surface area (1687 m² · g^–1) and high CO₂ adsorption capacities around room temperature (up to 172 cm³ · g^–1 at 273 K and 124 cm³ · g^–1 at 298 K).     

A 3D Luminescent Metal‐organic Framework Constructed from Cu4I4 Cubane Clusters and Triangular Imidazole Ligand

Abstract . The solvothermal reaction between cuprous iodide and the rigid triangular imidazole ligand in mixed N,N′‐dimethylacetamide (DMA)‐acetonitrile solvent leads to the isolation of the 3D metal‐organic framework [(Cu₄I₄)₃(TIPA)₄] · 7DMA ( 1 ) [TIPA = tri(4‐imidazolylphenyl) amine], which was characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Topologically, the structure of 1 is an unprecedented 3,3,4,4‐connected net with a point symbol of {4.8.10}₂{4.8²}₂{4².8².10²}₂{8⁴.12²}. Compound 1 exhibits orange‐red photoluminescence with an emission maximum at 622 nm at room temperature.     

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.     

Synthesis,Characterization and Photoluminescence of Lanthanide Metal‐organic Frameworks,Constructed from Triangular 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate Ligands

Eight isomorphous metal‐organic frameworks: [Ln₂(TATAB)₂(H₂O)(DMA)₆]·5H₂O (Ln = Sm ( 1 ), Eu ( 2 ), Gd ( 3 ), Tb ( 4 ), Dy ( 5 ), Er ( 6 ), Tm ( 7 ), Yb ( 8 )); TATAB = 4,4′,4″‐s‐triazine‐1,3,5‐triyl‐p‐aminobenzoate, DMA = N,N‐dimethylacetamide), were synthesized by the self‐assembly of lanthanide ions, TATAB, DMA and H₂O. Single‐crystal X‐ray crystallography reveals they are three dimensional frameworks with 2‐fold interpenetration. Solid‐state photoluminescence studies indicate ligand‐to‐metal energy transfer is more efficient for compounds 2 and 4 which exhibit intense characteristic lanthanide emissions at room temperature.     

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.     

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.     

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.     

Metal‐Ion Sensing Europium(III) Complexes with Bidentate Phosphine Oxide Ligands Containing a 2,2′‐Bipyridine Framework

Novel Eu^III complexes with bidentate phosphine oxide ligands containing a bipyridine framework, i.e., [3,3′‐bis(diphenylphosphoryl)‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(BIPYPO)]) and [3,3′‐bis(diphenylphosphoryl)‐6,6′‐dimethyl‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(Me‐BIPYPO)]), were synthesized for lanthanide‐based sensor materials having high emission quantum yields and effective chemosensing properties. The emission quantum yields of [Eu(hfa)₃(BIPYPO)] and [Eu(hfa)₃(Me‐BIPYPO)] were 71 and 73%, respectively. Metal‐ion sensing properties of the Eu^III complexes were also studied by measuring the emission spectra of Eu^III complexes in the presence of Zn^II or Cu^II ions. The metal‐ion sensing and the photophysical properties of luminescent Eu^III complexes with a bidentate phosphine oxide containing 2,2′‐bipyridine framework are demonstrated for the first time.     

Hydrogen‐bonded assemblies in the molecular crystals of 2,2′‐thiodiacetic acid with ethylenediamine and o‐phenylenediamine

Carboxylate molecular crystals have been of interest due to the presence of hydrogen bonding, which plays a significant role in chemical and crystal engineering, as well as in supramolecular chemistry. Acid–base adducts possess hydrogen bonds which increase the thermal and mechanical stability of the crystal. 2,2′‐Thiodiacetic acid (Tda) is a versatile ligand that has been widely explored, employing its multidendate and chelating coordination abilities with many metals; however, charge‐transfer complexes of thiodiacetic acid have not been reported. Two salts, namely ethylenediaminium 2,2′‐thiodiacetate, C₂H₁₀N₂²⁺·C₄H₄O₄S₂²⁻, denoted Tdaen, and 2‐aminoanilinium 2‐(carboxymethylsulfanyl)acetate, C₆H₉N₂⁺·C₄H₅O₄S⁻, denoted Tdaophen, were synthesized and characterized by IR, ¹H and ¹³C NMR spectroscopies, and single‐crystal X‐ray diffraction. In these salts, Tda reacts with the aliphatic (ethylenediamine) and aromatic (o‐phenylenediamine) diamines, and deprotonates them to form anions with different valencies and different supramolecular networks. In Tdaen, the divalent Tda²⁻ anions form one‐dimensional linear supramolecular chains and these are extended into a three‐dimensional sandwich‐type supramolecular network by interaction with the ethylenediaminium cations. However, in Tdaophen, the monovalent Tda⁻ anions form one‐dimensional zigzag supramolecular chains, which are extended into a three‐dimensional supramolecular network by interaction with the 2‐aminoanilinium cations. Thus, both three‐dimensional structures display different ring motifs. The structures of these diamines, which are influenced by hydrogen‐bonded assemblies in the molecular crystals, are discussed in detail.     

