Double Schiff Base Ligand Research Articles

Unprecedented Water Effect as a Key Element in Salicyl-Glycine Schiff Base Synthesis.

Salens, as chelating, double Schiff base ligands, are an important group utilized in transition metal catalysis. They have been used to build interesting functional metal-organic frameworks (MOFs). However, salens interacting with amino acids have also found applications in receptors. Here, we intended to form a “green” glycine-derived salen fragment, but the available literature data were contradictory. Therefore, we optimized the synthetic conditions and obtained the desired product as two different crystallographic polymorphs (orthorhombic Pcca and monoclinic P21/c space groups). Their structures differ in conformation at the glycine moiety, and the monoclinic form contains additional, disordered water molecules. Despite the high stability of Schiff bases, these newly obtained compounds hydrolyze in aqueous media, the process being accelerated by metal cations. These studies, accompanied by mechanistic considerations and solid-state moisture and thermal analysis, clarify the structure and behavior of this amino acid Schiff base and shed new light on the role of water in its stability.

Syntheses, spectroscopic characterization, SOD-like properties and antibacterial activities of dimer copper (II) and nickel (II) complexes based on imine ligands containing 2-aminothiophenol moiety: X-ray crystal structure determination of disulfide Schiff bases

A series of new dimer complexes of copper (II) and nickel (II) were designed and synthesized using the Schiff base ligands which was formed by the condensation of 2-aminothiophenol with 2- methoxybenzaldehyde, 3-formylbenzonitrile and 3-bromo-2-hydroxy-5-nitrobenzaldehyde, respectively. The synthesized metallic complexes were characterized by using different physicochemical and spectroscopic methods. The most plausible geometry for the 1:2 complexes appeared to be distorted square-planar or tetrahedral environments. All the synthesized metal complexes are found to be binuclear and confirmed by elemental analyses, magnetic susceptibility measurements and ESR spectroscopy. The Schiff base ligands (HL1/HL2/H2L) were coordinated to the metal ions through the ONS/SNN and/or N, S donor atoms. In order to prevent the oxidation of the thiol group during the formation of Schiff bases and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structures of the Schiff base ligands showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff bases as a new double Schiff base ligands (L1a/L2a/H2La). The L1b ligand is a bicyclic ring system of N, S-containing heterocyclic. The crystal structures of the double Schiff bases were determined by single crystal X-ray diffraction. The molar conductivity values of the complexes in DMSO implied the presence of non-electrolyte species. The SOD-like activity of Schiff bases and its complexes were investigated by NBT-DMSO assay and IC50 values were evaluated. Their biological properties have also been studied. These complexes were also tested for their in vitro antibacterial screening activities against three bacteria (Streptococcus aureus, Salmonella typhi, and Escherichia coli) comparing with the Schiff base ligands. Most of the complexes have higher antibacterial activities than those of the free Schiff bases, double Schiff bases and the control.

H-bonding directed formation of 1D-single chains, 2D-sheets, and 3D structures in magnetically coupled tetranuclear nickel(II) complexes with incomplete double cubane core

