Inorganic Chemistry Communications (v.43, #C)

Contents List (iii-xiii).

A novel chiral metal–organic framework based on copper(II) and mixed ligands [Cu(tsgluO)(4,4-bipy)1.5]n  · 2.7nH2O (1) (H2tsgluO =  N-tosyl- l -glutamic acid, 4,4-bipy = 4,4-bipyridine) has been synthesized and structurally characterized by single-crystal X-ray diffraction. The X-ray diffraction revealed that complex 1 is formed via self-assembly of 1D right-handed helical chain and 1D ladder-like double chain, and the two different 1D chains are further interpenetrated to give rise to a 3D porous framework which consists of 1D channel along the a axes. Interestingly, the host framework encapsulates unique octameric water clusters.A novel chiral 3D porous framework [Cu(tsgluO)(4,4-bipy)1.5]n•2.7n H2O (1) is formed via self-assembly of 1D right-handed helical chain and 1D ladder-like double chain. It presents the first examples of chiral porous MOFs constructed from amino acid derivatives between two distinct 1D polymer chains.Display Omitted
Keywords: Chiral metal–organic framework; 3D; Porous; Two different 1D chains; Octameric water clusters;

Waugh- and Silverton-type polyoxometalates (POMs) K3(NH4)3[MnMo9O32] and H8[CeMo12O42] are enwrapped by dioctadecyldimethylammonium (DODA+) forming the surfactant-encapsulated POMs (SEPs) (DODA)6[MnMo9O32]·16H2O (DODA-MnMo9) and (DODA)8[CeMo12O42]·9H2O (DODA-CeMo12), which exhibit typical thermotropic liquid-crystalline properties. Here, the Waugh- and Silverton-type polyoxoanions centered by metal cation were firstly introduced into liquid crystal materials. The chemical composition of these SEP complexes was determined by IR spectra, elemental analysis and TG analysis. Also, the polarized optical microscopy, differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VT-XRD) and transmission electron microscopes (TEM) were performed to characterize their liquid-crystalline behavior.The metal-centered polyoxometalates were introduced into the POM/surfactant system resulting in the organic–inorganic hybrid materials with characteristic thermotropic liquid-crystalline behavior.Display Omitted
Keywords: Polyoxometalate; Surfactant; Thermotropic liquid crystal; Lamellae structure; Smectic phase;

Three bridging ligands 5,5′-bis[(4,5-diazafluoren-9-ylimino)methyl]-2,2′-bipyridine (L1), 5,5′-bis[2-(4,5-diazafluoren-9-ylimino)phenoxymethyl]-2,2′-bipyridine (L2), 5,5′-bis[4-(4,5-diazafluoren-9-ylimino)phenoxymethyl]-2,2′-bipyridine (L3), and corresponding Ru(II) complexes [(bpy)6Ru3(L1–3)](PF6)6 (bpy = 2,2′-bipyridine) have been synthesized. The three ligands have two kinds of nonequivalent chelating sites: one involving the 2,2′-bipyridine moiety, and the other involving the 4,5-diazafluorene moiety. The emission intensities of complexes [(bpy)6Ru3(L2)]6 + and [(bpy)6Ru3(L3)]6 + are almost equal to that of complex [(bpy)6Ru3(L1)]6 + in CH3CN solution at room temperature, but weaker than that of complex [(bpy)6Ru3(L1)]6 + in EtOH–MeOH (4:1, v/v) glassy matrix at 77 K. Cyclic voltammetry and differential pulse voltammetry studies of the three complexes show one Ru(II)-centered oxidation at around 1.33 V for the RuII/III couple.Three bridging ligands composed of 2,2′-bipyridine and 4,5-diazafluorene fragments have been prepared. These complexes display interesting emission properties. Electrochemical studies of these complexes show one Ru(II)-centered oxidation at around 1.33 V for the RuII/III couple.Display Omitted
Keywords: Ru(II) complex; 2,2′-Bipyridine; 4,5-Diazafluorene; Photophysics; Electrochemistry;

Interfacial response of a novel gemini metallo-surfactant to ionic guest species by Gina E. Jaggernauth; Richard A. Fairman (15-18).
The surface properties of a novel metallosurfactant with twin dodecyl aza-crown aliphatic tails (L3) were studied by surface pressure isotherms on aqueous subphases of selected Group I and Group II metals. Mean molecular areas of the headgroup at the monolayer interface (gas phase) are observed to decrease in response to aqueous phase complexation of L3 by metal ions in the order Ca2 +, Li+, Mg2 +, Na+, Ba2 + and K+. The surface-tension derived critical micelle concentration of L3 at 25 °C was 0.072 mM, while atomic force microscopy of aggregates observed after preparing Langmuir Blodgett multilayers on mica confirmed the formation of vesicles of up to 100 nm diameter as opposed to wormlike micelles formed by the monomeric analogs.Synthesis of a novel gemini metallosurfactant and studies of its interfacial ion-sensitive response to aqueous guests as well as its aggregation in bulk solution are reported. A model of the conformational changes of the host molecule that is consistent with surface pressure measurements is described.Display Omitted
Keywords: Diamsar; Ion selective response; Langmuir isotherms;

A novel luminescent three-dimensional Ag(I) complex with 3-fold interpenetrating (3,8)-connected nets by Chun-Feng Yan; Yue-Xu Lin; Fei-Long Jiang; Mao-Chun Hong (19-22).
A novel luminescent Ag(I) coordination polymer, [Ag3(cpterpy)2]n·nNO3 (1) (Hcpterpy = 4-(4-carboxyphenyl)-2,2:4′,4-terpyridine), is built-up from Ag(I) ions and terpyridyl-carboxylate ligands with unusual three different coordination modes. The dinuclear [Ag2O2] units with cpterpy- ligands in 1 are linked to form 2D wave-like layers and further connected by [Ag4O6] units into a 3D network, which features 3-fold interpenetrating (3,8)-connected nets with a (41264812)(462)(462) topology. Complex 1 exhibits interesting solid-state photoluminescence and high thermal stability.A novel luminescent 3D Ag(I) coordination polymer [Ag3(cpterpy)2]n·nNO3 (1) is built-up from Ag(I) ions and terpyridyl-carboxylate ligands with unusual three different coordination modes. Complex 1 features a 3-fold interpenetrating (3,8)-connected network with a (41264812)(462)(462) topology, and exhibits interesting solid-state photoluminescence.Display Omitted
Keywords: Ag(I) coordination polymer; Terpyridyl-carboxylic acid; Coordination modes; Luminescence; Thermal stability;

