Carbazole Integrated Tetrakis-(1 H-pyrrole-2-carbaldehyde): A Highly Selective Fluorescent Probe for HP2O73.

A new carbazole-coupled tetrakis-(1 H-pyrrole-2-carbaldehyde) anion receptor 1 has been designed and synthesized. Anion binding studies in organic media using fluorescence and UV-vis spectroscopy revealed that receptor 1 is capable of sensing HP2O73- with high selectivity. Addition of HP2O73- to THF solution of 1 resulted in the emergence of a new broad band at longer wavelength along with quenching of the original emission band forming a ratiometric response. Based on dynamic light scattering (DLS) experiment and fluorescence lifetime measurement, we propose that the emergence of new emission band in the presence of HP2O73- ion is due to the aggregation-induced excimer formation.

Coligands Controlled Reactivities of Ruthenium(II) Precursors: Antiferromagnetically Coupled Ruthenium(III)-Phenoxyl versus Ruthenium(II)-Phenoxyl Forms.

The study disclosed that the reactivities of [RuII (PPh3)3Cl2] and [RuII(PPh3)3(CO)(H)Cl] precursors toward a trimethoxyarylimino-phenol derivative are sensibly different. The former promotes methoxy demethylation reaction affording a [Phenolato-RuIII-Phenolato] unit, while the latter containing π-acidic CO and hydride as coligands leads to C-H activation reaction, generating a [Phenolato-RuII-Aryl] unit. Notably, the oxidized analogues of these two forms produce antiferromagnetically coupled [RuIII-phenoxyl] and paramagnetic [RuII-phenoxyl] forms, which exhibit diverse reactivities. Surprisingly, the magnetically coupled [RuIII-phenoxyl] form obtained from [Phenolato-RuIII-Phenolato] motif leads to coligand, PPh3 oxidation and undergoes dimerization, making a Ru-Ru bond (2.599(2) Å), while the [RuII-phenoxyl] form obtained from [Phenolato-RuII-Aryl] motif leads to C-C coupling and H abstraction reactions. The coupling reaction affords a 4,4'-dibenzosemiquinonate anion radical complex, but the H-abstraction of the phenoxyl form gives a [RuII-Phenol] complex. For comparison, [RuII(IQR 0)] and [RuII(ISQR·-)] complexes were also isolated, where IQR 0 and ISQR·- are p-R-o-iminobenzoquinone and p-R-o-iminobenzosemiquinonate anion radicals. However, they fail to promote any bond-formation reaction. The molecular and electronic structures of the ruthenium (II/III) complexes were confirmed by single-crystal X-ray crystallography, EPR spectroscopy, and DFT calculations.

Correlation in Structural Architecture toward Fabrication of Schottky Device with a Series of Pyrazine Appended Coordination Polymers.

Energy is the center of importance for the survivability of civilization. Use of fossil fuel is going to be suspended, and renewable energy is technologically costlier. In the quest for new energy sources and to minimize fuel expenditure, the design of energy efficient devices is one of the solutions. Toward this objective, highly delocalized π-acidic N-hetreocycle pyrazine bridged Cd(II)-based coordination polymers (CPs), [Cd(tppz)(adc)(MeOH)] (1), [Cd(tppz)(trep)] (2), and [Cd(tppz)(2,6-ndc)] (3; tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) are synthesized in combination with π-accessible dicarboxylato linkers (acetylene dicarboxylic acid (H2adc), terephthalic acid (H2trep), and 2,6-naphthalene dicarboxylic acid (2,6 H2ndc)). The structures of the compounds, 1-3, have been confirmed by single-crystal X-ray diffraction measurements. Analysis of electrical property demonstrates that light irradiation enhances the conductivity and follows the order 3 > 2 > 1; compound 3 possesses the highest conductivity (1.93 × 10-3 (light), 1.12 × 10-4 S m-1 dark)), than 2 (1.80 × 10-4 (light), 1.10 × 10-4 S m-1 (dark)) and 1 (5.06 × 10-5 (light), 4.72 × 10-5 S m-1 (dark)). This light-induced electrical conductivity can pave the way toward fabrication of an active electronic device by using the discussed materials.

