Phen Molecules Research Articles

Two new Cd(II)-based coordination polymers derived from flexible linker: Highly sensitive and selective “turn off-on” fluorescent sensors for ferric and dichromate ions

Coordination polymers (CPs) are peculiar multidimensional materials that find utility as luminescent sensors for ions and molecules existing in wastewater discharge. Herein, two new Cd(II)-based CPs with formula [Cd(L)(phen)]·0.5H2O (1) and [Cd(L)(2,2'-bipy)] (2) (H2L = 3,3'-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid, phen = 1,10-phenanthroline and 2,2'-bipy = 2,2'-bipyridine) have been synthesized and characterized. The single crystal X-ray analysis for 1 reveals that, Cd(II)-based centre adopts an octahedral geometry and is coordinated to four carboxyl O atoms from three L2- ligands and two N atoms from phen molecules. While, in CP 2, the Cd(II) centre is seven coordinated, which is completed by five carboxylate O atoms from two distinct L2− ligands and two N atoms from the 2,2-bipy ligand. Both 1 and 2 have been used as turn-off fluorescence sensor for selective and sensitive detection of Fe3+ and Cr2O72-. The CP 1 exhibited superior selectivity and sensitivity than 2 with limit of detection (LOD) 1.732×10-5 M and 5.996×10-6 M against Fe3+ and Cr2O72- respectively. Interestingly, the emissive behaviour of 1 get restored on adding 2-hydroxybenzoic acid (2-hyd acid) (turn on) due to the competitive formation of 2-hyd acid @Fe3+ or 2-hyd acid@Cr2O72- and concomitant release of 1. The fluorescence recovery selectivity of 2-hyd acid over other antioxidants has been attributed to the synergistic effect of high EHOMO value and a small space steric hindrance. The sensing properties of the MOF have been addressed with the help of Hirshfeld surface and density functional theory analyses.

Photodetector for visible light based on Fe(phen)2(SCN)2 molecule

This paper describes a unique method that uses Iron (phen) molecule [phen: 1,10-phenanthroline] placed on a glass substrate to create a photodetector (PD) that is sensitive to visible light as a heterostructure device. The structural, morphological, and optical properties of the samples were investigated using techniques such as X-ray diffraction (XRD), energy dispersive X-ray spectra (EDX), field emission scanning electron microscopy (FESEM), and UV-Vis spectrophotometry. The photosensitivity of the Iron (phen) /glass PD was evaluated at different bias voltages (5, 10, 15, and 20 V) at wavelength of 510 nm. The photosensitivity values were found to be 58.45, 76.82, 84.9, and 87.83, indicating the PD's ability to generate a measurable electrical response to light stimuli in the visible range. Furthermore, the response and recovery times of the Iron (phen) PD were assessed when exposed to pulsed visible light at a wavelength of 510 nm and bias voltages of 5, 10, 15 and 20 V. The results indicated favorable response and recovery times, suggesting the PD's capability to quickly detect and recover from changes in light intensity. At a bias voltage of 20 V and under illumination with visible light at 510 nm, the Iron (phen) PD demonstrated a maximum current gain of 9.22 and a quantum efficiency (ƞ) of 28.17. These values indicate the PD's ability to amplify the generated electrical current and efficiently convert incident photons into detectable electrical signals. Overall, the fabricated Iron (phen) glass PD exhibited promising photosensitivity, response and recovery times, current gain, and quantum efficiency when exposed to visible light. The findings suggest the potential application of Iron (phen) as a material for visible light photodetection.