Self-assembled hybrid solids of luminescent Ru(II) polypyridyl complexes and polyoxometalates by Bangbo Yan; Yanfen Li; Steven R. Calhoun; Nicholas G. Cottrell; Divya Jyothi Lella; Aaron J. Celestian (23-26).
Two new hybrid compounds, [Ru(bpy)3][W6O19] (1) and [Ru(bpy)3]2[Mo8O26]∙6H2O (2) (bpy = 2, 2′-bipyridyl) have been synthesized hydrothermally and characterized using single crystal X-ray diffraction, TG, IR, FL, and UV–vis spectroscopy. Their crystal structures exhibit unique supramolecular interactions between [Ru(bpy)3]2 + and polyoxometalate units. Compound 1 shows anion–π interactions between the Linqvist unit W6O19 2 − and the aromatic ring of the [Ru(bpy)3]2 + complex. In compound 2, no significant anion–π interactions between the β-isomer of [Mo8O26]4 − and the [Ru(bpy)3]2 + unit were observed. Upon excitation at the λmax (450 nm) of the MLCT band of the [Ru(bpy)3]2 +, compound 1 shows an emission centered at 599 nm and compound 2 displays an emission centered at 613 nm.New hybrid compounds, [Ru(bpy)3][W6O19] (1) and [Ru(bpy)3]2[Mo8O26]∙6H2O (2) exhibit unique supramolecular interactions between [Ru(bpy)3]2 + and polyoxometalate units, and show emissions centered around 600 nm.Display Omitted
Keywords: Polyoxometalates; Crystal structure; Lindqvist; Ruthenium complex; Tungsten; Molybdenum;

A new acentric heterometallic–organic framework, [CdMg (btec)(DMF)(H2O)3] (1) (H4btec = 1,2,4,5-benzene tetracarboxylic acid), has been solvothermally synthesized. It features a 4-connected net with typical pts topology. To the best of our knowledge, compound 1 is the first example of Cd–Mg heterometallic organic framework based on the H4btec ligand. Compound 1 has potential unsaturated metal sites after the removal of coordination water molecules, so it shows good catalytic activity on the diethylzinc addition to benzaldehyde. The photoluminescent property of 1 is also investigated.Presented here is a new 3D heterometallic-organic framework characterized as 4-connected net with pts topology. Coordination water molecules in compound 1 can be removed, and thus exposes unsaturated metal sites which play a major role in catalytic activity on the diethylzinc addition to benzaldehyde.Display Omitted
Keywords: Metal–organic framework; Unsaturated metal sites; Catalytic property; Photoluminescence;

The extraordinary fluxionality of Ru66-C)(μ-CO)(CO)16 by John P. Canal; Ashfaq A. Bengali; Michael C. Jennings; Roland K. Pomeroy (31-34).
The 13C NMR spectrum of Ru66-C)(μ-CO)(CO)16 (1) in solution at − 125 °C indicates that the CO ligands of the equatorial Ru46-CO)(CO)10 unit are undergoing ultra-fast exchange estimated to be ≳ 3 × 107  s− 1. The variable temperature solution IR spectra of 1 shows bands that are attributed to the Ru46-CO)(CO)10 unit at − 58 °C that broaden and collapse almost to the baseline in the spectrum at + 70 °C. On the other hand, two of the three strong CO stretches of the Ru(CO)3 units of 1 observed in the low temperature spectra coalesce to a sharp signal typical of a C3v fac-L3M(CO)3 grouping. These results are interpreted in terms of the carbonyls of the equatorial Ru4(μ-CO)(CO)10 unit undergoing exchange on the IR timescale (~ 1012  s− 1) at room temperature, consistent with DFT calculations.Variable temperature NMR and IR studies indicate that carbonyl ligands of the equatorial Ru4(μ-CO)(CO)10 unit of Ru66-C)(μ-CO)(CO)16 undergo exchange on the infrared time scale consistent with DFT calculations.Display Omitted
Keywords: Fluxionality; Ultrafast spectroscopy; Carbonyl exchange; Metal cluster; Ruthenium;

Dinuclear copper(II) complexes bridged by imidazole-4,5-dicarboxylate by Salah S. Massoud; August A. Gallo; Merlin J. Dartez; Jacob G. Gautreaux; Ramon Vicente; Jörg H. Albering; Franz A. Mautner (35-38).
Two novel dinuclear Cu(II) complexes bridged by imidazole-4,5-dicarboxylate (HImdc) that derived from the tridentate amines N,N-bis(2-pyridylmethyl)methylamine (MeDPA) and 2,6-[bis(pyrazol-1H-yl)methyl]pyridine (bpzpy) are reported: [Cu2(MeDPA)24-HImdc)(H2O)(ClO4)] ClO4·3H2O (1) and [Cu2(bpzpy)24-HImdc)(H2O)2](ClO4)2·2 1/2 H2O (2).The complexes were characterized by single crystal structure determination, and spectral and magnetic measurements.In both single crystal structures, 4 + 2 geometries of the Cu(II) centers and bis-N,O chelate μ4-HImdc bridges in the dinuclear subunits are observed. Complexes 1 and 2 reveal moderate to strong antiferromagnetic coupling.The coupling parameters J  = − 67.9 cm− 1 (1) and J  = − 89.6 cm− 1 (2) correlate with the Cu―N⋯N(Imdc) angle α.The synthesis, single crystal structures and magnetic properties of two novel imidazole-4,5-dicarboxylate bridged dinuclear Cu(II) complexes, [Cu2(MeDPA)24-HImdc)(H2O)(ClO4)] ClO4·3H2O (1) and [Cu2(bpzpy)24-HImdc)(H2O)2](ClO4)2·2 1/2 H2O (2), are reported.Display Omitted
Keywords: Copper; Polynuclear complexes; Bridged carboxylate; Crystal structures; Magnetism; Imidazole dicarboxylate;

First stable nitrate-encapsulated sandwich type polyoxometalate: Synthesis, structural characterization, and catalytic performance by Mostafa Riahi Farsani; Bahram Yadollahi; Hadi Amiri Rudbari; Akbar Amini; Tom Caradoc-Davis; Jason R. Price (39-44).
A stable sandwich type Keggin polyoxometalate, Na4K5[K3Cu3(NO3)(A-α-PW9O34)2], has been synthesized and crystallized by a simple reaction method. Elemental analysis, FTIR, UV–vis, X-ray single crystal, thermal gravimetry, and cyclic voltammetry were used for the characterization of synthesized POM. The TBA salt of [K3Cu3(PW9O34)2]9 − revealed high catalytic activity and 74–99% selectivity in the liquid phase epoxidation of alkenes with aqueous H2O2. The X-ray structure of this complex reveals that three Cu(II) ions are sandwiched between two A-α-PW9O34 moieties and that a nitrate monoanion is encapsulated in the same plane as the three Cu(II) atoms. The nitrate is coplanar with the three copper atoms, which are each in a distorted square-pyramidal environment. After recrystallization, the NO3 group in the central belt didn't exit, in which this phenomenon is attributed to the type of counterion in the complex (as a result of mixing Na+ and K+ as counterions). This compound showed excellent stability in different pH and also didn't dissociate with hydrogen peroxide.The X-ray structure of stable Na4K5[K3Cu3(NO3)(A-α-PW9O34)2] reveals three Cu(II) ions sandwiched between two A-α-PW9O34 moieties and a nitrate monoanion which are encapsulated in the same plane as the three Cu(II) atoms. The TBA salt of [K3Cu3(PW9O34)2]  9− revealed high catalytic activity and selectivity in the liquid phase epoxidation of alkenes with aqueous H2O2.Display Omitted
Keywords: Sandwich type polyoxometalates; Nitrate-encapsulated; Catalysis; Epoxidation; Hydrogen peroxide;

