•Three novel Cu(Ⅱ)-based acylhydrazone porphyrin derivatives have been synthesized.•Versatile physicochemical means suggested Cu-Por3 has strongest binding affinity.•MTT tests showed Cu-Por3 with good cytotoxicity to A549, but weak for normal cell.•An extraction method was performed to quantified identify the cellular uptake.•Besides, Cu-Por3 induced A549 death mainly via apoptotic and arrested G1 phase.A panel of novel water-soluble Cu(Ⅱ)-based acylhydrazone porphyrin complexes (denoted as Cu-PorX, X = 1, 2 and 3. See Fig. 1) were prepared and characterized. Versatile physicochemical approaches indicated that whole compounds could effectively bind with ct-DNA through intercalative or intercalative coupled with end-stacking interaction, especially, Cu-Por3 has the strongest binding affinity compared with others. Additionally, the antiproliferative activity has been evaluated by MTT assay turned out that Cu-Por3 yet exhibits gratifying cytotoxicity towards A549 (non-small cell lung cancer) cell line, suggesting that Cu-Por3 is a potential candidacy among tested agents. We also carried out the cellular uptake measurement by using an extracted method to better comprehend the anticancer behaviors. Moreover, for gaining deeper insight into the mechanism of cell death of affected by the representative complex Cu-Por3, the influences of this new conjugate on the cell cycle and the induction of apoptosis were illustrated via employing flow cytometric analysis.Novel water-soluble Cu(Ⅱ)-based acylhydrazone porphyrin derivatives have been synthesized. Versatile physicochemical approaches indicated that all the complexes could effectually bind with ct-DNA via intercalative or end-stacking interactions, especially, Cu-Por3 has the strongest binding affinity compared with others. Meanwhile, the antiproliferative activity has been evaluated by MTT assay turned out that Cu-Por3 yet exhibits gratifying cytotoxicity in A549 human lung cancer cell lines, suggesting that Cu-Por3 is a potential candidacy among the tested agents. An extraction method was performed to quantified identify the cellular uptake to better comprehend the anticancer behaviors. Moreover, the mode of cell death effected by the representative Cu-Por3 complex has been explored by using various biochemical techniques like cell cycle and apoptosis through flow cytometric analysis.

•The document of coordination polymers appended anchoring porphyrin is very few.•Two coordination polymers have been investigated in photoelectrochemical device.•The transmission electron microscopy analyzes surface morphologies of assemblies.•Self-assemblies devices improve Jsc of DSSC with monomer anchoring porphyrin.Two new acetohydrazide zinc porphyrin with different donor units based Mn (Ⅱ) ion coordination polymers (CPsx, x=1,2) have been designed, synthesized, and well-characterized. Two coordination polymers and anchor porphyrin (ZnPA) self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. Our results reveal that the self-assemblies devices show significantly improved photocurrent conversion efficiency. Particularly, CPs1 based solar cell showed higher short circuit current density and conversion efficiency. Their optical performance, electrochemical impedance spectroscopy and transient photovoltage decay were also investigated to further understand the photoelectrochemical results. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy (TEM), theory calculations and energy dispersive X-ray spectroscopy (EDX).Two novel acetohydrazide zinc porphyrin-based coordination polymers (CPsx, x=1,2) and anchoring porphyrin (ZnPA) via zinc-to-ligand axial coordinated assemblies. Then these assemblies were immobilized on TiO2 electrode surface for impressive improvement of photocurrent response in supramolecular solar cell.

•Tetrad water-soluble cationic porphyrin Cu(II)-complexes have been firstly reported.•Cu-P4 has higher binding affinity than others due to its smaller molecular dimension.•All complexes reveal preferable cytotoxicity on tumor cells but weak on normal cells.•Cellular uptake tested by an extracted method to better understand the cytotoxicity.•The Cu-P4 induced cell death via mainly late apoptosis and arrested S phase cells.Tetrad novel Cu-complex containing multifarious meso-10,15,20-Tris (N-methyl-2′-pyridyl)-5-(4′-X-acylhydrazone) porphyrin ligands, where X respectively referred to salicylaldehyde (Cu-P1), o-Vanillin (Cu-P2), pyridine-2-carboxaldehyde (Cu-P3) and acetone (Cu-P4), have been successfully isolated and well characterized. Multiple physicochemical approaches reveal the complex Cu-P4 with preferable binding affinity than its analogues due to smaller molecular dimension. Moreover, the mechanism of the anti-neoplasm action of these conjugates have been appraised via MTT assay, manifesting all of them possess superior cytotoxicity towards A549 (non-small cell lung cancer) and HepG2 (liver hepatocellular carcinoma cells) but weak cell toxicity for Hs 578Bst (human normal breast cells) which might be boiled down to porphyrin derivatives could enrich around malignant neoplasms. The flow cytometric analysis illustrates that delegate compound Cu-P4 induced cell death predominantly through late apoptosis and arrested S phase cells.Cu-complexes based on tricationic porphyrin acylhydrazone ligands were synthesized. The physicochemical methods indicate that Cu-P4 with preferable DNA-binding constants due to its smaller molecular size. In addition, they exhibit superior cytotoxicity towards A549 and HepG2 carcinoma cells but weak for Hs 578Bst normal cells. Especially, the Cu-P4 displays better cytotoxicity in A549 than its analogues and induced cell death via chiefly late apoptosis and arrested S phase cells.Download high-res image (334KB)Download full-size image

