4‐(3,5‐Dimethyl‐1H‐pyrazol‐4‐ylmethyl)‐3,5‐dimethyl‐1H‐pyrazol‐2‐ium dihydrogen phosphate: a combined X‐ray and DFT study

The molecular structure of the title salt, C₁₁H₁₇N₄⁺·H₂PO₄⁻, has been determined from single‐crystal X‐ray analysis and compared with the structure calculated by density functional theory (DFT) at the BLYP level. The crystal packing in the title compound is stabilized primarily by intermolecular N—H...O, O—H...N and O—H...O hydrogen bonds and π–π stacking interactions, and thus a three‐dimensional supramolecular honeycomb network consisting of R₄²(10), R₄⁴(14) and R₄⁴(24) ring motifs is established. The HOMO–LUMO energy gap (1.338 eV; HOMO is the highest occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital) indicates a high chemical reactivity for the title compound.     

Syntheses,Crystal Structures,and Properties of Lead(II), ­Zinc(II), and Manganese(II) Complexes Constructed from 2, 3, 5, 6‐Tetraiodo‐1, 4‐benzenedicarboxylic Acid

Three new coordination compounds, [Pb(HBDC‐I₄)₂(DMF)₄]( 1 ) and [M(BDC‐I₄)(MeOH)₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for ( 3 ) (H₂BDC‐I₄ = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The Pb^II and Zn^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.     

Crystal Structure,Solution and Solid‐state Photoluminescence of a 2D Zinc(II) Supramolecular Architecture

A new 2D zinc(II) supramolecular complex [Zn(2,4‐D)(o‐phen)(H₂O)₂](NO₃) ( 1 ) (2,4‐D = 2,4‐dichlorophenoxyacetic acid, o‐phen = 1,10‐phenanthroline), was synthesized and characterized by single‐crystal X‐ray diffraction, elemental analyses, TG analysis, IR, and luminescence spectroscopy. For complex 1 , each Zn^II ion lies in a pentacoordinate distorted quadrilateral pyramidal configuration. The 8‐member‐ring hydrogen bonds clusters result in 1D ladder‐like supramolecular chains, which further stack up by face‐to‐face π–π stacking interactions into 2D supramolecular layers. The TG analysis shows that complex 1 has high thermal stability. The solution and solid‐state photoluminescence of 1 are reported.     

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.     

Synthesis,crystal structure and photophysical properties of 1,4‐bis(1,3‐diazaazulen‐2‐yl)benzene: a new π building block

A dimerized 1,3‐diazaazulene derivative, namely 1,4‐bis(1,3‐diazaazulen‐2‐yl)benzene [or 2,2′‐(1,4‐phenylene)bis(1,3‐diazaazulene)], C₂₂H₁₄N₄, (I), has been synthesized successfully through the condensation reaction between 2‐methoxytropone and benzene‐1,4‐dicarboximidamide hydrochloride, and was characterized by ¹H NMR and ¹³C NMR spectroscopies, and ESI–MS. X‐ray diffraction analysis reveals that (I) has a nearly planar structure with good π‐electron delocalization, indicating that it might serve as a π building block. The crystal belongs to the monoclinic system. One‐dimensional chains were formed along the a axis through π–π interactions and adjacent chains are stabilized by C—H…N interactions, forming a three‐dimensional architecture. The solid emission of (I) in the crystalline form exhibited a 170 nm red shift compared with that in the solution state. The observed optical bandgap for (I) is 3.22 eV and a cyclic voltammetry experiment confirmed the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The calculated bandgap for (I) is 3.37 eV, which is very close to the experimental result. In addition, the polarizability and hyperpolarizability of (I) were appraised for its further application in second‐order nonlinear optical materials.     