Biosensitive metal chelates from curcumin analogues: DNA unwinding and anti-microbial evaluation by Thiravidamani Chandrasekar; Narayanaperumal Pravin; Natarajan Raman (45-50).
Few curcumin based metallointercalators having the amino acid (cysteine) have been synthesized and characterized by IR, UV–vis, NMR, EPR and magnetic susceptibility measurements. The data show that the complexes have the composition of ML type. The electronic absorption spectral data of the complexes suggest a square planar geometry around the central metal ion. The interpretation of spectroscopic and magnetic moment data suggests that the ligand is coordinated via ketimine, carbonyl and enolic oxygen of curcumin analogue. The interaction of the complexes with DNA is explored using absorption spectra, cyclic votammetric, viscosity measurements and gel electrophoresis technique. The data reveal that the complexes are strong intercalators and potential nucleases as compared to curcumin based free ligand. The antimicrobial activities of the ligand and its complexes are also explored and it is found that the complexes exhibit better activity against bacteria and fungi than the ligand.Four novel curcumin analogues metal(II) chelates are synthesized and characterized by physico-chemical techniques. They are strong intercalators and potential nucleases as compared to curcumin based free ligand. This exploration reveals that Cu(II) complex has an admirable biological profile.Display Omitted
Keywords: Curcumin; Cysteine; Square planar; Intercalators; Microbes;

Assembling chiral salan–copper(II) complexes into a 2D-network with carboxylic acid functionalization by Guoqi Zhang; Edwin C. Constable; Catherine E. Housecroft; Jennifer A. Zampese (51-55).
In this work, we aim to assemble a polymeric copper(II) network by ligand modifications with carboxylic acid functional groups. A chiral, reduced salen ligand, salan R,R-H2 1 with pendant ester functionalities has been synthesized. Its copper(II) complex, [Cu(R,R-1)], has been isolated, and its crystal structure determined by X-ray crystallography. Hydrolysing the ester groups of R,R-H2 1 to carboxylic acids yields R,R-H4 2 as the hydrochloride salt R,R-H4 2·2HCl. Treatment of R,R-H4 2·2HCl with copper(II) acetate in the presence of triethylamine yields the complex [Cu(R,R-H2 2)] n and X-ray structural analysis reveals that this consists of a 2D polymeric network. Each copper(II) center is bound within the near square-planar N2O2 donor set of the Schiff base ligand [R,R-H2 2]2 − and pendant carboxylic acid groups of adjacent units coordinate through the CO2H carbonyl units in the axial sites of the copper ion to complete an axially distorted octahedral coordination environment. The sheets are stacked via interdigitation of the cyclohexyl domains, giving an overall porous assembly containing carboxylic acid functionalities. This has proven to be an effective strategy for adding the dimensionality of metal–organic complexes by carboxylic acid functionalization of ligands.Mononuclear copper(II) complex, [Cu(R,R-1)] based on a chiral salan ligand R,R-H2 1 with pendant ester functionalities was isolated, and structurally determined. Hydrolysing ester groups of R,R-H2 1 to carboxylic acids yields R,R-H4 2 as the hydrochloride salt,which was treated with copper(II) acetate to yield complex [Cu(R,R-H2 2)] n consisting of a 2D polymeric network.Display Omitted
Keywords: Copper(II); Salan ligand; Chirality; Self-assembly; Coordination network;

Crystals of {[Cu2(mal)2(bpfp)2(H2O)2]·10H2O} n (1, mal = malonate, bpfp = bis(4-pyridylformyl)piperazine) were prepared by slow diffusion of an ethanolic solution of bpfp into an aqueous solution of copper malonate. Single-crystal X-ray diffraction showed the presence of supramolecular stacks of ring-like [Cu2(mal)2(bpfp)2(H2O)2] neutral coordination complex molecules threaded by unique infinite water molecule tapes with a T6(6)4(4)4(3)4(3)A(2) classification. These feature six-membered chair conformation rings, four-membered rings, and are decorated by single water molecules. Hydrogen bonding acceptance by the formyl groups of the bpfp ligands proved critical in stabilizing the water molecule tapes within the nanotubular incipient channels.{[Cu2(mal)2(bpfp)2(H2O)2]·10H2O} n (mal = malonate, bpfp = bis(4-pyridylformyl)piperazine) possesses stacks of ring-like neutral coordination complex molecules threaded by unique infinite T6(6)4(4)4(3)4(3)A(2) water molecule tapes.Display Omitted
Keywords: Coordination complex; Copper; Crystal structure; Water chain;

A unique discrete octameric cluster of lattice water molecules in the lattice voids produces a 3D supramolecular architecture through hydrogen bonding interactions. These cubic water clusters have not been structurally documented so far and illustrate new modes of supramolecular association of water molecules.A novel discrete cubic water cluster has been reported which is sustained by weak interactions with chloride anions producing 3D supramolecular framework.Display Omitted
Keywords: Cubic water cluster; Intermolecular interactions; Supramolecular assembly; 3D architecture; Metal–organic framework;

A water-soluble amidinium-appended ferrocene moiety is characterized in which the amidinium functionality is fused directly to the ferrocene ring (Fcam1). This species is designed to form a building block for aqueous proton-coupled electron transfer in which proton transfer occurs to the bulk and electron transfer occurs to a chemical oxidant. pH-Dependent absorption spectroscopy and electrochemistry show that the electrochemical potential is directly linked to the protonation state of the amidinium. A thermodynamic square scheme is constructed for Fcam1. The square scheme serves as motivation and provides direction for incorporating this species into a covalently-bound system for the study of proton-coupled electron transfer.A thermodynamic square scheme reveals the complete thermodynamic characterization of the ferrocenyl-amidinium compound.Display Omitted
Keywords: Ferrocene; Ferrocene-derivative; Proton-coupled electron transfer (PCET); pH-Dependent oxidation potential; Square scheme; pH-Dependence;

Preparation of silver nanostructures from a new benzopyrazine silver(I) nitrate coordination polymer by Javad Mollaee; Fatemeh Molaei; Ali Morsali; Sang Woo Joo; Giuseppe Bruno; Hadi Amiri Rudbari (67-69).
A new two-dimensional silver(I) coordination polymer, [Ag(Quinoxaline)(NO3)]n (1); Quinoxaline = Benzopyrazine, has been synthesized and characterized by IR and 1H NMR spectroscopy. Silver nanorods were synthesized by calcination of compound 1 at 600 °C under air atmosphere. Also, silver nanopowders and silver spongy nanostructures were synthesized by calcination at 400 and 500 °C and sol–gel methods. The silver nanostructures were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and energy-dispersive X-ray (EDAX). The thermal stability of compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA).A new two-dimensional silver(I) coordination polymer, [Ag(Quinoxaline)(NO3)]n (1); Quinoxaline = Benzopyrazine, has been synthesized and characterized by IR and 1H NMR spectroscopy. Silver nanorods were synthesized by calcination of compound 1 at 600 °C under air atmosphere. Also, silver nanopowders and silver spongy nanostructures were synthesized by calcination at 400 and 500 °C and sol–gel methods.Display Omitted
Keywords: Silver(I) coordination polymer; Nanostructures; Quinoxaline; Silver;

