Copper(I) complexes of N-thioacylamido(thio)phosphates and triphenylphosphine

Heteroligand copper(I) complexes of bi- or bis-bidentate acylamidophosphates PhC(S)NHP(S)(OPr-i)₂, PhC(S)NHP(O)(OPr-i)₂, Et₂NC(S)NHP(S)(OPr-i)₂, PhNHC(S)NHP(S)(OPr-i)₂, N-(4-aminobenzo-15-crown-5)-C(S)NHP(S)(OPr-i)₂, N,N-(1,10-diaza-18-crown-6)-[C(S)NHP(S)(OPr-i)₂]₂, and triphenylphosphine were prepared and characterised. Copper is bound by two PPh₃ and one SCNPX (X = O, S) fragment of chelating ligand in all cases. Triphenylphosphine molecules reversibly dissociate in solution. Details of the X-ray structures of (Ph₃P)₂Cu[PhC(S)NP(S)(OPr-i)₂] and (Ph₃P)₂Cu[Et₂NC(S)NP(S)(OPr-i)₂] are reported.     

Aromatic N-oxide bridged copper(II) coordination polymers: Synthesis, characterization and magnetic properties

The complexes [Cu₂(o-NO₂-C₆H₄COO)₄(PNO)₂] (1), [Cu₂(C₆H₅COO)₄(2,2′-BPNO)]_n (2), [Cu₂(C₆H₅COO)₄(4,4′-BPNO)]_n (3), [Cu(p-OH-C₆H₄COO)₂(4,4′-BPNO)₂·H₂O]_n (4), (where PNO = pyridine N-oxide, 2,2′-BPNO = 2,2′-bipyridyl-N,N′-dioxide, 4,4′-BPNO = 4,4′-bipyridyl-N,N′-dioxide) are prepared and characterized and their magnetic properties are studied as a function of temperature. Complex 1 is a discrete dinuclear complex while complexes 2-4 are polymeric of which 2 and 3 have paddle wheel repeating units. Magnetic susceptibility measurements from polycrystalline samples of 1-4 revealed strong antiferromagnetic interactions within the {Cu₂}⁴⁺ paddle wheel units and no discernible interactions between the units. The complex 5, [Cu(NicoNO)₂·2H₂O]_n·4nH₂O, in which the bridging ligand to the adjacent copper(II) ions is nicotinate N-oxide (NicoNO) the transmitted interaction is very weakly antiferromagnetic.     

Syntheses and structures of bis(2,6-xylyl-nacnac) copper(I) complexes

The copper(I) complexes {(bis-2,6-dimethylphenyl-penta-2,3-diiminato)Cu}₂(μ-toluene), 3 has been prepared and its reactivity against Lewis bases and nitrous oxide investigated. Complex 3 crystallizes as a toluene-bridged dimer and forms mono- and dinuclear benzene adducts in C₆D₆ solution. It does not coordinate excess THF, but reacts quantitatively with 1 equiv. of acetonitrile. Reaction with 2,6-xylyl isonitrile yields (bis-2,6-dimethylphenyl-penta-2,3-diiminato)Cu(2,6-xylyl isonitrile), 5, (ν_CN = 2123 cm⁻¹), which was characterized by an X-ray diffraction study. Complex 3 does not react with nitrous oxide in either C₆D₆ solution (5 days 50 °C) or in diethyl ether (13 days at ambient temperature).     

Synthesis, mesomorphism and luminescence properties of palladium(II) and platinum(II) complexes with dimeric Schiff base liquid crystals

A series of ortho-metallated Pd and Pt complexes containing dimeric liquid crystals Schiff base as cyclometallated ligands and N-benzoyl thiourea derivatives as co-ligands were prepared and investigated for their liquid crystalline properties. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy while the mesogenic properties were investigated by DSC and polarising optical microscopy. The complexes show either monotropic or enantiotropic transitions with nematic and smectic A phases being displayed, with the mesomorphic behaviour strongly related to the type of N-benzoyl thiourea as well as the metal center used. The structure of a palladium(II) complex has been solved by X-ray diffraction.The platinum(II) complexes show photoluminescence properties both in solution and in solid state at room temperature, with the emission band centered around 600 nm. These are the first examples of metallomesogens based on Schiff base cyclometallated ligands that display luminescence properties.     