Enhanced luminescent properties of poly(sodium acrylate)-based composite and its selective interaction towards copper ions

This study investigates the luminescent properties and metal ion interactions of europium when combined with a polymer chain of poly (sodium acrylate) (PSA) and a phenanthroline (Phen) molecule, which acts as an efficient antenna. The study of interactions between lanthanide ions and various compounds in different matrices is crucial, providing valuable insights into the molecular environment, and enabling a deeper understanding of processes affecting their luminescence. In this study, we investigated the luminescent properties of the Eu(PSA)Phen complex and its remarkable capacity for selective interaction with Cu2+ ions in an aqueous solution. From this selective interaction, we conducted a series of detailed studies that provided valuable insights into the mechanisms of luminescence suppression, information about the europium chemical environment, and other related aspects. The luminescence of Eu(PSA)Phen is significantly quenched by Cu2+ ions, driven by both static and dynamic mechanisms. The presence of the PSA polymer chain and Phen molecules within the composite exerts a profound influence on energy transfer processes, enabling selective responses to Cu2+ ions, even in the presence of competing cations. Additionally, we observed a preferential interaction of the PSA molecule in the Eu(PSA)Phen composite with Cu2+ ions over the N groups of phenanthroline. These findings underscore the compound potential as a versatile tool in various fields, ranging from material science to biosensing, where rapid and selective metal ion detection is of paramount importance.

Exploiting the Coordination Effect in Fe-Phenanthroline Complex for the Catalytic Carbonization of Phenanthroline toward the High Capacity Anode Grade Carbon

Aromatic organic molecules (AOMs) present an appealing precursor option for anode-grade hard carbon for sodium-ion batteries (SIBs) because of their prevalence, diverse chemical functionalities, and huge scope for nanostructure engineering at the molecular level. However, most small organic molecules decompose before actual carbonization is initiated unless reactions are carried out under high pressures or in the presence of catalysts. Herein, we report a facile carbonization of aromatic monomeric phenanthroline (phen) by exploiting the strong molecule-level coordination effect of the Fe-phen complex and in situ catalysis affected by Fe. With this carbonization strategy, we achieve better scalability with appreciable carbon yield, while carbonization of simple phen molecule returns zero carbon yields. The as-prepared N-doped microporous carbon (NMC) possesses desirable microstructural features with optimum nitrogen content to be employed as an anode for SIB. As an anode, the NMC delivers a high reversible capacity of 271 mAh g–1 at 100 mA g–1, an ultrahigh rate capability of 101 mAh g–1 at 1 A g–1, and a stable cycle life. The galvanostatic intermittent titration technique (GITT) depicts sodium ion diffusion coefficients of the order of ∼10–13 (cm2 s–1) in the intercalation region, which implies a faster sodium ion diffusion rate compared to most of the reported hard carbons. Given the vast diversity of AOMs, this work encourages new research interests to produce advanced carbon materials with nanostructure engineering at the molecular level for sodium-ion battery applications.

High performance solution-processed red phosphorescent organic light-emitting diodes by co-doping europium complex as sensitizer

In this work, efficient red phosphorescent OLEDs (PHOLEDs) were designed and fabricated by solution processing method. Based on well optimized doping concentrations of emitter and ratio of mixed host materials, Eu(DBM) 3 Phen (DBM = 1,3-diphenylpropane-1,3-dion, Phen = 1,10-phenonthroline) was doped into the light-emitting layer (EML) which plays the role of sensitizer. Experimental results indicated that the incorporation of Eu(DBM) 3 Phen molecules can effectively trap the superfluous electrons within EML, which is helpful for balancing charges’ distribution and widening the recombination zone. Besides, the presence of Eu(DBM) 3 Phen molecules can accelerate the transfer of triplet energy from hosts to red emitters, therefore remarkably enhances device performance. By optimizing the doping concentrations of emitter and sensitizer, ratio of co-hosts and the functional layer thickness, recombination center was accurately adjusted to further broaden recombination zone, therefore causing decreased excitons density and suppressed excitons quenching. Eventually, the optimal solution-processed red PHOLED obtained the maximum current efficiency (47.12 cd/A) and external quantum efficiency (27.3%). High performance solution-processed red phosphorescent organic light-emitting diodes by incorporating trivalent rare earth europium complex Eu(DBM) 3 Phen (DBM = 1,3-diphenylpropane-1,3-dion, Phen = 1,10-phenonthroline) into light-emitting layer as sensitizer. • High performance solution-processed red phosphorescent OLED was designed by utilizing trivalent rare earth europium complex Eu(DBM) 3 Phen into light-emitting layer as sensitizer. • Co-doped sensitizer molecules function as electron trappers, which is helpful in balancing carriers' distribution and broadening recombination zone. • The optimal solution-processed red PHOLED obtained the maximum current efficiency up to 47.12 cd/A and external quantum efficiency up to 27.3%. • This work firstly demonstrated the efficacy of utilizing rare earth complex as sensitizer in realizing high performance solution-processed OLEDs.