Synthesis,spectroscopic (FT–IR and UV–Vis), crystallographic and theoretical studies,and a molecular docking simulation of an imatinib‐like template

The aim of the present study was to report the crystal structure and spectroscopic, electronic, supramolecular and electrostatic properties of a new polymorph of 4‐(pyridin‐2‐yl)pyrimidin‐2‐amine (C₉H₈N₄). The compound was synthesized under microwave irradiation. The single‐crystal X‐ray structure analysis revealed an angle of 13.36 (8)° between the planes of the rings, as well as molecules linked by Nsp²—H…N hydrogen bonds forming dimers along the crystal. The material was analyzed by FT–IR vibrational spectroscopy, while a computational approach was used to elucidate the vibrational frequency couplings. The existence of Nsp²—H…N hydrogen bonds in the crystal was confirmed spectroscopically by the IR peaks from the N—H stretching vibration shifting to lower wavenumbers in the solid state relative to those in the gas phase. The supramolecular studies confirmed the formation of centrosymmetric R₂²(8) rings, which correspond to the formation of dimers that stack parallel to the b direction. Other weak C—H…π interactions, essential for crystal growth, were found. The UV–Vis spectroscopic analysis showed a donor–acceptor process, where the amino group acts as a donor and the pyridine and pyrimidine rings act as acceptors. The reactive sites of the molecule were identified and their quantitative values were defined using the electrostatic potential model proposed in the multifunctional wave function analyzer multiwfn. The calculated interaction energies between pairs of molecules were used to visualize the electrostatic terms as the leading factors against the dispersion factors in the crystal‐growth process. The docking results showed that the amino group of the pyrimidine moiety was simultaneously anchored by hydrogen‐bonding interactions with the Asp427 and His407 protein residues. This compound could be key for the realization of a series of syntheses of molecules that could be used as possible inhibitors of chronic myelogenous leukemia.     

Synthesis,structure and characterization of two copper(II) supramolecular coordination polymers based on a multifunctional ligand 2‐amino‐4‐sulfobenzoic acid

Copper(II) coordination polymers have attracted considerable interest due to their catalytic, adsorption, luminescence and magnetic properties. The reactions of copper(II) with 2‐amino‐4‐sulfobenzoic acid (H₂asba) in the presence/absence of the auxiliary chelating ligand 1,10‐phenanthroline (phen) under ambient conditions yielded two supramolecular coordination polymers, namely (3‐amino‐4‐carboxybenzene‐1‐sulfonato‐κO¹)bis(1,10‐phenanthroline‐κ²N,N′)copper(II) 3‐amino‐4‐carboxybenzene‐1‐sulfonate monohydrate, [Cu(C₇H₆N₂O₅S)(C₁₂H₈N₂)₂](C₇H₆N₂O₅S)·H₂O, (1), and catena‐poly[[diaquacopper(II)]‐μ‐3‐amino‐4‐carboxylatobenzene‐1‐sulfonato‐κ²O⁴:O^4′], [Cu(C₇H₆N₂O₅S)(H₂O)₂]_n, (2). The products were characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid‐state UV–Vis spectroscopy and single‐crystal X‐ray diffraction analysis, as well as by variable‐temperature powder X‐ray diffraction analysis (VT‐PXRD). Intermolecular π–π stacking interactions in (1) link the mononuclear copper(II) cation units into a supramolecular polymeric chain, which is further extended into a supramolecular double chain through interchain hydrogen bonds. Supramolecular double chains are then extended into a two‐dimensional supramolecular double layer through hydrogen bonds between the lattice Hasba⁻ anions, H₂O molecules and double chains. Left‐ and right‐handed 2₁ helices formed by the Hasba⁻ anions are arranged alternately within the two‐dimensional supramolecular double layers. Complex (2) exhibits a polymeric chain which is further extended into a three‐dimensional supramolecular network through interchain hydrogen bonds. Complex (1) shows a reversible dehydration–rehydration behaviour, while complex (2) shows an irreversible dehydration–rehydration behaviour.     

A two‐dimensional anionic CdII polymer constructed through dicyanamide coordination bridges

In the search for potential ferroelectric materials, molecular‐based one‐, two‐ and three‐dimensional cadmium(II) organic–inorganic compounds have been of interest as they often display solid–solid phase transitions induced by a variation in temperature. A new cadmium dicyanamide complex, poly[4‐dimethylamino‐1‐ethylpyridin‐1‐ium [tri‐μ‐dicyanamido‐κ⁶N¹:N⁵‐cadmium(II)]], {(C₉H₁₅N₂)[Cd(C₂N₃)₃]}_n, was synthesized by the reaction of 4‐dimethylamino‐1‐ethylpyridin‐1‐ium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution. In the crystal structure, each Cd^II cation is octahedrally coordinated by six terminal N atoms from six anionic dicyanamide (dca) ligands. Neighbouring Cd^II cations are linked together by dicyanamide bridges to form a two‐dimensional coordination polymer. The organic cations are not involved in the formation of the supramolecular network.     