Aminoisophthalate Bridged Cd(II)-2D Coordination Polymer: Structure Description, Selective Detection of Pd2+ in Aqueous Medium, and Fabrication of Schottky Diode.

Photoluminescence activity of coordination polymers (CPs) has evoked intricate applications in the field of materials science, especially sensing of ions/molecules. In the present study, 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) and 5-aminoisophthalate (HAIPA-) coordinated to Cd(II) to architect a coordination polymer, {[Cd(HAIPA)(tppz)(OH)]·3H2O}n (CP1) which unveils blue emission in an aqueous acetonitrile (98% aqueous) suspension. The emission is selectively quenched by Pd2+ only without interference in the presence of as many as 16 other cations. The structure of CP1 shows the presence of a free -COOH group, and the interlayer (-CO)O(2)···O(7) (OC-) distance, 4.242 Å, along with the π···π interactions (3.990, 3.927 Å), may make a cavity which suitably accommodates only Pd2+ (van der Waal's radius, 1.7 Å) through the Pd(II)-carboxylato (-COO-Pd) coordination. The stability of the composite, [CP1 + Pd2+] may be assessed from the fluorescence quenching experiment, and the Stern-Volmer constant (KSV) is 7.2 × 104 M-1. Therefore, the compound, CP1, is a promising sensor for Pd(II) in a selective manner with limit of detection (LOD), 0.08 µM. The XPS spectra of CP1 and [CP1 + Pd2+] have proven the presence of Pd2+ in the host and the existence of a coordinated -COO-Pd bond. Interestingly, inclusion of Pd2+ in CP1 decreases the band gap from 3.61 eV (CP1) to 3.05 eV ([CP1 + Pd2+]) which lies in the semiconducting region and has exhibited improved electrical conductivity from 7.42 × 10-5 (CP1) to 1.20 × 10-4 S m-1 ([CP1 + Pd2+]). Upon light irradiation, the electrical conductivities are enhanced to 1.45 × 10-4 S m-1 (CP1) and 3.81 × 10-4 S m-1 ([CP1 + Pd2+]); which validates the highly desired photoresponsive device applications. Therefore, such type of materials may serve as SDG-army (sustainable development goal) to battle against the environmental issues and energy crisis.

Two pillared-layer metal-organic frameworks based on the pinwheel trinuclear carboxylate-clusters of Zn(II) and Co(II): synthesis, crystal structures, magnetic study, and Lewis acid catalysis.

Using a dicarboxylic acid, [1,1'-biphenyl]-4,4'-dicarboxylic acid (H2L1) and an exobidentate ligand, (1E,1'E)-N,N'-(1,4-phenylene)bis(1-(pyridin-4-yl)methanimine) (L2), two 3D interpenetrated networks, {[Zn3(L1)3(L2)]·9H2O}n (Zn-MOF) and {[Co3(L1)3(L2)(DMF)]·0.5DMF}n (Co-MOF), have been prepared in good yields. The crystal structure analysis of Zn-MOF and Co-MOF revealed that both have a 3D pillared-layer structure based on pinwheel trinuclear metal-carboxylate clusters as secondary building units (SBUs). Furthermore, the structures also exhibited three-fold interpenetration. Although the overall networks in Zn-MOF and Co-MOF showed significant resemblances, there are marked differences in their crystal structures, which are associated with the coordination environment of the metal centre and the binding modes of the carboxylates. Gas adsorption studies (N2 at 77 K and 1 bar) indicated that Co-MOF is more porous than Zn-MOF. Magnetic measurements on Co-MOF indicate a significant antiferromagnetic interaction (45 K to 303 K) between trimeric Co(II) S = 3/2 spins through syn-syn carboxylato bridges. Both MOFs were studied for the Lewis acid catalyzed Knoevenagel condensation reactions between benzaldehydes and malononitrile with an active methylene group, where Zn-MOF was found to be a better catalyst than Co-MOF. This was supported by the Monte Carlo simulations indicating the better substrate binding ability of Zn-MOF than Co-MOF.