Multifunctional Cd-CP for fluorescence sensing of Cr(VI), MnO4−, acetylacetone and ascorbic acid in aqueous solutions

The development of multifunctional fluorescent chemosensors for the detection of multiple targets remains challenging but of great importance. In this paper, one novel coordination polymer (CP), denoted as [Cd2(edda)(phen)2]∙H2O (compound 1, H4edda = 5,5′ (ethane-1,2-diylbis(oxy)) diisophthalic acid, phen = 1,10-phenanthroline) is successfully designed and prepared under hydrothermal conditions. Structural analysis indicates that compound 1 possesses a one-dimensional (1D) double chain structure, then self-assembles into a three-dimensional (3D) supramolecular framework via π…π interactions between phen molecules. Interestingly, compound 1 is found to be tolerant in wide range of acidic to alkaline aqueous solutions (pH = 2–13). Fluorescent spectral investigations reveal that compound 1 exhibits highly selective and sensitive fluorescence responses toward MnO4−, Cr(VI) ions, acetylacetone (acac) and ascorbic acid (AA) by fluorescence quenching in the aqueous phase. The detection limits are in the very low range, reaching μM level for the detection of MnO4−, Cr(VI) ions, nM for AA and ppm for acac detection. The distinguished multi-responsive performance suggests compound 1 to be a potential multifunctional probe. Furthermore, the possible quenching mechanisms have also been systematically investigated in this work.

Corrosion-sensing and self-healing dual-function coating based on 1,10-phenanthroline loaded urea formaldehyde microcapsules for carbon steel protection

In this work, a smart coating with corrosion-sensing and self-healing dual functions was developed on carbon steel by incorporating the urea formaldehyde (UF) microcapsules loaded with 1,10-phenanthroline (Phen) molecules. Phen as both the corrosion-sensing indicator and corrosion inhibitor was encapsulated into the UF microcapsules via the oil-water (O/W) emulsion in-situ polymerization method. When the coating was damaged, the Phen molecules released from UF/Phen microcapsules would react with the Fe2+ ions generated from the active anodic corrosion site of the carbon steel substrate, and displayed a prominent red color chelate compound for corrosion-sensing application. During the neutral salt spray test, the corrosion evolution underneath the damaged coating can be rapidly detected within 15 min. Besides, the corrosion activity near the coating scratch can be effectively inhibited due to the adsorption of released Phen on the exposed substrate surface. After 72 h of immersion in 3.5 wt% NaCl solution, the low frequency impedance modulus of the scratched coating containing 10 wt% UF/Phen microcapsules was almost 7 times that of the scratched blank coating. The smart coating can not only achieve timely corrosion sensing, but also suppress the corrosion activity, which is of great importance for practical corrosion protection applications.