Zinc complexes of a tripodal ligand containing three different N-heterocyclic donor functions

The coordination chemistry of a chiral tripodal ligand L containing pyridyl, imidazolyl and pyrazolyl donor functions has been investigated in combination with zinc(II). While the reaction of a racemic mixture of L with ZnX₂ (X = Cl, Br) leads to complexes LZnX₂ with tetrahedrally coordinated zinc centres (the pyridyl donor function remains pending), the employment of Zn(ClO₄)₂ leads to the sandwich complex [L₂Zn](ClO₄)₂ which due to the two possible configurations for L (S and R) occurs in form of two diastereomers (the meso form and the enantiomeric pair SS/RR). The crystal structures of all three compounds are discussed.     

Synthesis and coordination behaviors of 14-membered tetraaza macrocyclic copper(II) complexes bearing two N-propionic acid or N-propionic methyl ester groups

A di-N-functionalized 14-membered tetraaza macrocycle, [H₄L³](ClO₄)₂ (L³ = 1,8-bis(2-carboxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane), has been synthesized by acid hydrolysis of 1,8-bis(2-cyanoethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (L²). The copper(II) complexes [CuL²](ClO₄)₂ and [Cu(H₂L³)](ClO₄)₂ were prepared and characterized. The complex [Cu(H₂L³)]²⁺ readily reacts with methanol to yield [CuL⁴]²⁺ (L⁴ = 1,8-bis(2-carbomethoxyethyl)-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane). The N-CH₂CH₂COOH groups of [Cu(H₂L³)](ClO₄)₂ are not coordinated to the metal ion in the solid state but are involved in coordination in various non-aqueous solvents or in aqueous solutions of pH ? 1.0. Interestingly, [CuL⁴](ClO₄)₂ exists as two stable structural isomers, 1 (the pendant ester groups are not involved in coordination) and 2 (one of the two ester groups is coordinated to the metal ion), in the solid state; the two isomers can be prepared selectively by controlling ionic strength of a methanol solution of the complex. Crystal structures and coordination behaviors of the two isomers are described. The di-N-cyanoethylated macrocyclic complex [CuL²](ClO₄)₂ is rapidly decomposed in 0.1 M NaOH solution even at room temperature. On the other hand, [Cu(H₂L³)](ClO₄)₂ and [CuL⁴](ClO₄)₂ are quite inert against decomposition under similar basic conditions. In acidic or basic aqueous solutions, [CuL⁴]²⁺ is hydrolyzed to [Cu(H₂L³)]²⁺ or [CuL³].     

Copper(II) PMDTA and copper(II) TMEDA complexes: precursors for the synthesis of dinuclear dicationic copper(II) complexes

Copper(II) cations coordinated with PMDTA (pentamethyldiethylenetriamine) and TMEDA (tetramethylethylenediamine) possess a high synthetic potential. The synthesis of these cations was carried out by metathesis reactions with silver salts. The cationic copper(II) complexes, [Cu(PMDTA)(Me₂CO)Cl]⁺, [Cu(PMDTA)(H₂O)Cl]⁺, [Cu(PMDTA)(DMF)]⁺, [Cu(PMDTA)Cl]⁺, [Cu(PMDTA)OAc]⁺, [Cu(PMDTA)(MeCN)₂]²⁺, [Cu₂(TMEDA)₂Cl₃]⁺ and [Cu(TMEDA)(MeCN)₃]²⁺ were synthesised as PF₆ salts, crystallised and characterised by single-crystal X-ray diffraction.     

Crystal structure and fluorescence of a europium (III) complex: EuCl3(2,2′-bipyridine N,N dioxide) · 2CH3OH

We report the synthesis and characterization of a seven coordinate europium complex, [EuCl₃(C₁₀H₈N₂O₂) ·  2CH₃OH]. The growing interest in developing efficient light conversion molecular devices (LCMDs) necessitates the need for new fluorescent materials. Ideal physicochemical properties of the materials include ligand absorption, efficient metal to ligand transfer, and strong luminescence with a relatively long decay time. The design of such material requires distinct absorbing (ligand) and emitting (metal ion) components. While Eu³⁺ cation has a non-degenerate emitting level, 2,2′-bipyridine N,N dioxide is a heterocyclic ligand known to exhibit strong luminescence. Additional characterization is also described, including single crystal X-ray diffraction, IR and UV-Vis spectroscopies and elemental analysis.     