Structural diversity in Cu(II) and Cd(II) coordination complexes with 4-amino-1,2,4-triazole ligand by Pin-Ning Wang; Chun-Wei Yeh; Chi-Hui Tsou; Yuh-Wen Ho; Hsun-Tsing Lee; Maw-Cherng Suen (70-74).
The syntheses and structures of the series of metal complexes, namely [CuCl2(L)2·H2O)]n (L  = 4-amino-1,2,4-triazole), 1; {[Cu(L)4][ClO4]2.H2O}n, 2; and [Cd2Cl4(L)2.2H2O]n, 3 are reported. These were prepared by the self-assembly of Cu(II) and Cd(II) salts with L in MeOH/H2O system. All these complexes have been characterized by elemental analysis, IR spectrum, and single crystal X-ray diffraction. Complexes 12 show 1-D polymeric infinite chains, while complex 3 shows 2D pleated net. The anions Cl in complexes 1 and 3 act as bridging or terminal ligands to the metal atoms while the ClO4 anions in 2 are not coordinated to the metal centers.The syntheses and crystal structures of three new coordination polymers containing 4-Amino-1,2,4-triazole ligand are reported. Complexes 12 show 1-D polymeric infinite chains, while complex 3 shows 2D pleated net. The anions Cl in complexes 1 and 3 act as bridging or terminal ligands to the metal atoms while the ClO4 anions in 2 is not coordinated to the metal centers.Display Omitted
Keywords: Tridentate ligands; Supramolecular; Trans conformation; 4-Amino-1,2,4-triazole;

Zeolite L (ZL) is functionalized with europium ions through ion exchange and then 6-hydroxybenz[de]anthracen-7-one (HBAO) ligand is fabricated with coordination to Eu3 + by a so-called gas disperse (so-called ship-in-bottle) method. It is worthy pointing out that the europium hybrids show emission of both europium ion and HBAO, which can be integrated to show close white luminescence. This result provides a useful path to obtain white emissive lanthanide hybrids.The host–guest hybrids of europium ion functionalized zeolite L (ZL) are fabricated with 6-hydroxybenz[de]anthracen-7-one, which shows cool-white luminescence.Display Omitted
Keywords: Host–guest hybrids; Europium ion; Functionalized zeolite L; 6-Hydroxybenz[de]anthracen-7-one; Cool-white luminescence;

A cadmium (II) coordination polymer, namely {[Cd5(Ln)6Cl4]·2H2O}n (1, HLn  = 1-methyl-2-(3H-[1–3]triazol-4-yl)-1H-benzoimidazole), has been constructed from in situ generated HLn under hydrothermal condition. The unsuccessful synthesis of 1 under similar synthesis condition using HLn as reactant suggests the in situ reaction is crucial for the assembly of the compound. Crystallography study reveals that 1 processes layer structure in which chains of [Cd3(Ln)4Cl4]2 − were connected by a pair of Cd ions. These layers further stack in an AAA model to form a 3D supramolecular framework and hydrogen bonding as well as π–π interaction were formed between adjacent layers to stabilize the framework. TGA indicates that 1 is highly thermally stable up to about 380 °C. The luminescence of 1 in the solid state which may be assigned to intraligand transition shows a blue shift of 16 nm compared to that of HLn·HCl.A plicated layer complex of {[Cd5(Ln)6Cl4]•2H2O}n (HLn  = 1-methyl-2-(3H-[1,2,3]triazol-4-yl)-1H-benzoimidazole) was obtained under hydrothermal synthesis with in situ ligand decarboxylation. A 3D supermolecular was further constructed from hydrogen bonding as well as π–π interaction. The compound process high thermal stability and intraligand transition induced solid luminescence at ca. 397 nm.Display Omitted
Keywords: Cadmium(II) complex; Hydrothermal synthesis; In situ ligand reaction; Luminescence;

An unusual three-dimensional Co(II)-based pillar-layered coordination polymer [Co2(L)(bipy)(OH)(H2O)]n·nCH3CN (1, H3L = 2-(2′,4′-dicarboxylphenoxy)benzoic acid, bipy = 4,4′-bipyridine), has been successfully yielded via the mixed ligand approach under hydrothermal condition, and characterized carefully by elemental analysis, infrared spectra, and single crystal X-ray diffraction, and magnetic measurement. Single crystal X-ray analysis reveals that the framework of complex 1 is firstly assembled by the 2D undulated layers, and then further supported by bipy spacers into a 3D intricate framework. Topologically, 1 shows a 3D binodal (3,8)-connected tfz-d net with the Schläfli symbol of (43)2(46·618·84), which is less common and rarely found in the reported literatures. Moreover, the magnetic analysis indicates that 1 exhibits the antiferromagnetic coupling interaction between Co(II) ions.A three-dimensional (3D) pillar-layered Co(II)-based coordination polymer [Co2(L)(bipy)(OH)(H2O)]n·nCH3CN (1) via the mixed ligand approach, where H3L is 2-(2′,4′-dicarboxylphenoxy)benzoic acid and bipy is 4,4′-bipyridine. Complex 1 shows a (3,8)-connected tfz-d topology based on the tetranuclear Co(II) SBUs, and the magnetic measurements indicate the antiferromagnetic interaction within the neighboring Co(II) ions.Display Omitted
Keywords: Co(II)-based complex; Tetranuclear SBUs; tfz-d Topological net; Magnetic properties;

A novel compound [Cu21,1–N3)2(C2O4)(bpzm)2]n incorporating simultaneously azide and oxalate bridges has been synthesized and characterized in the context of its structural and magnetic properties. The crystal structure has been determined by single-crystal X-ray analysis. Additionally, the compound was characterized using IR, UV–vis and thermal analyses. The investigated complex [Cu21,1–N3)2(C2O4)(bpzm)2]n represents an interesting magnetic system of Cu(II) centers with alternating ferro- and antiferromagnetic coupling.The paper presents a novel and very rare example of a copper(II) complex incorporating simultaneously azide and oxalate bridges. The compound [Cu21,1–N3)2(C2O4)(bpzm)2]n adopts a zig-zag chain structure. The investigated complex [Cu21,1–N3)2(C2O4)(bpzm)2]n represents an interesting magnetic system of Cu(II) centers with alternating ferro - and antiferromagnetic coupling.Display Omitted
Keywords: Coordination polymer; Copper(II); Oxalate; Azide; X-ray; Magnetic measurements;

The first metal–organic 5-nitrotetrazolate, [Me3Sn(μ-OH)SnMe3(μ-OH)SnMe3(H2O)][NT] (2), has been prepared by a simple metathetical reaction between Me3SnCl and sodium 5-nitrotetrazolate dihydrate (= NaNT, 1). A single-crystal X-ray diffraction study revealed the presence of the trinuclear [Me3Sn(μ-OH)SnMe3(μ-OH)SnMe3(H2O)]+ cation to which the 5-nitrotetrazolate anion is coordinated via a ring-N atom. The NT anion is further engaged in four different O―H⋯N and O―H⋯N hydrogen bonds involving the remaining three ring-nitrogen atoms and one oxygen of the nitro group, leading to an extensive supramolecular hydrogen-bonded network in the solid state. Despite its very low N content of only 10.65%, compound 2 is highly impact-sensitive (< 2.5 J) and can be classified as a primary explosive.The first metal–organic 5-nitrotetrazolate, [Me3Sn(μ-OH)SnMe3(μ-OH)SnMe3(H2O)][NT] (2), has been prepared. X-ray diffraction revealed the presence of the trinuclear [Me3Sn(μ-OH)SnMe3(μ-OH)SnMe3(H2O)]+ cation to which the 5-nitrotetrazolate anion is coordinated via a ring-N atom. Compound 2 is highly sensitive to impact and can be classified as a primary explosive.Display Omitted
Keywords: Energetic compounds; Nitrotetrazolate anion; Tin; Organotin compounds; X-ray structure;