Supramolecular architectures and crystal structures of gold(III) compounds with semicarbazones

The synthesis and crystal structures of two novel semicarbazones and four gold(III) compound derivatives of these semicarbazones are presented. A pattern in the formation of the semicarbazones shows the association of Cl^– ions held together by intra- and intermolecular forces. [AuCl₄]^? and [AuBr₄]^? anions are co-crystallised with these semicarbazone ligands, and the packing architectures revealed by a single-crystal X-ray diffraction analysis showed the different influences of the anions and the association of these chemical species by intermolecular forces on the crystal packing. Crystal engineering led to gold(III) compounds that are stabilised by relevant hydrogen bonding networks, which demonstrated their importance to the supramolecular organisation of the studied compounds. Interestingly, Cl???Br interactions are observed and contribute to the formation of the supramolecular structures. Elemental analysis data and spectroscopic properties in the solid state and solution are also described.     

Synthesis and Luminescent Properties of Two Zinc(II) Coordination Polymers Constructed by 4‐(Pyridin‐4‐ylmethoxy)benzolic Acid Ligand

Two coordination polymers, namely [Zn(L)Cl] ( 1 ) and [Zn(L)₂] ( 2 ) [L = 4‐(pyridin‐4‐ylmethoxy)benzolic acid] were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analyses, powder X‐ray diffraction, and thermogravimetric analysis. Compounds 1 and 2 have a two‐dimensional square‐shaped structure (the dimensions are 15.43 × 15.43 Å for 1 and 12.064 × 15.017 Å for 2 ) with (4⁴ · 6²) topology. Moreover, compounds 1 and 2 exhibit a 3D supramolecular structure made up by strong π–π interactions from the adjacent layers. Furthermore, compounds 1 and 2 show good fluorescence properties in the solid state at room temperature.     

A new stepped tetranuclear copper(II) complex: synthesis,crystal structure and photoluminescence properties

Binuclear and tetranuclear copper(II) complexes are of interest because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetranuclear copper(II) complexes, there are limited reports on the crystal structures and solid‐state photoluminescence properties of `stepped' tetranuclear copper(II) complexes. A new Cu^II complex, namely bis{μ₃‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}bis{μ₂‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}tetracopper(II), [Cu₄(C₁₁H₁₃NO₃)₄], has been synthesized and characterized using elemental analysis, FT–IR, solid‐state UV–Vis spectroscopy and single‐crystal X‐ray diffraction. The crystal structure determination shows that the complex is a stepped tetranuclear structure consisting of two dinuclear [Cu₂(L )₂] units {L is 3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolate}. The two terminal Cu^II atoms are four‐coordinated in square‐planar environments, while the two central Cu^II atoms are five‐coordinated in square‐pyramidal environments. The solid‐state photoluminescence properties of both the complex and 3‐[(2‐hydroxy‐4‐methoxybenzylidene)amino]propanol (H₂L ) have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H₂L displays a green emission at 515 nm.     

Macromolecular Self‐Assembly of Organotin(IV) Squarates and Croconates – Preparation and Crystal Structures of [SnMe2(H2O)2]C4O4, [SnMe3]2C4O4, and [SnMe3(H2O)]2C5O5

The new organotin(IV) squarates and croconates [SnMe₂(H₂O)₂]C₄O₄ ( 1 ), [SnMe₃]₂C₄O₄ ( 2 ), and [SnMe₃(H₂O)]₂C₅O₅ ( 3 ), were prepared by salt metathesis from the appropriate sodium salts, and characterized by single‐crystal X‐ray diffraction and infrared spectroscopy. While 1 and 2 are coordination polymers with bridging C₄O₄^2– anions, compound 3 exists as a monomer in the solid state. In the hydrated compounds 1 and 3 , the molecules are interconnected by various types of O–H ··· O bridges between non‐coordinated carbonyl oxygen atoms and water ligands, resulting in a supramolecular layer ( 1 , 2 ) or network structure ( 3 ), respectively.     