Metal‐4,4′‐azobis(3,5‐dimethyl‐1H‐pyrazole) Complexes with Seven‐ and Nine‐membered Hydrogen‐bonded Rings Originating from the Pyrrolic NH Function

The metal complexes [Cu(NO₃)₂(H₂O)₂(H₂azbpz)₂] · 2H₂O ( 1 ) and [Ni(H₂O)₄(H₂azbpz)₂](NO₃)₂ · 2H₂O ( 2 ) of 4,4′‐azobis(3,5‐dimethyl‐1H‐pyrazole) (H₂azbpz) incorporate the bipyrazole as a monodentate ligand and are associated into supramolecular architectures by hydrogen bonds and azo‐pz π interactions in the solid state. In 1 a cis configuration is integrated and the NH function adjacent to the metal‐coordinating nitrogen atom gives rise to a seven‐membered anion‐assisted hydrogen‐bonded ring around the central metal atom bringing the NH function in endo‐position to the azo‐bridge. The interplay of hydrogen‐bonds and dimeric azo‐pz π interactions in 1 forms one‐dimensional supramolecular chains, which are further interconnected by a heterodromic D_2h symmetric tetrameric water ring. In 2 a trans form of H₂azbpz is mono‐coordinated and the synergy of hydrogen‐bonded rings around the central metal atom and continuous azo‐pz π interactions form a two‐dimensional supramolecular network structure. The supramolecular packings of 1 and 2 is further underpinned by the analysis of their Hirshfeld surface areas.     

Synthesis,Reactions, Characterization and Biological Evaluation of 2,3′‐Bipyridine Derivatives (III)

1‐Pyridin‐3‐yl‐3‐(2‐thienyl of 2‐furyl)prop‐2‐en‐1‐ones 1a , 1b reacted with 2‐cyanoethanethioamide 2 to afford the corresponding 4‐(thiophen‐2‐yl or furan‐2‐yl)‐6‐sulfanyl‐2,3′‐bipyridine‐5‐carbonitriles 3a , 3b . The synthetic potentiality of compounds 3a , 3b were investigated in the present study via their reactions with several active halogen containing compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 5 , 5a , 5b . Our aim here is the synthesis of 4‐(2‐thienyl or 2‐furyl)‐6‐pyridin‐3‐ylthieno[2,3‐b]pyridin‐3‐amines 6a , 6b , 6c , 6d , 6e , 6g , 6h , 6i , 6j , 6k , 6l , 6m , 6n ,via 6‐(alkyl‐thio)‐4‐(2‐thienyl or 2‐furyl)‐2,3′‐bipyridine‐5‐carbonitriles 5a , 5b , 5c , 5d , 5e , 5i , 5j , 5k , 5l , 5m . The structures of all newly synthesized heterocyclic compounds were elucidated by considering the data of IR, ¹H‐NMR, mass spectra, as well as that of elemental analyses. Anti‐cancer, anti‐Alzheimer, and anti‐COX‐2 activities were investigated for all the newly synthesized heterocyclic compounds.     

A Supramolecular Hydrogen‐Bonded Network as a Diffusion Barrier for Metal Adatoms

Confined in a molecular corral : A supramolecular network changes the mechanism by which underpotential deposition (UPD) of copper proceeds on a gold electrode modified by a self‐assembled monolayer (SAM). Lateral diffusion of Cu adatoms is suppressed between adjacent cells of a network/SAM hybrid structure. Instead, UPD occurs by direct deposition into the SAM filled pores of the network, where the Cu adatoms are confined.

     

Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Studying the self‐assembly of uracil derivatives has great importance for biochemistry and nanotechnology. For example, modification of the sorbent surfaces by 5‐hydroxy‐6‐methyluracil (HMU ) enhances their adsorption activity. It is assumed that these changes are caused by the self‐assembly of the network‐like supramolecular associates of the uracil derivative on the sorbent surface. In the present work, the relative stabilities of 15 hydrogen‐bonded dimers HMU have been studied by the TPSSh /TZVP density functional theory method and the strengths of the noncovalent interactions analyzed in terms of the reduced density gradient and natural bond orbital approaches. It was found that the symmetric dimer stabilized by two intermolecular hydrogen bonds N1 –H∙∙∙O–C2 (dimer 1‐1) is the most stable. This suggests that the self‐assembly of HMU should occur through the intermediate formation of the dimer 1‐1. The results may be useful for understanding the processes of self‐assembly of the uracil derivatives and the rationalized design of the uracil‐based supramolecular structures with specific properties.     

Tuning of Supramolecular Architectures of l‐Valine‐Containing Dicyanoplatinum(II) 2,2′‐Bipyridine Complexes by Metal–Metal, π–π Stacking,and Hydrogen‐Bonding Interactions

A series of newly synthesized dicyanoplatinum(II) 2,2′‐bipyridine complexes exhibits self‐assembly properties in solution after the incorporation of the l ‐valine amino units appended with various hydrophobic motifs. These l ‐valine‐derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature‐dependent studies. On the other hand, systematic transformation from less uniform aggregates to well‐defined fibrous and rod‐like structures via Pt???Pt and π–π stacking interactions has also been observed in the mixed‐solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.