Complexes of N-thiophosphorylthioureas RNHC(S)NHP(S)(OiPr)2 (HL) (R = pyridin-2-yl, pyridin-3-yl, 6-amino-pyridin-2-yl) with copper(I): Crystal structures of Cu(PPh3)nL (n = 1, 2)

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RNHC(S)NHP(S)(OiPr)₂ [R = pyridin-2-yl (HL^a), pyridin-3-yl (HL^b), 6-amino-pyridin-2-yl (HL^c)] with Cu(PPh₃)₃I in aqueous EtOH/CH₂Cl₂ leads to mononuclear [Cu(PPh₃)₂L^a,b-S,S′] (1, 2) and [Cu(PPh₃)L^c-S,S′] (3) complexes. Using copper(I) iodide instead of Cu(PPh₃)₃I, polynuclear complexes [Cu_n(L-S,S′)_n] (4-6) were obtained. The structures of these compounds were investigated by IR, ¹H, ³¹P{¹H} NMR spectroscopy, ES-MS and elemental analyses. The crystal structures of Cu(PPh₃)₂L^b (2) and Cu(PPh₃)L^c (3) were determined by single-crystal X-ray diffraction.     

Preparation of new tetraaza macrocyclic nickel(II) and copper(II) complexes bearing N-propionic methyl ester groups

A 14-membered tetraaza macrocycle, 2,13-bis(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.^1.180^7.12]docosane (L²) bearing two N-CH₂CH₂COOMe groups, and its nickel(II) and copper(II) complexes have been prepared and characterized. The nickel(II) and copper(II) complexes of 2-(2-carbomethoxyethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.^1.180^7.12]docosane (L³) containing one N-CH₂CH₂COOMe group have also been prepared. The crystal structure of [NiL²](ClO₄)₂ shows that the complex has a slightly distorted trans-octahedral coordination geometry with two relatively short axial Ni-O (N-CH₂CH₂COOMe group) bonds (2.136(3) Å). In various solvents, however, a considerable proportion of [NiL²]²⁺ exists as a square-planar form, in which the functional pendant arms are not involved in coordination. The proportion of the square-planar isomer varies with solvents in the order of nitromethane ? acetonitrile < H₂O < DMF ? DMSO. In the case of [CuL²](ClO₄)₂, only one N-CH₂CH₂COOMe group is involved in coordination. The N-CH₂CH₂COOMe group of [NiL³](ClO₄)₂ is not directly involved in coordination even in the solid state, though the functional group of [CuL³](ClO₄)₂ is coordinated to the metal ion.     

Synthesis of two configurational isomers of a 14-membered tetraaza macrocycle bearing N-CH2CH2CONH2 pendent arms and their copper(II) complexes: Crystal structures of the complexes

Two isomers of 1,8-bis(N-carbamoylethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L²) bearing two N-CH₂CH₂CONH₂ groups, C-meso-L² and C-racemic-L², have been prepared and characterized. Each isomer reacts with Cu(II) ion to form a five-coordinate complex, [Cu(C-meso-L²)](ClO₄)₂ (1) or [Cu(C-racemic-L²)](ClO₄)₂ (2), in which only one pendent amide group is coordinated to the metal ion. The crystal structure of 1 · CH₃CN shows that the complex possesses trans-III-type N-configuration and has a slightly distorted square-pyramidal coordination geometry with a relatively long axial Cu-O (N-CH₂CH₂CONH₂) bond (2.207(3) Å). On the other hand, 2 exhibits trans-V configuration and has a slightly distorted trigonal bipyramidal coordination geometry with a very short equatorial Cu-O (N-CH₂CH₂CONH₂) bond (2.007(3) Å); the Cu-O distance is distinctly shorter than the Cu-N distances (2.062(4)-2.090(4) Å). The complex 1 exhibits a d-d transition band at approximately 565 nm, whereas the band for 2 is observed at approximately 770 nm.     