Reactions of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and 2-amino-1,3-propanediol (APD) in the presence of nickel(II) salts, NiX2 (X=CH3CO2−, NO3−, Cl−, ClO4−, BF4−)/sodium azide (NaN3), and triethylamine (TEA), in one pot self-assemble giving tetranuclear coordination complexes of nickel(II) with an incomplete double cubane structural core: [Ni4(H2L−1)2(μ-CH3CO2)2(μ3-X)2(μ-1,1-N3)2]·2CH3OH {X=1,1,1-N3 (1A) and OCH3 (1B)}, [Ni4(H2L−1)2(μ-1,1-N3)2(N3)2(μ3-OCH3)2 (H2O)2] (2), [Ni4(H2L−1)2(μ3-1,1,1-N3)2(μ-1,1-N3)2(CH3OH)2Cl2]·4CH3OH (3), [Ni4(H4L1−1)2(μ3-1,1,1-N3)2(μ-1,1-N3)2(CH3OH)2(OH)2]·2H2O (4), and [Ni4(HL2−2)2(APD−1)2][ClO4]2·2H2O·2CH3OH (5). In 1–3, H2L−1, in 4, H4L1−1, and in 5, HL22− represent a singly deprotonated chiral, potentially pentadentate trianionic double Schiff base ligand, H3L; a singly deprotonated potentially heptadentate pentaanionic double Schiff base ligand, H5L1; and a doubly deprotonated potentially tetradentate trianionic single Schiff base ligand, H3L2 respectively. In 1A, 3, and 4 two dinickel (Ni2) units are connected through two doubly bridging end-on (EO) μ-azido and two triply bridging EO μ3-azido bridges and in 2, though two EO μ-azido and two μ3-1,1,1-methoxy bridges generating tetranuclear units. In each dinuclear unit two nickel centers are bridged through one μ-phenolate oxygen from H2L−1, one μ-CH3CO2−, and one EO μ3-azido nitrogen (1) and through one μ-phenolate oxygen from H2L−1/H4L1−1 and one μ3-methoxy oxygen (2)/one μ3-azido nitrogen (3 and 4). In 5, two nickel(II) ions in the dinuclear unit are bridged though phenoxide oxygen and alkoxide oxygen bridges and two dinuclear units are interconnected via six symmetry related alkoxide bridges forming tetranickel units. In 1–4 neutral tetranuclear [Ni4] units and in 5, cationic tetranickel [Ni4]2+ units are interconnected by a symmetrical network of H-bonding between coordinated/uncoordinated hydroxido groups in the side arms of the double Schiff-base ligands, coordinated hydroxide ion/chloride ion, and uncoordinated methanol/water molecules producing H-bonding stabilized 2D-sheet structures (1, 2, 4), a 1D-single chains (3), and a 3D structure (5). Bulk magnetization measurements on 1–4 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Ni(II) ions with coupling constants (J1, J2, and J3) ranging from 13.19 to 22.10, (−9.05) to (1.74), and 14.79 to 25.59cm−1 respectively (in the Ĥ=-2J1(Ŝ1Ŝ3+Ŝ2Ŝ4)-2J2(Ŝ1Ŝ4+Ŝ2Ŝ3)-2J3(Ŝ1Ŝ2)+D(ŜZ12+ŜZ22+ŜZ32+ŜZ42) expression). [Display omitted]

Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

Facile high-yield synthesis of unsymmetric end-off compartmental double Schiff-base ligands: easy access to mononuclear precursor and unsymmetric dinuclear complexes

Novel approach to unsymmetric end-off compartmental ligands with a selective high-yield synthesis and access to unsymmetric dinuclear complexes.

Microwave Irradiated and Conventional Syntheses of Halogenated Symmetric Double Schiff Bases, their Spectral and Microbial Study

The aim of the present work was to discover various synthetic route of biological active halogenated symmetric double Schiff bases of 1,1’-bis (4-aminophenyl) cyclohexane, their spectral and microbial study. Symmetric double Schiff base ligands of halogenated benzaldehyde and 1,1’-bis (4-aminophenyl) cyclohexane were synthesized by conventional and green chemistry approach. The purity of Schiff bases was checked by Thin Layer Chromatography (TLC). The structures of these ligands were elucidated by UV, FTIR, 1HNMR and MS; and assayed for their antibacterial activity against Escherichia coli (E. coli), Bacillus megaterium (B.mega), Proteus vulgaris (P. vulgaris, Staphylococcus aureus (S. aureus) and Aspergillus niger (A. niger)The minimum inhibition concentrations (MIC) of the compounds were studied by cup plate method. Schiff bases revealed moderate antimicrobial activity and good antifungal activity against chosen standard drugs and microorganisms.