Two novel silver(I) complexes, [Ag2(H2L)2(NO3)2]2(NO3)8 (1) and [Ag1.5L]n(NO3)1.5n·nH2O (2) (L = 1,2-bis(3′-pyridylmethylamino)ethane), have been constructed from bis(pyridyl) ligand with chelating spacer through controlling experimental condition. This two complexes exhibit [2 + 2] metallomacrocyclic motif and snake-shape chain. Complex 1 may present a classic case that incorporates an inorganic anion induced supramolecular system in the coordination complex.Two novel silver(I) complexes have been constructed from bis(pyridyl) ligand with chelating spacer, which exhibit [2 + 2] metallomacrocyclic motif and snake-shape chain.Display Omitted
Keywords: Silver(I) complex; Bis(pyridyl) ligand; Metallomacrocyclic motif; Chelating spacer;

By employing di-palladium complex [(bpy)2Pd2(NO3)2](NO3)2 (where bpy = 2, 2′-bipyridine) as corners and tetrapyrazolate calix[4]arene-based ligand (L 4 −) as linkers, a novel cavity-containing high-positively-charged polypyrazolate-bridged metallo-macrocycle [Pd16L4]16 +·16NO3 with Pd(II)⋯Pd(II) dimetal-coordination motifs has been synthesized by a directed coordination driven self-assembly with spontaneous deprotonation of the 1H-bipyrazole ligands in aqueous solution. The counter ions NO3 were trapped within the amphiphilic 3-D microporous channels in the solid state.3-D amphiphilic channel structure with microporous constructed from the self-assembled [Pd16L4] metallo-macrocycle subunits through novel self-inclusion interaction in the solid state (see picture).Display Omitted
Keywords: Self-assembly; Macrocycles; Pyrazolate; Palladium;

Three new vanadoborates functionalized with zinc complexes by Xing Liu; Rongqing Zhao; Jian Zhou; Meihua Liu (101-104).
Three new vanadoborates [Zn4V10B34O84H10](H2dap)4(dap)2·9H2O (1), [Zn(H2teta)2V12B18O54-(OH)6]·4H3O (2) and [Zn(H3tepa)V12B18O54(OH)6][H2en]2·H3O·3H2O (3) have been hydrothermally synthesized and structurally characterized. 1 consists of new cluster [Zn4V10B34O84H10]8 − with the rare [Zn4B4O18] unit, protonated H2dap2 +, free dap and H2O molecules. Both 2 and 3 contain [V12B18O54(OH)6(H2O)]10 − clusters, which are connected by [Zn(H2teta)2]2 +/[Zn(H3tepa)]2 + groups as bridges into 1-D chain. The magnetic susceptibility of 3 shows the antiferromagnetic interaction between VIV cations.The integration of tetrahedral [ZnO4] units into B–O–V cluster framework gives an interesting vanadoborate cluster [Zn4V10B34O84H10]8 −.Display Omitted
Keywords: Hydrothermal synthesis; Vanadium; Borate; Polyoxovanadate; Crystal structures;

Synthesis and structural characterization of two open-framework zinc phosphites with (3,4)-connected networks by Guo-Ming Wang; Jin-Hua Li; Ji-Qing Jiao; Xiao Zhang; Xiao-Meng Zhao; Xue Yin; Jun-Shuai Huang; Ying-Xia Wang; Jian-Hua Lin (105-109).
Two new organically templated zinc phosphites, [H2 dmpip][Zn3(HPO3)4] (1) and [HMedmpip][Zn3(HPO3)4] (2), where dmpip  = 2,6-dimethyl-piperazine and Medmpip  =  N-methyl-2,6-dimethyl-piperazinium, have been synthesized and structurally characterized. Note that the new Medmpip 2 + template in 2 is generated from in situ N-methylation reaction between CH3OH and the dmpip amine precursor, which is used to serve as template in 1. Such direct N-methylation transformation is unique, and quite different from conventional Eschweiler–Clarke methylation in which an excess of formic acid and formaldehyde was required. Both compounds are constructed from strictly alternating ZnO4 and HPO3 units, and possess different (3,4)-connected interrupted frameworks with intersecting 8-, 10- and 12-ring channels (for 1), and 8-, 12-ring channels (for 2), respectively. The occurrence of helical channels in the open structure of 1, and fascinating hydrogen-bonded helices between the host inorganic chains and guest organic templates are also noteworthy.Two new open-framework zinc phosphites were synthesized under different solvent systems. New Medmpip template in compound 2 derives from dmpip in 1 by in situ N-methylation transformation. They exhibit different (3,4)-connected frameworks constructed from strict alternation of ZnO4 and HPO3 groups.Display Omitted
Keywords: In situ; N-methylation; Zinc phosphite; Helical channel; Crystal structure;

In this paper, we reported the C―F and C―H bond activation of polyfluoroimine ligands induced by CoMe(PMe3)4. The reaction of pentafluorophenylmethylidene-2,6-diisopropylaniline 1 with CoMe(PMe3)4 afforded an ortho-chelated cobalt(I) complex [Co(PMe3)3(C6F4-ortho-CH = N-C6H3(iso-Pr)2(ortho, ortho))] (5) via C―F bond activation and subsequent elimination of methyl fluoride. Under similar reaction conditions, the reactions of polyfluoroaryl imines 24 with CoMe(PMe3)4 afforded the penta-coordinate cobalt(I) complexes 68 via C―H bond activation and subsequent elimination of methane [Co(PMe3)3(C6H2F2(meta, meta)-ortho-(CH = N-C6H4Cl para )] (6), [Co(PMe3)3(C6H2F2(meta, para)-ortho-(CH = N-C6H4Cl para )] (7), and [Co(PMe3)3(C6HF3(meta, meta, para)-ortho-(CH = N-C6H4Cl para )] (8). Complexes 58 were characterized through IR, 1H NMR, 31P NMR, 19F NMR and elemental analyses. The crystal and molecular structures of complexes 5, 6 and 8 were determined by X-ray single crystal diffraction. The reactions of 8 with MeI and EtBr afforded organic fluorides 910. A proposed formation mechanism of 910 with the oxidative addition of RX at the cobalt(I) center of 8 and reductive elimination via C,C-coupling was discussed.Four organocobalt(I) complexes were prepared by reactions of polyfluorinated imines with CoMe(PMe3)4 via C―F or C―H activation with imine as an anchoring group. Demetallation of these organocobalt(I) complexes by MeI and EtBr afforded organic fluorides via C,C-coupling. The molecular structures of three organocobalt(I) complexes were determined by X-ray diffraction.Display Omitted
Keywords: C―H activation; C―F activation; Cobalt complex; C,C-coupling; Trimethylphosphine;