Corrosion self-diagnosing and self-repairing polymeric coatings based on zeolitic imidazolate framework decorated hydroxyapatite nanocontainer on steel

• Novel ZIF decorated HA nanocontainer with stimulus responsiveness were developed. • Encapsulation of Phen in nanocontainer can be easily achieved by one-step method. • Localized corrosion can be timely and precisely located and reported. • Coating exhibits barrier, corrosion self-diagnosing and self-repairing traits. Polymeric coatings with long life, strong environmental adaptability and high durability are of great significance for practical applications. This work presents a facial strategy to construct a smart nanocomposite coating with excellent shielding, corrosion self-diagnosing and self-repairing functions by integrating nanocontainers into epoxy resin. The nanocontainers were synthesized through decorating the hydroxyapatite sheets with zeolitic imidazolate frameworks (HA-ZIF), which were employed to encapsulate corrosion probe (Phenanthroline, Phen). With the occurrence of localized corrosion, Phen molecules could be timely released and reacted with the metal ions to form conspicuous red color at damaged sites, achieving real time corrosion diagnosing function. Given the stimulus responsive property of ZIF, the corrosion propagating process can be significantly inhibited by the released benzimidazole. As contrast of the traditional nanocontainers applied in anticorrosion coating, the inhibitors were used directly to synthesis the HA-ZIF nanocontainer rather than subsequent loading, which greatly improved inhibitors content in nanocontainers. Moreover, the impermeability of composite coating has been remarkably enhanced by the presence of HA sheets, ensuring the long-term protective performance. Importantly, the integrating multi functions in one coating is realized in the ingeniously designed nanocontainers. It is envisioned that the facial and feasible strategy provides insights in improving the longevity, functionality and reliability of protective coatings.

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity.

The electron-rich squarate ion (C4O42-, SA2-) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal-organic complexes with the SA2- group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4'-bipyridine (bpy), 4,4'-bipyridine-N,N'-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4'-vinylenedipyridine (vidpy), and in situ formed oxalate (OA2-) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA2- and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a "sandwich-like" structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (Ea) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA2- → SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA2- organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

A Mechanistic Understanding of Electrochemical Bistability Induced By the Presence of 1,10-Phenanthroline in the Cathodic Deposition of Copper

We report herein a precise control of the electrochemical bistability induced by surface area changes during the cathodic deposition of copper. Small additions of 1,10-phenanthroline (Phen) in the reaction media present an inhibiting effect on the global rate mainly due to the adsorption of protonated Phen. The increase of its concentration favors a shrinkage of the bifurcation diagram and shifts it to less negative potentials. The dynamic instability is verified by impedance measurements, and a negative impedance is clearly found. We calculated the apparent molar mass of the adsorbents using in situ gravimetric monitoring in the electrochemical experiments, and the results indicate that mass changes occur mainly due to the reduction of copper from bivalent ions dissolved in the reaction media. Importantly, the adsorption of protonated Phen molecules does not show a considerable contribution in mass variations but prevents the formation of a copper course grained morphology over the surface. Imaging analysis indicates finer nodulations at the lower branch compared to the upper branch in the bistability domain. On the basis of these observations, a kinetic mechanism is proposed and a good agreement is obtained between the apparent molar mass extracted from experiments and the theoretical values. Altogether, our results contribute to a detailed physicochemical description of the nonlinear behavior, bringing new insights about this reaction and pointing out the possibility to design switchable surface electrodes by taking advantage of the bistable behavior.Rospendowiski, J.; Pinto, M. R.; Hessel, C.; Sitta, E.; Nagao, R. ACS Omega 2018, 3, 13636.

Nanoscale supramolecular architectures assembly of copper cyanide, organotin, and 1,10‐phenanthroline coordination polymers: Design and biological applications