Diastereo- and regioselective petasis aryl and allyl boration of ninhydrins towards synthesis of functionalized indene-diones and dihydrobenzoindeno-oxazin-ones.

Petasis aryl and allyl borations were accomplished using substituted ninhydrins, boronic acids or 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 1,2-aminophenols in Hexafluoroisopropanol (HFIP) without any catalysts to synthesize different aryl and allyl derivatives of ninhydrins. The nature of substitution in the boronic acids and 1,2-amino phenols was the key factor in determining the diastereo-regioselectivity and the type of product distributions. The products were isolated and characterized by HMBC, HSQC, 1H, 13C NMR experiments and X-ray single crystallographic analysis. A probable reaction pathway involves in situ formation of acyclic and cyclic ninhydrin-amino alcohol adducts, with the positioned hydroxyl group determining the stereo-regioselective outcome via tetracoordinated boron intermediates. A metal free diastereo- and regioselective Petasis aryl and allyl boration of ninhydrins.

Rational synthesis of a pyridyl-imidazoquinazoline based multifunctional 3D Zn(II)-MOF: structure, luminescence, selective and sensitive detection of Al3+ and TNP, and its semiconducting device application.

In the age of sustainable development, the exploration of multifunctional materials is of high priority due to their economic benefits and environmental suitability. A stable luminescent coordination polymer, [Zn2(tdc)4(pdiq)3] (1), (pdiq = pyridyl-imidazoquinazoline; H2tdc = 2,5-thiophenedicarboxylic acid) has been prepared and structurally confirmed by single-crystal X-ray diffraction analysis. The 3D framework consists of a distorted octahedral geometry with a ZnO4N2 coordination sphere where four carboxylato-O donations come from two tdc2- as bridging ligands and two pyridyl-Ns come from two pdiq. The π⋯π interactions between the imidazolium and phenyl groups bestow robustness on the architecture. The compound is chemically stable to water, shows tolerance to acid/base aqueous solutions (pH = 2-12), and is stable to the impact of organic solvents. The high dispersibility of Zn-MOF (1) in acetonitrile may enhance the fluorescence intensity compared to that in water, which prompted fluorescence measurements in the former solvent and it is used for the efficient and selective turn-off ratiometric sensing of Al3+ ions (LOD, 1.39 × 10-7 M). In addition, the fluorescence emission of 1 is instantly quenched by trinitrophenol (TNP) and the LOD is 1.54 × 10-7 M. The Tauc's plot is used to measure the semiconducting band gap (3.33 eV) and the electrical conductivity is significantly increased upon illumination (Λ: 1.14 × 10-3 S m-1 (dark), 5.35 × 10-3 S m-1 (light)) and the energy barrier declines marginally (FB: 0.57 (dark), 0.49 (light)). Transit time (τ) and diffusion length (LD) at the quasi-Fermi level were analyzed to offer information on the charge transport mechanism of the compound. The better performance on photo-irradiation signifies the enhanced charge transfer kinetics of a Zn-MOF coated thin-film device (TFD 1), which encourages its application in semiconductor devices.

Activation of O2 across a C(sp3)-C(sp3) bond.

The activation of atmospheric molecular dioxygen (O2) is reported, which occurred across a C(sp3)-C(sp3) bond of a piperazine derivative without any catalyst at ambient conditions under the formation of 1,2,4,7-dioxadiazoctane, an 8-membered (larger-ring) cyclic organic peroxide.

Idiosyncatic recognition of Zn2+ and CN- using pyrazolyl-hydroxy-coumarin scaffold and live cell imaging: depiction of luminescent Zn(II)-metallocryptand.