Luminescent nanocrystal metal organic framework based biosensor for molecular recognition by Pawan Kumar; Parveen Kumar; Lalit M. Bharadwaj; A.K. Paul; Akash Deep (114-117).
A nanocrystal metal organic framework (NMOF1) has been investigated for molecular recognition. NMOF1 {[Cd(atc)(H2O)2]n} has been synthesized by the reaction of Cd(II) ions with the sodium salt of ‘atc’ (‘atc’ = 2-aminoterephthalic acid) in aqueous medium at room temperature. Pendent ―COOH group of the organic linker was activated using EDC [(1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide] intermediated organic reaction, followed by the bioconjugation of NMOF1 with anti-BSA (anti-bovine serum albumin). NMOF1/anti-BSA complex has been used for the sensing of BSA (bovine serum albumin) based on the fluorescence quenching phenomena. Estimated limit of detection of the proposed molecular probe is 7 mg/mL.NMOF1 {[Cd(atc)(H2O)2]n} has been synthesized, and pendent―COOH group of the organic linker activated. NMOF1 was tagged with anti-BSA to develop a molecular sensing platform. Fluorescence quenching experiments suggested that the above molecular sensor was sensitive and specific.Display Omitted
Keywords: MOF; Cd(II); atc; Bioconjugation; Sensing; Anti-bovine serum albumin;

A nanocomposite of luminescent europium organic framework (EuOF) and gold nanoparticles (AuNPs) has been investigated for photoluminescence (PL) quenching based highly sensitive detection of trinitrotoluene (TNT). The nanocomposite ‘EuOF/AuNP’ has been synthesized by initiating the growth of EuOF in the presence of AuNPs. The successful synthesis of the product has been verified with the help of electron microscopy and X-ray diffraction analysis. EuOF/AuNP nanocomposite offers reproducible and stable measurements of TNT. The linear dynamic range of detection is 5–800 ppb with the estimated detection limit of 18 ppb. The presence of other closely related aromatic compounds such as phenol, o-cresol, toluene, benzene, nitrobenzene and nitrophenol do not influence the sensing of TNT.Nanocomposite of europium organic framework (EuOF) and Gold Nanoparticles (AuNPs) has been synthesized. EuOF/AuNP is exploited for the photoluminescence quenching based detection of trinitrotoluene. The sensing method provides sensitive and stable measurements; and is selective with respect to several other closely related aromatic compounds.Display Omitted
Keywords: Metal organic framework; Trinitrotoluene; Chemosensing; Gold nanoparticles; Nanocomposite; Photoluminescence;

Assembly of two tripodal multicarboxylic ligands, namely rigid 3,4-bis(4-carboxyphenyl)-benzoic acid (H3 L1 ) and flexible 3,5-bis(4-carboxyphenoxy)-benzoic acid (H3 L2 ) with MnCl2 under hydrothermal conditions afforded two distinct metal-organic frameworks (MOFs), {[Mn3(L1 )2(H2O)4](H2O)2} n (1) and {[Mn3(L2 )2(H2O)4](H2O)4} n (2), respectively. Interestingly, both complexes possess different 3D networks of novel self-interpenetrating prototype, constructing from different 2D [Mn(COO)2] n polymeric motifs. Furthermore, the thermal and magnetic properties of 1 and 2 are studied.Two magnetic MnII MOFs with rigid or flexible tripodal multicarboxylate ligands have been successfully constructed, which exhibits the different self-interpenetrating topological networks.Display Omitted
Keywords: Manganese(II) MOFs; Tripodal multicarboxylate ligands; Self-interpenetrating topological nets; Magnetic properties;

Anion-triggered structural diversity of binuclear-based Ag(I) coordination architectures and rich luminescence properties by Jiyong Hu; Chunli Liao; Shufang Chen; Peng Jin; Jin'an Zhao; Haipeng Zhao (126-130).
To pursuit the subtle influence exerted on the structure by the anions, two new complexes, namely [Ag(pbmb)·SO3CF3]n 1, and [Ag(pbmb)·ClO4]n 2 have been constructed by the reaction of a V-shaped flexible ligand 1-((2-(pyridin-2-yl)-1H-benzoimidazol-1-yl)methyl)-1H-benzotriazole (pbmb) and corresponding silver salts under solvothermal conditions. Single crystal analysis shows that the binuclear-based 1 and 2 are 1D motifs with different structural features, especially for complex 1 with the shortest Ag⁎⁎⁎Ag distance of 2.928 Å. Both complex 1 and 2 exhibit rich luminescent behaviors at temperatures 10–298 K, whereas complex 1 manifests stronger phosphorescence by comparison with 2.Two new complexes, namely [Ag(pbmb)·SO3CF3]n 1, and [Ag(pbmb)·ClO4]n 2 have been constructed. The binuclear-based 1 and 2 are 1D motifs with different structural features. Both complex 1 and 2 exhibit rich triplet state luminescent behaviors at 10–298 K, whereas complex 1 manifests stronger phosphorescence by comparison with 2.Display Omitted
Keywords: V-shaped ligand; Anion effect; Ag(I) complex; Luminescence behavior;

Three-dimensional molecular-based magnet of octacyanometalate-based tungstate(V)-cobalt(II) bimetallic assembly with T C  = 26 K by Zhi Kun Gao; Qing Wei Gao; Hai Sheng Liu; Bing Hui Yang; Ying Wang; Bin Ding; Ju Yan Liu; Xiao Jun Zhao (131-134).
A three-dimensional (3D) octacyanotungstate(V)-based molecular based magnet containing Co(II) ions, {[CoII 4(H2O)6(C2O4)][WV(CN)8]2·6H2O}n (1), has been synthesized in acidic solution and structurally characterized. X-ray determination indicates that in 1 each [W(CN)8]3 − structural unit is linked by seven neighboring Co(II) ions forming 2D Co–W–CN inorganic connectivity layers. Further short conjugated oxalate bridges join these neighboring 2D layers ultimately forming the 3D framework. Magnetic investigation of complex 1 reveals that long-range ferromagnetic ordering occurs below the Curie temperature of 26 K. The beautiful butterfly-shaped magnetic hysteresis loop at 10 K between − 70 KOe and 70 KOe exhibits a rather high coercive field (H C  = 3010 Oe). The remnant magnetization M r is equal to 3055 cm3  mol− 1. To our best knowledge, complex 1 is the first example of 3D cyano-based magnets bridged by C2O4 2 − anions.A three-dimensional (3D) octacyanotungstate (V) magnet was synthesized in acidic solution and structurally charaterized. Magnetic investigation reveals that long range ferromagnetic ordering occurs below the Curie temperature of 26 K.Display Omitted
Keywords: Octacyanotungstate; Co4W2; Bimetallic assembly; Magnetic hysteresis loop;

A unique tetranuclear Mn(II) cluster bridged by carboxyl substituted nitronyl nitroxide radical: Crystal structure and magnetic properties by Yungai Li; Yaowei Guo; Haixia Tian; Peng Hu; Zan Sun; Yue Ma; Licun Li; Daizheng Liao (135-137).
One unique radical-bridged Mn(II) cluster [Mn4(hfac)6(NIToBA)2(HIMoBAH)(H2O)3] (1) (hfac = hexafluoroacetylacetonate, NIToBAH = 2-(2-carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-oxide, HIMoBAH = 2-(2-carboxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-hydroxy) has been synthesized and structurally and magnetically characterized. The core of complex 1 features four Mn(II) ions bridged by three carboxyl groups and two nitroxide groups to form a crown-like ring structure. This complex exhibits strong antiferromagnetic interaction because the NO groups are directly coordinated to the metal ions.One unique radical-bridged Mn(II) cluster has been synthesized by using carboxyl substituted nitronyl nitroxide radical. This complex exhibits strong antiferromagnetic interaction because the NO groups are directly coordinated to the metal ions.Display Omitted
Keywords: Nitronyl nitroxide radical; Manganese; Crown-like ring structure; Magnetic properties;