Synthesis, structure and catalytic activity of low-spin dicyano iron(III) complexes of N,N-bis(quinolyl)malonamide derivatives

Two low-spin Fe(III) dicyano-dicarboxamido complexes have been prepared from N,N^′-bis(8-quinolyl)malonamide derivatives. Crystal structures show that the four nitrogen donors available to complex the metal are arranged in the equatorial plane with the two cyanides trans to each other in the axial positions when the malonyl moiety is disubstituted. In contrast, the unsubstituted malonyl results in only three nitrogens in the equatorial plane with the fourth in an apical position and the two cyanides occupying cis sites, one equatorial and the other axial. NMR analyses show that the solid state structure of both complexes is retained in solution. Both types of configurational complexes catalyze cyclic olefin oxidations with H₂O₂ but only the cis-dicyano complex catalyzes stilbene oxidation with formation of epoxides, diols and benzaldehyde.     

Bridged dinucleating N-heterocyclic carbene ligands and their double helical mercury(II) complexes

A series of six 3,6-bis(imidazolium-3-yl)pyridazine derivatives with different imidazole-N substituents have been synthesized and isolated as the salts [H₂L]Cl₂ (1a)-(6a) and [H₂L](PF₆)₂ (1b)-(6b). Solid state structures have been determined crystallographically for eleven out of the twelve compounds, revealing diverse hydrogen bonding patterns that involve the imidazolium-C²H units and the anions. N-heterocyclic carbene (NHC) mercury(II) complexes [Hg₂L₂](PF₆)₄ (7)-(9) are readily formed in good yields from ligand precursors [H₂L](PF₆)₂ and Hg(OAc)₂, as long as imidazole-N substituents are not too bulky. X-ray crystallography reveals double helical bimetallic arrangements for the stable [Hg₂L₂]⁴⁺ cations. Ligand scrambling in [Hg₂L₂]⁴⁺ occurs only in the presence of free carbene precursor, presumably via an associative mechanism.     

Reactions and structures in the gallium(III)/indium(III)-N,N-dimethylthioformamide systems

The structure of the N,N-dimethylthioformamide (DMTF) solvated gallium(III) ion has been determined in solution by means of extended X-ray absorption fine structure (EXAFS) spectroscopy. The gallium(III) ion is four-coordinate in tetrahedral fashion with a mean Ga-S bond distance of 2.233(2) Å in DMTF solution. At the dissolution of indium(III) perchlorate or trifluoromethanesulfonate in DMTF coordinated solvent molecules are partly reduced to sulfide ions, and a tetrameric complex with the composition [In₄S₄(SHN(CH₃)₂)₁₂]⁴⁺ is formed. The structure of the solid tetrameric complex in the perchlorate salt was solved with single crystal X-ray diffraction. Four indium(III) ions and four sulfide ions form a highly symmetric heterocubane structure where each indium binds three bridging sulfide ions and each sulfide ion binds three indium(III) ions with a mean In-S bond distance of 2.584(1) Å, and S-In-S angles of 90.3(1)°. Each indium(III) additionally binds three DMTF molecules at significantly longer mean In-S bond distance, 2.703(1) Å; the S-In-S angles are in the range 80.3-90.4°. Large angle X-ray scattering data on a DMTF solution of indium(III) trifluoromethanesulfonate show that the same tetrameric species characterized in the solid state is also present in solution, whereas the EXAFS measurements only give information about the In-S bond distances due to the short core hole lifetime.     

Rh(I) complexes containing tris(pyrazolyl)amine and bis(pyrazolyl)amine ligands: synthesis and NMR studies

The tris(pyrazolyl)amine ligands: tris[2-(1-pyrazolyl)methyl]amine (tpma), tris [3,5-dimethyl-1-pyrazolyl)methyl]amine (tdma), tris[2-(1-pyrazolyl)ethyl]amine (tpea), tris[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (tdea) and bis(pyrazolyl)amine ligands: bis[2-(1-pyrazolyl)ethyl]amine (bpea) and bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (bdea) react with [RhCl(cod)]₂ in presence of NaBF₄ (tpma, tdma and bdea) or AgBF₄ (tpea, tdea and bpea) to lead to [Rh(cod)L] (BF₄) (L=tpma (1), tdma (2), bdea (3), tpea (4), tdea (5) and bpea (6)). These complexes have been characterised by elemental analyses, conductivity, IR, ¹H and ¹³C NMR spectroscopy and liquid mass (with electrospray) spectrometry. The ¹H NMR spectra of 1, 2 show the presence of two isomers in solution in a 3:1 ratio (coordination κ² or κ³ type) in a thermodynamic equilibrium. The steric bulk of cyclo-octa-1,5-diene causes it to prefer the κ² mode of bonding as majority. Similar to previous published results, complexes 4 and 5 exist in a sole form in solution (probably κ² isomer). Finally, the complexes 3 and 6 are fluxional. A NMR study shows that this fluxional process is not frozen at 183 K.     