Multi-responsive and selective sensor design is one of the stimulating research areas in the sensors field. We have designed a pyrazolyl-hydroxy-coumarin scaffold, 7-hydroxy-4-methyl-8-(((5-phenyl-1H-pyrazol-3-yl)imino)methyl)-2H-chromen-2-one (H2L) and characterized it by spectroscopic techniques (1H NMR, 13C NMR, ESI-MS, IR). The single crystal X-ray diffraction measurement confirms the molecular structure of the probe. It shows the selective sensing of Zn2+ in the presence of sixteen other cations with 'Turn On' approach through the enhancement of green florescence ((λem = 499 nm; λex = 390 nm) in CH3CN/H2O (99 : 1, v/v; HEPES buffer, pH 7.5) medium with the limit of detection (LOD) of 34.76 nM. The structural depiction of the isolated Zn2+ complex reveals cage like metallocryptand cyclic hexamer, [Zn6L6] with 30.9% void of cavity along the crystallographic c axis of approximate dimension of 7.502 × 7.050 × 7.068 Å3. The diffusion NMR study reveals only one type of complex in the solution, having 1 : 1 composition, i.e., Zn2+ : H2L, which affirms the isolated form of the complex. On the other hand, the receptor, H2L, recognizes the very noxious anion CN- out of sixteen anions. The product identification using spectroscopic techniques supports the nucleophilic addition of CN- across the exocyclic imine (CN) bond, which shows blue emission ((λem = 447 nm; λex = 390 nm), and the LOD was 19.91 nM. The composition of [H2L-Zn2+] and [H2L-CN-] was established by 1H NMR titration, Job's method, ESI-MS, and FTIR spectra. The efficacy of the probe was further studied using MTT assay in MDA-MB 231 and WI-38 cell line as well as for the intracellular imaging of Zn2+ and CN- using a fluorescence microscope. Flow Cytometry was further performed for the quantitative analysis of Zn2+ distribution in MDA-MB 231 cells.

Green synthesis of C5-C6-unsubstituted 1,4-DHP scaffolds using an efficient Ni-chitosan nanocatalyst under ultrasonic conditions.

A heterogeneous and magnetically recyclable Ni-chitosan nanocatalyst was synthesized and thoroughly characterized by powder Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray (EDX) spectroscopy, etc. It was effectively utilized in the eco-friendly synthesis of new C5-C6-unsubstituted 1,4-DHPs under ultrasonic irradiation. The important focus of the methodology was to develop an environmentally friendly protocol with a short reaction time and a simple reaction procedure. The other advantages of this protocol are a wide substrate scope, a very good product yield, the use of an eco-friendly solvent and a recyclable nanocatalyst, as well as reaction at room temperature.

A Reusable Efficient Green Catalyst of 2D Cu-MOF for the Click and Knoevenagel Reaction.

[Cu(CPA)(BDC)]n (CPA = 4-(Chloro-phenyl)-pyridin-4-ylmethylene-amine; BDC = 1,4-benzenedicarboxylate) has been synthesized and structurally characterized by single crystal X-Ray diffraction measurement. The structural studies establish the copper (II) containing 2D sheet with (4,4) square grid structure. The square grid lengths are 10.775 and 10.769 Å. Thermal stability is assessed by TGA, and subsequent PXRD data establish the crystallinity. The surface morphology is evaluated by FE-SEM. The N2 adsorption-desorption analysis demonstrates the mesoporous feature (∼6.95 nm) of the Cu-MOF. This porous grid serves as heterogeneous green catalyst with superficial recyclability and thermal stability and facilitates organic transformations efficiently such as, Click and Knoevenagel reactions in the aqueous methanolic medium.

A combined experimental and theoretical study on a single, unsupported oxo-bridged Mn(III,III) dimer coordinated to two iminobenzosemiquinone π-radical anions.