Silver(I) Complexes with Dithioether Ligands: Syntheses,Crystal Structures,and Fluorescence Properties

Two new dithioether ligands, 1,4‐bis[(phenylsulfanyl)methyl]naphthalene ( L¹ ), and 4,4′‐bis[(tert‐butylsulfanyl)methyl]biphenyl ( L² ) were synthesized and their silver(I) complexes were studied. Both Ag^I complexes, [Ag L¹ (NO₃)]_n ( 1 ) and [Ag L² (NO₃)]₂ ( 2 ), were synthesized at ambient temperature and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction analysis. Single‐crystal X‐ray analysis shows that complex 1 has a one‐dimensional helical chain structure with the neutral repeating unit [Ag(μ₂‐ L¹ )(NO₃)], whereas complex 2 has a centrosymmetrical neutral dinuclear structure. Moreover, complexes 1 and 2 are further extended into three‐dimensional supramolecular frameworks by hydrogen bonding and π–π stacking interactions, respectively. In addition, complexes 1 and 2 display strong blue emission in the solid state at room temperature.     

A Novel Mixed‐Ligand Manganese(II) Complex Containing a V‐shape Water Trimer: Synthesis,Structure and Magnetic Properties of {[Mn(azpy)2(dca)(H2O)2](ClO4)(azpy)(H2O)2}n

A novel mixed‐ligand complex {[Mn(azpy)₂(dca)(H₂O)₂](ClO₄)(azpy)(H₂O)₂}_n ( 1 ) has been synthesized and characterized by single crystal X‐ray analysis, elemental analysis, IR spectroscopy and variable temperature magnetic measurement. The 4,4′‐azopyridine and dicyanamide ligands are abbreviated as azpy and dca, respectively. The crystal structure of 1 revealed that the 1D covalent bonding chains constructed by μ_1,5‐dca bridging the Mn^II ions are linked together via O–H···N and O–H···O hydrogen bonds and π‐π stacking interactions into a 3D supramolecular structure. V‐shape (bent) water trimers were also found in the structure. The water clusters play an important role in the formation of the 3D supramolecular structure. The determination of the variable temperature magnetic susceptibilities (2–300 K) shows the existence of a very weak antiferromagnetic interaction with a J value of ?0.16 cm^?1.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

3D–2D–0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic–Inorganic Hybrid Host

The supramolecular salt [H₂pip]₃[Ge(hedp)₂]?14 H₂O ( 1 ) [H₂pip²⁺=piperazine cation C₄H₁₂N₂²⁺; hedp^5?=deprotonated form of etidronic acid, C₂H₃P₂O₇^5?) is reported. This consists of an organic–inorganic hybrid hydrogen‐bonded nanoporous framework, the internal surface of which acts as a template for the three‐dimensional (3D) clustering of water molecules. The structure and molecular dynamics of this material are characterised by single‐crystal X‐ray diffraction, thermogravimetric analysis, Raman (H/D isotopic substitution) spectroscopy, and ²H solid‐state (wide‐line and MAS) NMR spectroscopy. Material 1 is shown to be unusual because 1) few nanoporous materials exhibit a well‐organised 3D framework of water molecules, 2) it provides a unique opportunity to follow experimentally and to rationalise the deconstruction of a 3D water framework and 3) despite the fact that the hybrid framework is a supramolecular salt, the structure does not collapse after dehydration and the final material is crystalline.     

Strong Solid‐state Luminescence Enhancement in Supramolecular Assemblies of Polyoxometalate and “Aggregation‐Induced Emission”‐active Phospholium

Two new supramolecular fluorescent hybrid materials, combining for the first time [M₆O₁₉]^2? (M=Mo, W) polyoxometalates (POMs) and aggregation‐induced emission (AIE)‐active 1‐methyl‐1,2,3,4,5‐pentaphenyl‐phospholium ( 1⁺ ), were successfully synthesized. This novel molecular self‐assembling strategy allows designing efficient solid‐state emitters, such as (1)₂[W₆O₁₉] , by directing favorably the balance between the AIE and aggregation‐caused quenching (ACQ) effects using both anion‐π⁺ and H‐bonding interactions in the solid state. Combined single‐crystal X‐ray diffraction, Raman, UV‐vis and photoluminescence analyses highlighted that the nucleophilic oxygen‐enriched POM surfaces strengthened the rigidity of the phospholium via strong C?H???O contacts, thereby exalting its solid‐state luminescence. Besides, the bulky POM anions prevented π–π stacking interactions between the luminophores, blocking detrimental self‐quenching effects.     