Microwave Irradiated and Conventional Syntheses of Halogenated Symmetric Double Schiff Bases, their Spectral and Microbial Study

The aim of the present work was to discover various synthetic route of biological active halogenated symmetric double Schiff bases of 1,1’-bis (4-aminophenyl) cyclohexane, their spectral and microbial study. Symmetric double Schiff base ligands of halogenated benzaldehyde and 1,1’-bis (4-aminophenyl) cyclohexane were synthesized by conventional and green chemistry approach. The purity of Schiff bases was checked by Thin Layer Chromatography (TLC). The structures of these ligands were elucidated by UV, FTIR, 1HNMR and MS; and assayed for their antibacterial activity against Escherichia coli (E. coli), Bacillus megaterium (B.mega), Proteus vulgaris (P. vulgaris, Staphylococcus aureus (S. aureus) and Aspergillus niger (A. niger)The minimum inhibition concentrations (MIC) of the compounds were studied by cup plate method. Schiff bases revealed moderate antimicrobial activity and good antifungal activity against chosen standard drugs and microorganisms.

Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands

A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150mVs−1 scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction.

Synthesis, crystal structure and electrocatalytic behavior of a copper (II) complex derived from acylpyrazolone double Schiff bases

A new double Schiff base complex, Cu(PMαFP)2en (HPMαFP = 1‐phenyl‐3‐methyl‐4‐(2‐furoyl)‐5‐pyrazolone, en = ethylenediamine), has been synthesized and characterized by elemental analysis, IR, UV, fluorescence spectra, thermal analysis, X‐ray single crystal diffraction and cyclic voltammetry (CV). Its crystal structure is monoclinic with space group Pbca and cell parameters: a = 22.263(3)Å, b = 13.671(2)Å, c = 10.0920(16)Å, Z = 4, S = 1.028, R1 = 0.0500 and wR2 = 0.1285. It was found that the Cu2+ ion is located in the coordination center. The Cu(II) has a slightly distorted plane quadrilateral coordination environment with two oxygen atoms and two nitrogen atoms of double Schiff base ligand in the equatorial plane. The complex has a one‐dimensional chain supramolecular structure, which is connected by CH…N bonding interactions. In the electrochemical experiments, the CV curve displays an oxidation peak in the presence of uric acid with Ep = 0.216V in pH = 7.0, showing that the Cu(PMαFP)2en/glassy carbon modified electrode has an electrocatalytic activity toward uric acid.

Cd(II)-Schiff-Base Metal–Organic Frameworks: Synthesis, Structure, and Reversible Adsorption and Separation of Volatile Chlorocarbons

A new Cd(II)-MOF (1) was successfully synthesized on the basis of a new long double Schiff-base ligand and Cd(SCN)2. Its crystal structure was determined by X-ray diffraction. In 1, each pair of Cd(II) nodes is bridged by two inversely related μ-SCN– to form infinite inorganic chains with the remaining two trans-positions being occupied by two Schiff-base ligands to generate a 3D framework with rhombus-like channel (∼9 × 9 A). 1 can reversibly absorb CH2Cl2 and CHCl3 at different temperature without collapsing of the host framework. Furthermore, it displays a strict size selectivity and can completely separate these volatile chlorocarbons of CH2Cl2 and CHCl3 in liquid and vapor phases.

Two Cd(II) Complexes with One New Polydentate Double Schiff Base Ligand Derived from 1,10-phenanthroline and Two Anionic Ligands: Syntheses, Structures, and Fluorescent Properties

Two Cd(II) coordination compounds of a polydentate double Schiff base ligand 1,10-phenanthroline-2,9-dicarboxaldehyde-di-2-hydroxybenzoylhydrazone (L), [Cd(L)(dca)2]·0.5H2O (dca = dicyanamide) (1) and [Cd(L)(SCN)2]·CHCl3·DMF (DMF = N, N′-dimethylformamide) (2) were synthesized and structurally characterized. Compounds 1 and 2 crystallized in monoclinic system with the space group C2/C and P21/n, respectively. The ligand L, acting as a hexadentate chelate, is coordinated to one Cd(II) atom with rare hexagonal bipyramid coordination geometry in these two compounds. Fluorescent measurements showed that these two compounds all strongly emit at 570 nm with the excitation of ultraviolet light at 360 nm.