Ligand H2LAP comprises a non-innocent 2-aminophenol unit and an innocent bis(pyridin-2-ylmethyl)amine unit. The ligand, upon reaction with an equivalent amount of Mn(ClO4)2·6H2O in the presence of Et3N under air in MeOH, provided a mono(oxo)-bridged dinuclear Mn2 complex ({[(LISQ)MnIII-O-MnIII(LISQ)][(ClO4)]2}; 1). X-ray crystal structure analysis of complex 1 revealed that in the dicationic unit, the physical oxidation state of each Mn ion was +III and the 2-aminophenol unit of ligand H2LAP was in its one-electron oxidized iminobenzosemiquinone form. 1H-NMR measurement of complex 1 confirmed that the complex acquired a diamagnetic ground state (St = 0). Thus, antiferromagnetic couplings among the paramagnetic centers were realized. The UV-Vis-NIR spectrum of complex 1 was consisted of ligand-to-metal charge-transfer transitions in the visible region, while ligand-to-metal and metal-to-ligand charge-transfer transitions were noticed in the near-infrared region due to the presence of iminobenzosemiquinone radical units. The cyclic voltammogram of the complex showed three one-electron oxidation waves and two one-electron reduction waves. While the first two oxidation processes were metal-based, the two successive reductions were ligand-centered. DFT-based theoretical studies confirmed the assignment.

Sunlight assisted SCSC dimerization of a 1D coordination polymer impacts the selectivity of Pd(II) sensing in water.

A one-dimensional coordination polymer (1D CP) [Cd(4-nvp)2(5-ssa)]·(4-nvp) (1) [4-nvp = 4-(1-naphthylvinyl)pyridine and 5-ssa = 5-sulfosalicylic acid] undergoes topochemical [2+2] cycloaddition by sunlight irradiation to generate a two-dimensional (2D) CP [Cd(rctt-4-pncb)0.5(4-nvp)(5-ssa)]·(4-nvp) (1') [rctt-4-pncb = 1,3-bis(4'-pyridyl)-2,4-bis(naphthyl)cyclobutane] in a single-crystal to single-crystal manner. Interestingly, 1' can be reverted back to 1 by heating and both the CPs selectively recognize Pd2+ in aqueous medium; however, the limit of detection is improved after photodimerization.

Mixed-valence di-ruthenium(II,III) complexes of redox non-innocent N-aryl-o-phenylenediamine derivatives.

A mononuclear ruthenium(ii), [(L1IQ)Ru2+(PPh3)2Cl2]·CHCl3 (1·CHCl3), a di-ruthenium(ii,ii), [(L2IQ)2Ru24+Cl4(PPh3)2] (2) and a mixed-valence di-ruthenium(ii,iii), [(L3IQ)Ru25+Cl5(PPh3)2]·MeOH (3·MeOH) complex, where L1IQ, L2IQ and L3IQ are, respectively, o-diiminobenzoquinone forms of redox non-innocent N-(5-nitropyridyl)-o-phenylenediamine (L1H2), N-(2,4-dinitrophenyl)-o-phenylenediamine (L2H2) and N-(3-nitropyridyl)-o-phenylenediamine (L3H2) derivatives, were successfully isolated. The molecular and electronic structures of 1·CHCl3, 2 and 3·MeOH were confirmed by single-crystal X-ray crystallography, EPR, UV-Vis-NIR spectroscopies and density functional theory (DFT) calculations. Both 1·CHCl3 and 2 exhibited reversible anodic waves due to the Ru(iii)/Ru(ii) redox couple, while the cyclic voltammogram of 3·MeOH displayed two successive cathodic waves due to ruthenium(iii)/ruthenium(ii) and (L3IQ/L3ISQ) redox couples. EPR spectroscopy and DFT calculations inferred that 1+ is a ruthenium(iii) complex of L1IQ, [(L1IQ)Ru3+(PPh3)2Cl2]+, 2+ is a mixed-valence di-ruthenium(ii,iii) complex of L2IQ, [(L2IQ)2Ru25+Cl4(PPh3)2]+ and 3- is a di-ruthenium(ii,ii) complex, [(L3IQ)Ru24+Cl5(PPh3)2]-, while 32- is a di-ruthenium(ii,ii) complex of L3ISQ, [(L3ISQ)Ru24+Cl5(PPh3)2]2-, where L3ISQ is the o-diiminobenzosemiquinonate anion radical form of the L3H2 with a significant contribution of the mixed-valence di-ruthenium(iii,ii) form, [(L3AM)Ru25+Cl5(PPh3)2]2- (L3AM is the di-amido form of the L3H2 ligand). The spin density obtained from the Mulliken spin population analyses of the broken-symmetry (BS) DFT calculations was localized on Ru(2) in 3, while it was delocalized over both Ru(1) and the o-phenylenediamine fragment in 32-. The inter-valence charge-transfer (IVCT) transitions of 2+ and 3 were relatively weaker and occurred at 1680 and 1685 nm, respectively, while 32- exhibited a broader NIR absorption band at 1500-2000 nm. The calculated electronic-coupling parameters (Hab) using the Mulliken-Hush equation for 3 and 2+ ion, respectively, were 62 and 103 cm-1, defining these as Robin-Day class II mixed-valence systems.