A new ZnII coordination polymer based on 4‐(pyridin‐4‐yl)benzoic and formic acids: in‐situ synthesis,crystal structure and luminescence properties

The title compound, poly[(μ₂‐formato‐κ³O,O′:O)[μ₂‐4‐(pyridin‐4‐yl)benzoato‐κ³N:O,O′]zinc(II)], [Zn(C₁₂H₈NO₂)(HCOO)]_n, has been synthesized in situ and characterized by thermogravimetric analysis (TGA) and single‐crystal and powder X‐ray diffraction analyses. The polymer contains two independent structural units in the asymmetric unit. These are constructed from Zn²⁺ ions, 4‐(pyridin‐4‐yl)benzoate (4‐pbc) bridges and in‐situ‐generated formate ligands, forming two similar two‐dimensional (2D) layer structures. These similar 2D layers are arranged alternately and are linked with each other by dense C—H…O hydrogen bonds to generate a three‐dimensional (3D) supramolecular framework. The crystal is pseudomerohedrally twinned about [201]. Compared with free 4‐Hpbc, the polymer exhibits a red shift and significantly enhanced solid‐state luminescence properties.     

Two threefold Interpenetrating 3D Supramolecular Networks Based on 1D Chains and Hydrogen‐bond Interactions

The coordination compounds, [Cu₂(Htba)(tba)Cl] ( 1 ) and [Ag₂(Htba)(tba)(NO₃)] ( 2 ), were synthesized under solvothermal conditions by using a triazolate‐carboxylate bifunctional organic ligand 4‐(4H‐1,2,4‐triazol‐4‐yl)benzoic acid (Htba). X‐ray single crystal diffraction analyses for the two complexes revealed that compounds 1 and 2 exhibit one‐dimensional (1D) chain structures with uncoordinated carboxylic groups, which are further connected by O–H ··· O hydrogen bonds into 3D, threefold interpenetrating supramolecular frameworks with different topologies belonging to 4‐connected and (2,4)‐connected nets with the (4²·8²·10²)(4³·6²·8)₂(4⁴·6²) and (12⁵·16)(12)₂ Schläfli symbols, respectively. The photoluminescent measurements reveal that both 1 and 2 exhibit bluish‐purple emissions in the solid state at room temperature. In addition, the compound 2 can serve as an antenna for sensitizing the visible‐emitting of the lanthanide cations to display their characteristic emissions.     

Synthesis,structure and property of diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene]tyrosinates

Five new diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene] tyrosinates, R₂Sn[2‐O‐3‐MeOC₆H₃CH=NCH (CH₂C₆H₄OH‐4)COO] (R = Me, 1 ; Et, 2 ; Bu, 3 ; Cy, 4 ; Ph, 5 ), have been synthesized and characterized by elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectra, and the X‐ray single crystal diffraction. In non‐coordinated solvent, complexes 1 – 5 have penta‐coordinated tin atom. In the solid state, 1 – 3 are centrosymmetric dimmers in which each tin atom is seven‐coordinated in a distorted pentagonal bipyramid, and 4 displays discrete molecular structure with distorted trigonal bipyramidal geometry, and the tin atom of 5 is hexa‐coordinated and possess the distorted octahedral geometry with a coordinational methanol molecule. The intermolecular O‐H???O hydrogen bonds in 1 – 4 link molecules into the different one‐dimensional supramolecular chain with R₂² (30) or R₂² (20) macrocycles, and the molecules of 5 are joined into a two‐dimensional supramolecular network containing R₄⁴ (24) and R₄⁴ (28) two macrocycles. Bioassay results against human tumour cell HeLa indicated that 3 ‐ 5 belonged to the efficient cytostatic agents and the activity decreased in the order 4 > 3 > 5 > 2 > 1. The fluorescence determinations show the complexes may be explored for potential luminescent materials.