A low-cost and large-scale synthesis of nano-zinc oxide from smithsonite by Yucheng Zhang; Jinxia Deng; Jun Chen; Ranbo Yu; Xianran Xing (138-141).
Nano-zinc oxide was prepared through a series of complex chemical reactions from smithsonite ores and the sensitivity of products to alcohol was measured. The smithsonite ores were calcined and decomposed into ZnO at 400 °C, and then were leached by sodium hydroxide solution. The leaching solution was purified by adding sodium sulfide, and the amount ratio of lead removal agent to lead ions (Na2S·9H2O/Pb) was 4.37. The zinc ions were precipitated in the form of Zn(OH)2(s) by regulating the pH. Finally, the precipitate was calcined in muffle furnace at 500 °C and decomposed into nano-ZnO. The optimum operating temperature of sensitivity to alcohol was 160 °C, and the sensitivity of the products with polyethylene glycol (PEG) rose at lower temperature and attained higher maximum value than that of the product without PEG. Especially, the sensitivity of ZnO prepared with 3 wt.% PEG to alcohol could be about 35 at 160 °C.The sensitivity of ZnO to alcohol was shown in the figure. All of the sensitivity curves presented a increase-maximum-decay trend with the increase of temperature and attained maximum at 160 °C. The addition of PEG made the sensitivity rise at lower temperature and attain a higher maximum value.Display Omitted
Keywords: Zinc oxide; Smithsonite; Precipitation; Sensitivity;

C-carboranylation of a quasi-aromatic iron(II) cage complex and its organic aromatic analog by the metal-catalyzed (promoted) cross-coupling reactions by Simyon V. Svidlov; Oleg A. Varzatskii; Tamara V. Potapova; Anna V. Vologzhanina; Sergey S. Bukalov; Larisa A. Leites; Yan Z. Voloshin; Yurii N. Bubnov (142-145).
One-pot reaction a quasi-aromatic diiodoclathrochelate precursor with the carboranylating agent, generated in situ from equimolar amounts of lithium 1-ortho-carboranyl and trimethoxyborate, in the presence of a palladium catalyst afforded a ribbed-functionalized iron(II) mono-ortho-carboranoclathrochelate. Such a formation of С(carborane)―C(clathrochelate) bond is accompanied by hydrodeiodination in a vicinal position and a monomethinemonocarborane macrobicyclic complex was isolated and characterized by the single crystal X-ray diffraction. The geometry of its FeN6-coordination polyhedron is intermediate between a trigonal prism and a trigonal antiprism with the distortion angle φ of 24.9° and the height h of this polyhedron is equal to 2.32 Å; Fe―N distances vary from 1.889(2) to 1.921(2) Å and the average bite angle α is approximately 39.1°. The model reaction of this carboranylating agent with 4-iodobiphenyl, giving the corresponding aryl carborane, proceeds only in vigorous reaction conditions with a palladium catalyst and copper(I) iodide as a promotor. The compounds obtained were characterized using elemental analysis, ESI and EI mass spectrometry, IR, Raman, UV–vis, 1H, 11B, 19F and 13C{1H} NMR spectroscopy. Thus, palladium-catalyzed Suzuki–Miyaura (copper-promoted in the case of an aryl iodide) cross-coupling reactions of a generated in situ derivative of carboranylboronic ester have been successfully used, for the first time, for one-pot synthesis of a quasi-aromatic hybrid carboranoclathrochelate with an inherent polyhedral ribbed substituent and its aromatic analog 4-(1-ortho-carboranyl)biphenyl. The developed strategy has been then found useful in the organic chemistry as a versatile approach towards carborane-based organic compounds.The one-pot C-carboranylation of a quasi-aromatic cage metal complex and its organic aromatic analog by palladium-catalyzed Suzuki–Miyaura and, in the case of aryl iodide, copper-promoted cross-coupling reaction with a derivative of o-carboranylboronic ester as carboranylating agent gave the first hybrid carboranoclathrochelate with an inherent polyhedral ribbed substituent and corresponding arylcarborane, respectively.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Ligand reactivity; Carboranylation; Cross-coupling reaction;

Four new cyclometalated phenylisoquinoline-based Ir(III) complexes: Syntheses, structures, properties and DFT calculations by Zhi-Gang Niu; Dong Liu; Da-Chao Li; Jing Zuo; Jian-Ming Yang; You-Hui Su; Yi-Ding Yang; Gao-Nan Li (146-150).
Four new cyclometalated phenylisoquinoline-based iridium(III) complexes [Ir(CN)2(bipy)]PF6 (5a5d) (bipy = 2,2′-bipyridine) have been synthesized and fully characterized, where the CN ligands are 1-(4-(trifluoromethyl)phenyl)isoquinoline, 4-(isoquinolin-1-yl)benzaldehyde, 4-(isoquinolin-1-yl)benzonitrile and 1-(3-fluoro-4-methylphenyl)isoquinoline, respectively. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of these new complexes 5a5d have been studied. All Ir(III) complexes exhibit orange phosphorescence in dichloromethane solution at room temperature with a maximum at 593–618 nm, quantum yield of 0.046–0.16. The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 5a5d have been calculated with density functional theory (DFT) and time-dependent DFT (TD-DFT).Four new cyclometalated phenylisoquinoline-based Ir(III) complexes 5a-5d have been synthesized and characterized. The crystal structures of 5a and 5c have been determined. The photophysical and electrochemical properties of all complexes have been investigated, and the lowest-energy electronic transitions have been analyzed by means of time-dependent density functional theory.Display Omitted
Keywords: Iridium(III) complex; Phenylisoquinoline; Syntheses; Crystal structures; Photoluminescence; DFT calculation;

Mixed anion-induced Salen-based Zn2Ln3 (Ln = Nd, Yb or Er) complexes with near-infrared (NIR) luminescent properties by Heini Feng; Zhao Zhang; Weixu Feng; Peiyang Su; Xingqiang Lü; Daidi Fan; Wai-Kwok Wong; Richard A. Jones; Chengyong Su (151-154).
A series of mixed anion-induced Zn2Ln3 complexes [Zn2(L)3Cl22-OH)(μ3-OH)2Ln3(N3)2] (Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) have been obtained by the self-assembly of the precursor [Zn(L)(MeCN)] (H2L  = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with LnCl3·6H2O (Ln = La, Nd, Yb, Er or Gd) and NaN3 in alcohol-containing solutions. In these reactions, transmetallation of the partial precursor leads to the coexistence of two Zn2 + ions and one Ln3 + ion in the inner cis-N2O2 core and the other two Ln3 + ions in the outer O2O2 moieties of three deprotonated ligands. Photophysical studies suggest that the characteristic near-infrared (NIR) luminescence of Nd3 + and Yb3 + ions is sensitized through both the excited singlet 1LC and triplet 3LC states of the depronated ligand (L)2 −, despite the luminescent quenching with three OH oscillators arround the Ln3 + ions.With [Zn(L)(MeCN)] (H2L  = N,N′-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) as the precursor,   series of mixed anion-induced luminescent Zn2Ln3 complexes [Zn2(L)3Cl22-OH)(μ3-OH)2Ln3(N3)2] (Ln = La, 1; Ln = Nd, 2; Ln = Yb, 3; Ln = Er, 4 or Ln = Gd, 5) are obtained, respectively, where transmetallation of the partial precursor leads to the coexistence of two Zn2 + ions and one Ln3 + ion in the inner cis-N2O2 core and the other two Ln3 + ions in the outer O2O2 moieties of three deprotonated ligands.Display Omitted
Keywords: Hetero-pentanuclear Zn2Ln3-arrayed complexes; Transmetallation; Mixed anions; Sensitization of NIR luminescence;