X-ray structure of two Schiff bases: TURN-ON sensing of Fe3+ and Al3+ in the HepG2 cell line.

The efficiency of the fluorescence sensitivity of a sensor may be tuned by the modulation of the steric and electronic parameters in the structure. In this study, the thiophenyl Schiff base (E)-N1-(phenyl(pyridin-2-yl)methyl)-N2-(thiophen-2-ylmethylene)benzene-1,2-diamine (HL') exhibited very high selectivity and a sensitive fluorescence enhancement towards Fe3+ with violet emission (λem, 385 nm; LOD, 3.8 nM). On the other hand, the naphthyl Schiff base (E)-1-(((2-((phenyl(pyridin-2-yl)methyl)amino)phenyl)imino)methyl)naphthalen-2-ol (H2L'') exhibited fluorescence sensitivity towards Al3+, showing blue emission (λem, 502 nm; LOD, 3.3 nM) in H2O (HEPES buffer, pH 7.4) medium. The emission enhancement of HL' upon binding to Fe3+ may be considered to be due to the restriction of intramolecular rotation, while the selectivity of H2L'' towards Al3+ may be due to the turn on emission through the restriction of excited state intramolecular proton transfer (ESIPT) and the introduction of chelation enhanced fluorescence (CHEF). Furthermore, DFT computation supported the sensing strategy and the probes were applied for intracellular detection of Fe3+ and Al3+ in HepG2 cell lines.

Electrically conductive Cu(II)-based 1D coordination polymer with theoretical insight.

A nitro-functionalized Cu(ii)-based one-dimensional coordination polymer (1D CP) [Cu(nip)(4-phpy)2]n (1) (H2nip = 5-nitroisophthalic acid and 4-phpy = 4-phenylpyridine) was synthesized and characterized by elemental analysis, powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SCXRD). In the solid-state self-assembly of 1, two sets of weak intermolecular forces, CHπ interaction among the axially bound 4-phpy ligands and ππ interaction among bridging nip ligands from adjacent 1D coordination polymeric chains led to 3D supramolecular packing. Interestingly compound 1 exhibited electrical conductivity in the semiconducting regime and behaved as a Schottky barrier diode.

A Chemodosimetric Approach for Fluorimetric Detection of Hg2+ Ions by Trinuclear Zn(II)/Cd(II) Schiff Base Complex: First Case of Intermediate Trapping in a Chemodosimetric Approach.

The present work discloses the application of two fluorescent zinc and cadmium complexes (1 and 2) for sensing of Hg(II) ions through a chemodosimetric approach. The ligand under consideration in this work is a N2O donor Schiff base ligand (E)-4-bromo-2-(((2-morpholinoethyl)imino)methyl)phenol (HL), which has been harnessed to generate complexes [Zn3L2(OAc)4] (1) and [Cd3L2(OAc)4] (2). X-ray single crystal diffraction studies unveil the trinuclear skeleton of complexes 1 and 2. Both complexes have been found to be highly fluorescent in nature. However, the quantum efficiency of Zn(II) complex (1) dominates over the Cd(II) analogue (2). The absorption and emission spectroscopic properties of the complexes have been investigated by density functional theory. Complexes 1 and 2 can detect Hg2+ ions selectively by fluorescence quenching, and it is noteworthy to mention that the mechanism of sensing is unique as well as interesting. In the presence of Hg2+ ions, complexes 1 and 2 are transformed to mononuclear mercuric intermediate complex (3) and finally to a trinuclear mercuric complex (4) by hydrolysis. We have successfully trapped the intermediate complex 3, and we characterized it with the aid of X-ray crystallography. Transformation of complexes 1 and 2 to intermediate complex 3 and finally to 4 has been established by UV-vis spectroscopy, fluorescence spectroscopy, ESI-MS spectroscopy, 1H NMR spectroscopy, and X-ray crystallography. The spontaneity of the above conversion is well supported by thermodynamic aspects as reflected from density functional theoretical calculations.