Versatile nuclearity in copper complexes with ortho functionalized 1,3-bis(aryl)triazenido ligands

The synthesis, characterization and crystal structures of three new copper complexes derived from 1,3-bis(aryl)triazenido ligands bearing either a methoxycarbonyl, methylthio or a hydroxymethyl group in the ortho position of one of the aromatic rings are reported. In addition to the coordination of the triazenido fragment, the Lewis basic groups coordinate to the copper centers to form complexes with different nuclearity: {1-[2-(methoxycarbonyl)phenyl]-3-[4-methylphenyl]}triazene and {1-[2-(methylthio)phenyl]-3-[4-methylphenyl]}triazene form stable dinuclear and tetranuclear Cu(I) complexes, respectively. Reaction of {1-[2-(hydroxymethyl)phenyl]-3-[4-methylphenyl]}triazene with either Cu(I) or Cu(II) results in a novel Cu(II) hexanuclear macrocyclic complex.     

Mononuclear and dinuclear bromo bridged iridium(I) complexes with N-allyl substituted imidazolin-2-ylidene ligands

The reaction of 1-methyl-3-(2-propenyl)imidazolium bromide (1) or 1,3-bis(2-propenyl)-imidazolium bromide (2) with [Ir(μ-OMe)(cod)]₂ afforded the five coordinated iridium(I) carbene complexes [IrBr(L)(cod)] (3) (L=1-methyl-3-(2-propenyl)imidazolin-2-ylidene) and (4) (L=1,3-bis(2-propenyl)imidazolin-2-ylidene). The reaction proceeds via an in situ deprotonation of the imidazolium salt. Molecular structure determinations on 3 and 4 confirmed the coordination of the carbene ligands via the carbene carbon atom and one allyl group in both complexes. Treatment of complex 3 with an excess of AgBF₄ gave the dinuclear bromo bridged complex [(Ir(μ-Br)(L)(cod)]₂BF₄ (5) (L=1-methyl-3-(2-propenyl)imidazolin-2-ylidene). The reaction of complex 4 with an excess of AgBF₄ led to the mononuclear complex [Ir(L)(cod)]BF₄ (6) (L=1,3-bis(2-propenyl)imidazolin-2-ylidene) where both N-allyl substituents are coordinated to the iridium(I) center.     

Synthesis and transition metal complexes of 3,3-bis(1-vinylimidazol-2-yl)propionic acid, a new N,N,O ligand suitable for copolymerisation

The new N,N,O heteroscorpionate ligand 3,3-bis(1-vinylimidazol-2-yl)propionic acid (Hbvip) (5) was synthesised in five steps starting from 1-vinylimidazole. This ligand is closely related to 3,3-bis(1-methylimidazol-2-yl)propionic acid (Hbmip), but contains two vinyl linker groups which can be used for radical-induced polymerisation reactions. The κ³-N,N,O coordination behaviour of 5 was proven by the synthesis of the tricarbonyl complexes [Re(bvip)(CO)₃] (6), [Mn(bvip)(CO)₃] (7) and [Cu(bvip)₂] (8). To obtain good yields of 6, it was synthesised in water instead of THF. The ligand as well as all three complexes were characterised by X-ray crystallography. Copolymerisation of 5 with pure methyl methacrylate (MMA) or a combination of MMA and ethylene glycol dimethacrylate (EGDMA) led to the solid phases P1 and P2. Polymer-bound rhenium and manganese tricarbonyl complexes could be obtained by the reaction of deprotonated P1 with [MBr(CO)₅] (M = Re, Mn) and also by copolymerisation of 6 and 7 with MMA. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymers. Furthermore, the content of metal incorporated in the polymers was determined by elemental analysis, AAS or ICP-OES measurements. Reaction of the deprotonated solid phase P1 with copper(II) chloride led to a blue solid-phase (P1-Cu). The UV-Vis absorption maximum of P1-Cu is found at 615 nm, which is almost identical to that found for 8. Thereby, it seems likely that P1 is flexible enough to form bisligand complexes with copper(II). This means that the copper centres act as a kind of crosslinking agents. In contrast, the heterogeneous reaction of P2 with copper(II) chloride yielded a lime green solid phase (P2-Cu). The bathochromic shift of the absorption maximum by 102 nm suggests one-sided bound copper centres.     