Two di-nuclear Cd(II) and Mn(II) complexes with one new poly-dentate double Schiff base ligand derived from 1,10-phenanthroline: Syntheses, structures, and physical properties

A new poly-dentate double Schiff base ligand 1,10-phenanthroline-2,9-dicarboxaldehyde-di-2-hydroxybenzoylhydrazone (H 2 L) was synthesized and structurally characterized. Two Cd II and Mn II dimers of this ligand were also synthesized, and their crystal structures and photoelectronic spectra were characterized. In the two dimers, ligand L acts as a bridge in the interesting mono–poly-dentate bridging mode. The ligand and its Cd II complex strongly emit at 525 nm and 570 nm, respectively, and thus can be utilized as potential fluorescent materials. Furthermore, magnetization measurements for its Mn II dimer in the range 5–300 K indicate two magnetic orderings, at high temperature ( T > 230 K) a ferromagnetic ordering is observed, and below this temperature, an antiferromagnetic behavior takes place.

One Cadmium(II) Complex of a New Polydentate Double Schiff Base Ligand Derived from 1,10-phenanthroline: Syntheses, Structures, and Fluorescent Property

One Cd(II) complex of a new polydentate double Schiff base ligand 1,10-phenanthroline-2,9-dicarboxaldehyde-di-picolinohydrazone (L), [Cd(L)(SCN)2], was synthesized and structurally characterized. This compound belongs to a monoclinic system with space group C2/c. In this monomer, the cadmium metal center is coordinated to four nitrogen atoms and two oxygen atoms from one organic ligand L acting as a hexadentate chelate, and two nitrogen atoms from two distinct SCN− anions, forming an uncommon distorted hexagonal bipyramid coordination geometry. Furthermore, fluorescent and thermal properties of the complex were performed on the powder sample. The complex strongly emits at 467 nm with the excitation of 410 nm and is thermally stable up to 300°C, and thus can be utilized as one potential fluorescent material.

Copper Coordination Polymers Based on Single-Chain or Sheet Structures Involving Dinuclear and Tetranuclear Copper(II) Units: Synthesis, Structures, and Magnetostructural Correlations

Reactions between the potentially pentadentate (N(2)O(3)), trianionic double Schiff-base ligand 2,6-bis[[(2-hydroxyethyl)imino]methyl]-4-methylphenol (H(3)L) and Cu(CH(3)CO(2))(2) or Cu(ClO(4))(2), in the presence of NaN(3), give novel coordination polymers with chain {[Cu(2)(H(2)L)(N(3))(3)](2).H(2)O}(n) (1) or sheet [Cu(2)(H(2)L)(N(3))(3)](n) (2) and [Cu(2)(HL)(N(3))](n)[ClO(4)](n) (3) structures, respectively. These clusters are comprised of repeating dinuclear units (1) or their dimers (2 and 3). In these compounds, H(3)L acts as a tridentate (N(2)O) monoanionic (1), tetradentate (ON(2)O) monoanionic (2), or pentadentate (O(3)N(2)) dianionic (3) ligand. Compound [Cu(2)(HL)(N(3))(2)(H(2)O)].0.5CH(3)OH (4) formed from the reaction of Cu(CH(3)CO(2))(2) with H(3)L under reflux, which did not afford crystals suitable for X-ray studies. X-ray structure determinations have revealed that the basic building block in 1-3 comprises two copper centers bridged through one mu-phenolate O atom from H(2)L(-) or HL(2-) and one mu-azido(N1,N1) ion. Compounds 1-3 unveil three different ways in which this Cu(2) basic unit may be organized in the crystalline phase at the supramolecular level through a variety of bridging interactions involving additional azide ligands or alkoxide groups from the side arms of the ligand H(3)L. Bulk magnetization measurements have served to demonstrate that the magnetic interactions are completely dominated by the strong antiferromagnetic coupling occurring within the Cu(2) building block, with coupling constants ranging from 330 to 560 cm(-1) (in the H = -JS(1)S(2) convention). These results together have been incorporated with data from the few related copper dimers reported exhibiting the same bridging pattern into a study aimed at extracting possible magnetostructural correlations within this Cu(2) unit. An earlier predicted correlation between J and the angle formed by the phenoxide bridge and the Cu(2) core has been identified for the first time.