Coordination polymers of Ag(i) and Hg(i) ions with 2,2'-azobispyridine: synthesis, characterization and enhancement of conductivity in the presence of Cu(ii) ions.

The cationic coordination polymers (CPs) of the types [Hg2(abpy)2]n[PF6]2n (1) and [Ag(abpy)]n[PF6]n (2) (abpy = 2,2'-azobispyridine) were synthesized and characterized. Experimentation using the crystals confirmed that 1 and 2 are conductors of electricity. The relative conductivity of 1 is 62 times greater than that of 2. The conductivity of 1 increases 70 fold when it reacts with Cu2+ ions.

Biporous Cd(II) Coordination Polymer via in Situ Disulfide Bond Formation: Self-Healing and Application to Photosensitive Optoelectronic Device.

A heteroporous metal-organic framework, [Cd2(2,2'-DSB)2(INH)2(H2O)2]n (1), is fabricated by the reaction of CdI2, 2-mercaptobenzoic acid (2-MBAH), and isoniazid (INH). The X-ray structure of the compound 1 shows the bridging INH and 2,2'-disulfanediyldibenzoic acid (H22,2'-DSBA) around the Cd(II) ion center. 2-MBAH has been in situ dimerized to the formation of 2,2'-DSB2- (S-S-bonded dianion), which has further extended to form the 2D network. However, supramolecular assembly via π···π and hydrogen bonds strengthens the structural motif within the 3D array. Optical stimulation generated the thiol radical under an argon environment followed by the electron paramagnetic resonance (EPR) study, but upon exposure to air, the EPR signal gradually disappeared by the formation of the S-S bond, which was commonly known as a self-healing property. Again, compound 1 exhibited as a semiconducting material with a band gap of 3.7 eV. The I-V characteristics of 1 show that the conductivity is intensified by an optical response. The Schottky diode property of 1 shows a lower barrier height, a lower resistance, and a higher conductivity upon illumination at 360 nm.

Designing of Pb(II)-Based Novel Coordination Polymers (CPs): Structural Elucidation and Optoelectronic Application.

[Pb2(bdc)1.5(aiz)] n (1) and [Pb2(bdc)1.5(aiz)(MeOH)2] n (2) (H2bdc = 1,4-benzene dicarboxylic acid, aiz = (E)-N'-(thiophen-2-ylmethylene)isonicotinohydrazide) have been synthesized, and structural characterization has been established by X-ray analysis and thermogravimetric analysis (TGA). Here, bdc2- links two Pb(II) centers and the aiz ligand binds the metal centers in two different manners: chelating and monodonating. Thus, polymerizations have taken place from the combination of mixed ligand system. Optical band gaps have been studied via UV measurements. Again, the experimental and calculated (from density functional theory (DFT)) band gaps agree well and the semiconducting properties of synthesized polymeric materials have been approved. Thus, optoelectronic and photonic devices can be made by this type of coordination polymers (CPs). The I-V representative curves of 1 (device-A) and 2 (device-B) in both dark and illuminated conditions show that device-A has a higher magnitude of current than device-B. Dark- and photo-conductivity values of device-A are calculated as 2.94 × 10-6 and 6.12 × 10-6 S m-1, respectively, whereas for device-B, the values of dark- and photo-conductivity are 2.92 × 10-7 and 3.66 × 10-7 S m-1, respectively, at room temperature.