Synthetic, structural and spectroscopic studies of complexes derived from the copper(II) perchlorate/succinamic acid/N,N′-donor tertiary reaction systems

The use of succinamic acid (H₂sucm) in Cu(ClO₄)₂·6H₂O/N,N′-donor [2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 4,4′-dimethyl-2,2′-bipyridine (dmbpy), 4,4′-bipyridine (4,4′-bpy)] reaction mixtures yielded compounds [Cu₂(Hsucm)₃(bpy)₂](ClO₄)·0.5MeOH (1·0.5MeOH), [Cu₂(Hsucm)(OH)(H₂O)(bpy)](ClO₄)₂ (2), [Cu₄(Hsucm)₅(dmbpy)₄]_n(ClO₄)_3n·nH₂O ·0.53nMeOH (3·nH₂O·0.53nMeOH), [Cu₂(Hsucm)₂(dmbpy)₂(H₂O)₂](ClO₄)₂·2H₂O (4·2H₂O), [Cu₂(Hsucm)₂(phen)₂(H₂O)₂](ClO₄)₂·1.8MeOH (5·1.8MeOH), [Cu₂(Hsucm)₂(phen)₂(MeOH)₂](ClO₄)₂·MeOH (6·MeOH) and [Cu(Hsucm)₂(H₂O)(4,4′-bpy)]_n (7). The succinamate(−1) ligand exists in five different coordination modes in the structures of 1-7, i.e. the common syn, syn μ₂-κO:κO′ in 1-6, the μ₂-κ²O in 1, the μ₂-κ²O:κO′ in 1, the μ₃-κ²O:κ²O′ in 3, and the monodentate κO in 7. The primary amide group of Hsucm⁻ remains uncoordinated and participates in intra- and intermolecular hydrogen bonding interactions leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm⁻ ligands. The thermal decomposition of representative complexes was monitored by TG/DTG and DTA measurements.     

Crystal structures and third-order NLO properties in DMF solution of Co(II)-bpfp coordination polymers (bpfp=N,N-bis(pyridylformyl)piperazine)

Two novel Co(II) coordination polymers {[Co(H₂O)₂(CH₃OH)₂(4-bpfp)](NO₃)₂}_n1 (4-bpfp=N,N^′-bis(4-pyridylformyl)piperazine) and [Co(NCS)₂(CH₃OH)₂(3-bpfp)]_n2 (3-bpfp=N,N^′-bis(3-pyridylformyl)piperazine) have been synthesized and characterized by single crystal X-ray diffraction. Both the polymers consist of one-dimensional chains constructed by bridging bpfp ligands and Co(II) ions. The existence of O?H-O hydrogen bond in 1 and S?H-O hydrogen bond in 2 play important roles in creating interesting supramolecular structures. Their third-order nonlinear optical (NLO) properties in DMF solution have been studied by Z-scan technique. The results reveal that polymers 1 and 2 exhibit strong NLO absorption effects (α₂=9.00×10⁻¹¹ m W⁻¹ for 1; 1.41 × 10⁻¹⁰ m W⁻¹ for 2) and self-focusing performance (n₂=3.24×10⁻¹⁶ esu for 1; 3.05 × 10⁻¹⁶ esu for 2) in DMF solutions. The corresponding effective NLO susceptibilities χ⁽³⁾ values are 3.08 × 10⁻¹² esu (1) and 4.70 × 10⁻¹² esu (2). All of the values are comparable to those of the reported good NLO materials. Additionally, the TG-DTA results of the two polymers are in agreement with the crystal structures.