The nanosized supramolecular coordination polymers (SCPs)3∞[Cu(μ2CN)2]2.(Me3Sn)2.(phen)2],SCP1,and [Cu2(CN)4(Ph3Sn)2(phen)],SCP2, were prepared utilizing self‐assembly method under ultrasonic irradiation. Single crystal X‐ray diffraction (XRD) of SCP1supports the presence of two anionic [Cu(μ2CN)2]−fragments connected by two (Me3Sn)+cations, while the two phenanthroline (phen) molecules coordinate to the Cu atoms. The two Cu atoms are crystallographically different, while they are chemically identical forming tetrahedral geometry. The structure of SCP2was achieved by calculations using DFT (the density functional theory) and spectroscopic studies. The geometries around the Cu atoms adopt triagonal plane and tetrahedral structure. Spectroscopic data, energy‐dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), and analytical analysis confirm the chemical formula of SCP2. The nanosized tested compounds1and2are designed to investigate their action on viability and proliferation of five human cancer cell lines. In addition, 2, 2'‐azino‐bis (3‐ethyl benzthiazoline‐6‐sulfonic acid) (ABTS) assay and rate erythrocyte hemolysis were used to test the antioxidant activity of the nanosized SCP1and SCP2. Also, the SCP1and2exhibit good antimicrobial activity keeping them as promising drug candidates for the treatment of bacterial and fungal infections.

Synthesis, crystal structure and properties of a yttrium complex based on mixed functional ligands

A new yttrium complex, [Y 2 (H 2 Dhbds) 3 (phen) 2 ]·[Y 2 (H 2 Dhbds) 2 (H 2 Thbs)(phen) 2 ] ( 1 ) (Na 2 H 2 Dhbds = 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt; NaH 3 Thbs = 2,3,5-trihydroxy-1-benzenesulfonic acid sodium salt), has been synthesized and structurally characterized. Complex 1 consists of two dinuclear structural units bridged by H 2 Dhbds 2- and H 2 Thbs 2- ligands, where phen molecules act as N, N-bidentate ligands, chelating Y atoms. The dinuclear structural units are connected by π-π stacking interactions between phen molecules, generating a one-dimensional chain structure. In addition, complex 1 exhibits the broad fluorescent emission band at 365 nm, which originates from intraligand charge transitions.

Hydrothermal Synthesis, Characterization, and Property of a Thulium Dinuclear Complex Based on Sulfonate-Phenol Ligand and 1,10-Phenanthroline

A new lanthanide metal complex [Tm2(H2L)3(phen)2] (1) (Na2H2L = 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt, phen = 1,10-phenanthroline) was synthesized by hydrothermal method. It has been characterized by single crystal X-ray diffraction, elemental analysis and thermogravimetric (TG) analysis. The X-ray diffraction analysis revealed that the dinuclear thulium complex is formed with three bridged H2L2– ligands and one phen molecule around each thulium center. The center thulium atoms are eight-coordinate in distorted double-capped triangular prism and dodecahedral geometries, respectively. Each bridged H2L2– acts as a tetradentate ligand with a non-coordinated sulfonate group. To the best of our knowledge, complex 1 is the first example of a dinuclear H2L2–-bridged lanthanide complex with phen molecules. It exhibits the fluorescent emission at 475, 538, and 615 nm, which are attributed to the 1G4-3H6, 1D2-3H4, and 1G4-3H4 transitions of thulium ion, respectively.

Two Hybrid Polymeric Iodoargentates Incorporating Aromatic N-Heterocycle Derivatives as Electron Acceptors.

Two new hybrid polymeric iodoargentates, [Ag2I2(phen)]n (1; phen = 1,10-phenanthroline) and [AgI(bpt)]n (2; bpt = 3,5-bis(pyrazinyl)-1,2,4-triazole), were prepared by the hydrothermal methods. 1 displays a new type of taenioid, [Ag2I2(phen)]n, chain incorporating phen molecules, while 2 exhibits a unique 2D hybrid iodoargentate based on a combination of the [AgI]n layer and bpt molecules as electron acceptors. Such a 2D layer is the first example of an inorganic iodoargentate layer covalently bonding to aromatic N-heterocycle derivatives within the iodoargentates. 1 and 2 exhibit photocurrent response properties.

Copper Complexes with 1,10-Phenanthroline Derivatives: Underlying Factors Affecting Their Cytotoxicity.