Structural studies on Cd(II) complexes incorporating di-2-pyridyl ligand and the X-ray crystal structure of the chloroform solvated DPMNPH/CdI2 complex by Ismail Warad; Mohammad Azam; Saud I. Al-Resayes; Mohd Shahnawaz Khan; Pervez Ahmad; Mohammed Al-Nuri; Shehdeh Jodeh; Ahmad Husein; Salim F. Haddad; Belkheir Hammouti; Mousa Al-Noaimi (155-161).
A series of novel Cd(II) complexes incorporating ligand, di(2-pyridinyl)methanone N-(2-pyridinyl)hydrazone (DPMNPH), has been investigated. The ligand, DPMNPH, and its corresponding complexes have been characterized with the help of a number of techniques: microanalysis, FT-IR, 1H and 13C NMR, UV/vis spectroscopy, thermal studies and MS–FAB mass spectrometry. In addition, single crystal X-ray diffraction measurement studies are also employed in one of the complexes showing a distorted trigonal bipyramidal geometry. Furthermore, the existence of NH⋯Npy intramolecular hydrogen bonding interactions in the ligand and its corresponding complexes has also been reported.A series of novel Cd(II) complexes incorporating ligand, di(2-pyridinyl)methanone N-(2-pyridinyl)hydrazone (DPMNPH), has been investigated. Single crystal X-ray diffraction measurement studies show that complexes have a distorted trigonal bipyramidal geometry. Furthermore, intramolecular hydrogen bonding N―H⋯NPy is also observed in ligand and complexes.Display Omitted
Keywords: Cd(II) complexes; DPMNPH ligand; X-ray single crystal structure; Intramolecular hydrogen bonding;

Photophysical characterization of [Ir(ppy)2(dmb)][PF6] towards application in light-emitting electrochemical cells (LECs) by Kassio Papi Silva Zanoni; Mario Sabro Sanematsu; Neyde Yukie Murakami Iha (162-164).
A detailed photophysical characterization of [Ir(ppy)2(dmb)]+, ppy = 2-phenilpyridyne and dmb = 4,4′-dimethyl-2,2′-bipyridyne, was performed in dichloromethane and films to be evaluated as active layers in light-emitting devices. The complex showed suitable photophysical features (ϕ  = 0.22 and τ  = 0.60 μs) in different media and was successfully applied, for the first time, as a thin spin-coated emissive layer in an ionic transition metal complex (iTMC) light-emitting electrochemical cell (LEC). The optoelectronic characterization of the FTO/PEDOT:PSS/[Ir(ppy)2(dmb)][PF6]/Al device was carried out outside of a glovebox, with CIE coordinates of x = 0.48 and y = 0.50 and current efficiency up to 59.7 cd A− 1. This iTMC LEC, which turned on even under air, stands as a bridge between molecular devices and manufacture engineering to contribute for affordable LEC fabrication processes.The graphical abstract demonstrates the use of [Ir(ppy)2(dmb)]+ in the active layer of a LEC and the employed device architecture, with pictures of both photo and electroluminescence. It properly summarizes the developed work, which serves as a bridge between conventional photoluminescence characterization and application in electroluminescent devices.Display Omitted
Keywords: Iridium complex; Phosphorescence; Triplet emitter; Light-emitting electrochemical cell; LEC;

Single-crystal to single-crystal photochemical structure transformation of a ladder-like coordination polymer with dinuclear Zn(II) platform by Gui-Lian Li; Wei-Dong Yin; Guang-Zhen Liu; Lu-Fang Ma; Lei-Lei Huang; Lin Li; Li-Ya Wang (165-168).
A new coordination polymer, namely [Zn(Hnbdc)2(bpe)]n (1) (H2nbdc = 3-nitrobenzene-1,2-dicarboxylic acid and bpe = 1,2-bi(4-pyridyl)ethylene), has been hydrothermally synthesized and characterized preliminarily by elemental analysis, infrared spectroscopy, thermal analysis, and X-ray diffractions. Single crystal X-ray diffraction showed that compound 1 possesses a ladder-like topology structure featuring carboxyl-bridged dinuclear Zn(II) spaced by parallel bpe coligand pairs and has the capacity of undergoing a 100% photochemical [2 + 2] cycloaddition reaction to transform into compound [Zn(Hnbdc)2(rctt-tpcb)]n (2) in a single-crystal to single-crystal form. In addition, the fluorescent property of 1 was also investigated.A ladder-like coordination polymer with dinuclear Zn(II) platform displays a single-crystal to single-crystal photochemical structure transformation upon UV radiation.Display Omitted
Keywords: Zinc(II); Luminescence; Hydrothermal reaction; Coordination polymer; Photochemical [2 + 2] cycloaddition reaction;

A novel {− Ni12Na2-Ni-}n chain has been characterized from the reaction between 2-pyridylcyanoxime, (pyC{CN}NOH), and nickel(II) sulfate. The template synthesis around a Na+ cation gives an unprecedented arrangement of four nickel triangles coordinated to the central sodium ion by sulfato bridges.Nickel sulfate and 2-pyridylcyanoxime in the presence of Na+ templating cations leads to {Ni12Na} units with four {Ni3(μ 3-OH)(SO4)(R-NO)2}+ triangular subunits linked to the central sodium by sulfato bridges.Display Omitted
Keywords: Supramolecular; Template synthesis; Sulfato complexes; Metallamacrocycle; Magnetic measurements;

4-Amino-1,8-naphthalimide-based fluorescent sensor with high selectivity and sensitivity for Zn2 + imaging in living cells by Da-Ying Liu; Jing Qi; Xiao-Yan Liu; Hua-Rui He; Jia-Tong Chen; Guang-Ming Yang (173-178).
A new 4-amino-1,8-naphthalimide-based fluorescent sensor with iminodiacetic acid as receptor, was synthesized and characterized. Under physiological pH conditions, it demonstrates high selectivity and sensitivity for sensing Zn2 + with about 50-fold enhancement in fluorescence intensity. The fluorescent sensor exhibited a characteristic emission band of 4-amino-1,8-naphthalimide with a green color centered at ~ 550 nm and was successfully applied to image Zn2 + in living cells. Upon sensing of Zn2 + the fluorescence emission spectrum is “switched on” demonstrating the suppression of PET from the receptor to the fluorophore.A new 4-amino-1,8-naphthalimide-PET-based fluorescent sensor, with iminodiacetic acid as receptor, demonstrates high selectivity and sensitivity for sensing Zn2 +. It was successfully applied to image Zn2 + in living cells.Display Omitted
Keywords: Fluorescent sensor; Naphthalimide; Iminodiacetic acid; Zinc;