Self-assembly of mixed-valence Co(ii/iii) and Ni(ii) clusters: azide-bridged 1D single chain coordination polymers comprised of tetranuclear units, tetranuclear Co(ii/iii) complexes, ferromagnetically coupled azide-bridged tetranuclear, and hexanuclear Ni(ii) complexes: synthesis, structural, and magnetic properties

One-pot reactions between 2,6-diformyl-4-methylphenol (DFMP) and 2-aminoethanol (AE) in the presence of cobalt(II) salts [Co(ClO4)2, CoCl2, Co(CH3CO2)2, Co(NO3)2] and sodium azide result in the self-assembly of novel one-dimensional single chain mixed-valence cobalt coordination polymers {[Co2(II)Co2(III) (HL)2(OCH3)2(N3)3]ClO(4).5H2O.CH3OH}n (1), {[Co2(II)Co2(III) (HL)2(OCH3)2(N3)3]Cl.H2O}n (2) in which tetra-cobalt cationic units are bridged by symmetrical 1,3-azides, forming single chains; mixed valence neutral tetranuclear clusters [Co2(II)Co2(III) (HL)2(OCH3)2(N3)4]CH3OH.2H2O (3), [Co2(II)Co2(III)(HL)2(OCH3)2(N3)2(CH3CO2)2].2CH3OH.2H2O (4), and the cationic cluster [Co2(II) Co2(III) (HL)2(OCH3)2(CH3OH)2(N3)2](NO3)2 (5). In all these reactions, H3L, the potentially pentadentate (N2O3), trianionic double Schiff base ligand 2,6-bis[(2-hydroxy-ethylimino)-methyl]-4-methylphenol is formed. The reaction between DFMP and AE in the presence of nickel(ii) salts and sodium azide in methanol-water mixture results in the self-assembly of ferromagnetically coupled hexanuclear complexes [Ni6(H2L)2(HL-1)2(H2O)2(N3)6](ClO4)(2).2CH3OH (6), and [Ni6(H2L)2(HL-1)2(CH3OH)2(N3)6](BF4)2 (7), involving double (H3L) and single (H2L-1) Schiff base ligands, and a neutral tetranuclear complex [Ni4(H2L)2(OCH3)2(CH3CO2)2(N3)2] (8) with only double Schiff-base (H3L). In these complexes, the nature of the anion and the reaction conditions seem to play an important role in directing the formation of tetranuclear, hexanuclear or polymeric clusters. All complexes involve divacant double cubane-type cores containing three to four different types of bridging ligands (phenoxy, azido, methoxy/alkoxy, and acetate). Variable temperature magnetic properties of these spin coupled clusters have been investigated and magneto-structural correlations have been established.