The interpretation of in vitro cytotoxicity data of Cu(II)-1,10-phenanthroline (phen) complexes normally does not take into account the speciation that complexes undergo in cell incubation media and its implications in cellular uptake and mechanisms of action. We synthesize and test the activity of several distinct Cu(II)-phen compounds; up to 24 h of incubation, the cytotoxic activity differs for the Cu complexes and the corresponding free ligands, but for longer incubation times (e.g., 72 h), all compounds display similar activity. Combining the use of several spectroscopic, spectrometric, and electrochemical techniques, the speciation of Cu-phen compounds in cell incubation media is evaluated, indicating that the originally added complex almost totally decomposed and that Cu(II) and phen are mainly bound to bovine serum albumin. Several methods are used to disclose relationships between structure, activity, speciation in incubation media, cellular uptake, distribution of Cu in cells, and cytotoxicity. Contrary to what is reported in most studies, we conclude that interaction with cell components and cell death involves the separate action of Cu ions and phen molecules, not [Cu(phen)n] species. This conclusion should similarly apply to many other Cu-ligand systems reported to date.

Influence of Composite Additive on Gold Electrodeposition in DMH-Based Electrolyte: Combined Experimental and Theoretical Study

The comparison of macroscopic appearance and microscopic morphology of gold electrodeposit determined PHEN as the main brightener for its effective influence on refining the grains, resulting in a golden bright and shiny deposit. Improving the flatness of deposit when used together with PHEN, PDDA was the auxiliary brightener, thereby obtaining thicker deposits. Results of TEM and XRD showed that the average size of refined gold crystals was about 20 nm. We speculated from the patterns of XPS that the action of the additive molecule is to adsorb on the metal surface. Combined electrochemical measurements and MD simulations revealed that both PHEN and PDDA molecules could steadily adsorb on the surface of Ni and Au, increasing the polarization of the cathode surface and promote the refinement of grains. PHEN was the main additive when used as a composite additive for its higher adsorption energy than PDDA. The effective adsorption of PHEN and PDDA molecules led to the enhancement of cathodic polarization, causing the negative shift of potential and the decrease of current in cyclic voltammetry of the second step reduction. The chronoamperometry measurements indicated that the nucleation process was a progressive model. The grain growth was significantly inhibited when the additives were used.

Unexpected luminescent and photochemical properties of europium(III) cinnamates - Theoretical and experimental study.

The luminescent and photochemical properties of europium(III) cinnamates [Eu(Cin)3]n (I) and Eu(Cin)3·(phen) (II) were investigated in theoretical and experimental aspects. The high photostability of the complex I was explained. The complex II displays weak luminescence and low photostability in spite of the presence of a powerful antenna ligand 1,10-phenantroline in its coordination sphere. The unexpected luminescent and photochemical properties of europium(III) cinnamates were interpreted by the quantum chemistry methods. It was revealed that inclusion of phen molecule into Eu(Cin)3 complex results in lengthening of Eu-Cin distances that promotes weakening of antenna effect. In the process of photoexcitation of this complex noticeable lengthening of Eu-Cin-2 bond takes place and Cin-3 ligand is detached from the molecule that is the cause of low photostability and weak luminescence of II.

A methylenediphosphonate bridged copper(II) tetramer: Synthesis, structural, thermal, and magnetic characterization of [Cu4(H2O)2(phen)4(μ-P2O6CH2)2]·21H2O

A novel tetracopper(II) complex namely, [Cu4(H2O)2(phen)4(μ-P2O6CH2)2]·21H2O (1) was synthesized by using copper(II) chloride, 1,10-phenanthroline (phen), and methylene diphosphonic acid (MDP). The structure of 1 was characterized by single crystal X-ray diffraction and spectroscopy. Compound 1 crystallizes in the triclinic system, P1¯ space group and its crystal structure consists of neutral centrosymmetric tetranuclear copper(II)-methylene diphosphonate units where each peripheral {Cu(phen)(P2O6CH2)}2− fragment adopts the bidentate(Oeq-P-Oeq)/monodentate (Oax) bridging mode towards each of the two inner {Cu(phen)}2+ entities resulting in a “clamshell”-like orientation. The two crystallographically independent copper(II) ions in 1 (Cu1/Cu2) are five-coordinate with two nitrogen atoms from a bidentate phen molecule and two phophonate-oxygens building the basal plane (Cu1/Cu2) and either a water molecule (Cu2) or a phosphonate-oxygen (Cu1) filling the apical position of somewhat distorted square pyramidal surroundings. The values of the intramolecular copper–copper separation are 3.3219(8) and 3.2062(8) Å for Cu1⋯Cu2 and Cu1⋯Cu1i, respectively. Cryomagnetic measurements on a polycrystalline sample of 1 reveal the occurrence of an overall antiferromagnetic behaviour leading to a diamagnetic low-lying spin state. The values of the intramolecular magnetic interactions are J1 = −22.60(4) cm−1 (across the bis-bidentate methylene diphosphonate) and J2 = +4.9(3) cm−1 (through the double-oxo(phosphonate) bridge), the spin Hamiltonian being defined as H = −J1(SCu1·SCu2 + SCu1i·SCu2i) − J2(SCu1·SCu1i). These values are analyzed through simple orbital symmetry considerations and compared with those for related systems in the literature.

Coordination Polymers Based on [Re4Te4(CN)12]4− Cluster Anion, Lanthanide Cations and 1,10-Phenantroline

The cubane chalcocyanide cluster anion [Re4Te4(CN)12]4− was used as a pre-made building block for construction of a series of seven new coordination polymers (CPs) based on cationic complexes of Ln3+ ions and 1,10-phenantroline (phen). Together with three previously known compounds of this type, 1D CPs based on [Re4Te4(CN)12]4− anion formed a representative series which includes ten compounds (Ln = La, Pr, Nd, Sm–Ho, Yb). The main structural motif in the new compounds is the 1D chains composed of alternating cluster anions and [Ln(H2O)n(phen)m]3+ cationic fragments. Topology of the chains was found to be independent from the ionic radius and coordination number of the lanthanide ion. However, different number and orientation of coordinated phen and H2O molecules in the coordination environment of the lanthanide ions led to formation of several types of the supramolecular structures formed by non-covalent interactions between H2O, phen and CN− ligands. Influence of coordination environment of the lanthanide ions and conditions of the synthesis to the supramolecular structures is discussed in this work as well as structural relations with 1D coordination polymers based on mononuclear cyanometallate building blocks.

Synthesis, structure, and physicochemical properties of triply-bridged binuclear copper(II) complex [Cu2Phen2(µ-CH3CO2)2(µ-OH)]2[B10Cl10

The reaction between copper(II) acetate and Phen in the presence of [B10Cl10]2− anion affords mononuclear copper(II) complex [CuPhen2(CH3CO2)]2[B10Cl10]·[CuPhen(CH3CO2)2]. Continuous heating of the latter in DMSO results in triply-bridged binuclear copper(II) complex [Cu2Phen2(CH3CO2)2OH]2[B10Cl10] isolated from the reaction solution as a DMSO solvate hydrate [Cu2Phen2(CH3CO2)2OH]2[B10Cl10]·3DMSO·0.5H2O. Both complexes are studied by IR, 11B NMR, and X-ray diffraction; the binuclear complex is studied by 35Cl NQR and EPR spectroscopies as well as X-ray powder diffraction technique. Despite the short Cu−Cu distance revealed by X-ray diffraction analysis in the binuclear cationic complex (3.234 Å), no interactions between copper atoms are detected by EPR spectroscopy. According to 35Cl NQR studies, chlorine atoms bound with equatorial boron vertices of the boron cage participate in non-covalent interactions with H atoms of Phen molecules.