Meta-Phenylene-bridged double Schiff base copper(II) complexes as building blocks for 1D coordination polymers: Synthesis, crystal structure and magnetic properties

The new double Schiff-base ligands H 6ipa-hyhb and H 6ipa-hyhh were synthesized by condensation of a 4,6-diformylresorcinol derivative (ipa) with 4-hydroxy-butanoic acid hydrazide (hyhb) and 6-hydroxy-hexanoic acid hydrazide (hyhh). The reaction with copper(II) perchlorate in the presence of an appropriate co-ligand (Him = imidazole, Hpz = pyrazole) leads to the novel coordination polymers {[Cu 2(H 4ipa-hyhb)(Hpz) 2](ClO 4) 2} n ( 1), {[Cu 2(H 4ipa-hyhb)(Him) 2](ClO 4) 2} n ( 2), and {[Cu 2-(H 4ipa-hyhh)(Hpz) 2](ClO 4) 2} n ( 3). These coordination polymers are composed of primary building blocks with the general formula [Cu 2(H 4ipa-X)(L) 2] 2+ (X = hyhb, hyhh; L = Him, Hpz) which are linked by coordination of the hydroxyl groups of the ligand side chains at the apical position of copper(II) centers of adjacent building blocks. The resulting chains possess different topologies and therefore different supramolecular structures due to the variation in length of the ligand alkyl side chains. For the complexes 1 and 2 double hydroxyalkyl-bridged distorted ladder like chains are formed. Whereas in case of complex 3 single hydroxyalkyl-bridged chains are obtained which assemble to hydrogen bonded double chains. In the case of 1 and 2 these chains are cross-linked by hydrogen bonding interactions with the perchlorate counterions, whereas for 3 additional π–π stacking interaction are observed. The temperature-dependent magnetic measurements indicate weak antiferromagnetic interactions with coupling constants J = −26.1 cm −1 ( 1), J = −28.2 cm −1 ( 2), and J = −26.5 cm −1 ( 3). The magnetic exchange interaction is solely the result of a coupling within the dinuclear complex moieties through the central resorcinol moiety.

Ag(I) Complexes Generated from Double Schiff-Base Ligand with Thiazole as the Terminal Binding Sites

A double Schiff-base ligand 1,4-bis(2-thiazolyl)-2,3-diaza-1,3-butadiene (L8) has been synthesized, and its coordination chemistry with various silver salts AgX (X = SbF6-, SO3CF3-, H2PO4-, and NO3-) has been investigated. The resulting molecular structures are delicately dependent on the nature of the counterions and the solvent intermedia. Uncoordinating counterions (X = SbF6- and SO3CF3-) generated the hydrogen-bonded frameworks based on discrete molecular complex building blocks, whereas coordinating anions (X = H2PO4- and NO3-) formed polymeric complexes driven by the metal−anion interactions. Furthermore, the luminescent and electrical conductive properties of some new complexes were investigated.

Novel One- and Two-Dimensional Ag(I) Networks Generated from Double Schiff Base Ligands with Disubstituted Quinoxaline Diazenes as the Terminal Binding Sites

The new double Schiff base ligand L7 (2,5-bis(2-benzodiazine)-3,4-diaza-2,4-hexadiene) with disubstituted quinoxaline diazenes was synthesized. Four new polymeric Ag(I) complexes based on L7, namely {Ag3(L7)3(BF4)3(CH2Cl2)3(H2O)}n (1), {Ag2.5(L7)1.5(ClO4)2.5(H2O)2}n (2), {Ag4(L7)3(PF6)4}n (3), and {Ag4(L7)3(SbF6)4}n (4), have been synthesized successfully. They were fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In compound 1, two Ag(I) atoms are held together by two L7 ligands through the inside middle chelating N donors to generate a binuclear “X-shaped” helical secondary building block. In compounds 2−4, three Ag(I) atoms are held together by three L7 ligands through the inside middle chelating N donors to afford a trinuclear crownlike secondary building block. These spontaneous self-organized supramolecular secondary building blocks were further linked together into the higher extended hierarchy through outside N−Ag(I) coordination interactions. Compound 1 features a two-dimensional net containing a molecular cage, and compounds 2−4 feature two- (2 and 3) and one-dimensional (4) molecular crown-containing polymeric complexes in the solid state, respectively.