•A new 1,2,4-Triazole-based Cu(II) coordination polymer 1 have been designed, synthesized, and well-characterized.•The novel 3D coordination polymer 1 including two chiral helical chains and was synthesized via hydrothermal reaction.•PXRD pattern and TG analysis indicating that complex 1 has excellent phase purity and good thermal stability.•Magnetical studies have shown that there exists strong antiferromagnetic interaction between copper ions in complex 1.A novel Cu (II)-MOF, namely [Cu(Hhmt)]n (1) was obtained by employing copper nitrate and a triazole ligand (H3hmt) under hydrothermal conditions, where H3hmt = 3,5-bis (hydroxymethyl)-1,2,4-triazole. Single crystal X-ray analysis reveals that complex 1 crystallizes in the chiral tetragonal space group P43212 with a right-handed 43 and a left-handed 21 helical chains which lead to the formation of a 3D supramolecular structure. The phrase purity, IR spectra, thermal stabilities of 1 were also investigated. The nature of antiferromagnetic exchange of complex 1 is discussed based on the structure.A novel 1,2,4-Triazole-based 3D coordination polymer 1 ([Cu(Hhmt)]n) with two chiral helical chains was synthesized via hydrothermal reaction. Complex 1 has good thermal stability and exists strong antiferromagnetic interaction between copper ions.Download high-res image (101KB)Download full-size image

We prepared in this work an anchoring porphyrin and a series of hat-porphyrins. The zinc atom of the hat-porphyrins can be coordinated axially with the pyridine moiety of the anchoring porphyrin which is anchored on the titania surface by a carboxyl group. The structures of the assemblies were confirmed using computational calculations, transmission electron microscopy (TEM) and energy dispersive spectrometry (EDS). Solar cell devices of the monomer anchoring porphyrin and its assemblies were fabricated and the photovoltaic performances were measured under standard AM 1.5 sunlight irradiance. We found that the assembly devices showed higher JSC and lower VOC than that of the monomer anchoring porphyrin device. However, the comprehensive influence of JSC and VOC led to an enhancement in the solar-to-electric power-conversion efficiency (PCE) of the assemblies. We also studied the variation of JSC and VOC using electronic absorption and emission spectroscopy, charge extraction measurements, transient photovoltage decay measurements and electrochemical impedance spectroscopy.

Four novel cobalt(II) complexes {[Co3(L)2(dib)3(H2O)2]·2H2O}n (1), {[Co3(L)2(4,4′-bibp)3(H2O)4]·2H2O}n (2), {[Co(HL)(bidpe)]·H2O}n (3) and {[Co2(L)(bib)0.5(μ3-OH)]·2H2O}n (4) have been prepared by employing Co(II) nitrate, a tricarboxylate ligand (H3L) and different N-containing ligands under hydrothermal conditions, where H3L = 3-((6-carboxynaphthalen-2-yl)oxy)phthalic acid, dib = 1,4-di(1H-imidazol-1-yl)benzene, 4,4′-bibp = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl, bidpe = 1,1′-(oxybis(4,1-phenylene))bis(1H-imidazole), bib = 4,4′-bis((2-methyl-1H-imidazol-1-yl)methyl)-1,1′-biphenyl. Single crystal X-ray analysis reveals that complex 1 exhibits an infinite 2D framework formed by the L3− and dib ligands, complex 2 displays a 3D supramolecular architecture linked by hydrogen bonds, complex 3 features a 1D chain in which lattice water molecules locate with the help of hydrogen bonds, complex 4 is a homochiral 3D network with right-handed 43 and 21 helices. The phase purity, IR spectra and thermal stabilities of 1–4 have been investigated. Additionally, the magnetic behaviors for 1–4 have also been studied, revealing antiferromagnetic interactions between Co(II) ions in them.

•We study synthesized two metal–organic frameworks materials that used a semi-rigid carboxylic acid organic ligand. Complex 1 is a high multi-cored three-dimensional (3D) network with a (4,4)-connected topology and a symbol of (63.83)4(86).•The fascinating is that compound 1 shows rapid uptake for methyl orange (MO) and iodine (I2) molecule.•Compound 2 is a very fluorescent excellent sensor for detecting Fe3+ in aqueous solution.Two metal–organic frameworks (MOFs), [Ag2(H2L)(4,4′-bipy)(μ3-OH)]n (1) and [Zn3(L)2(bpe)2(H2O)2]n (2) were synthesized under hydrothermal conditions using the tricarboxylate and N-containing ligands (H3L = 3-(3-carboxyphenoxy) phthalic acid, 4,4′-bipy = 4,4′-bipyridine, bpe = 1,2-di(pyridine-4-yl)ethene), and structurally characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA), furthermore, fluorescent spectra and absorption properties are discussed. Structural analysis reveals that Complex 1 is built from H3L, 4,4′-bipy and trinucleated Ag to form a three-dimensional (3D) network with a (4,4)-connected topology and a symbol of (63.83)4(86). As for 2, a trinucleate secondary building units (SBU), linked by the H3L ligand generated a one-dimensional (1D) chain, then the two adjacent 1D chains are joined together by bpe ligand, yielding a 1D trapezoidal chain. Our successive application studies indicate that complex 1 shows rapid uptake for methyl orange (MO) and iodine (I2), compound 2 is an impressive Zn-MOF based sensor for detecting Fe3+ ions in aqueous solution.Two metal–organic frameworks (MOFs), [Ag2(H2L)(4,4′-bipy)(μ3-OH)]n (1) and [Zn3(L)2(bpe)2(H2O)2]n (2) were synthesized under hydrothermal conditions. The compounds 1 shows rapid uptake for methyl orange (MO) and iodine (I2), compound 2 is a very excellent Zn-MOF based sensor for detecting Fe3+ in aqueous solution.Figure optionsDownload full-size imageDownload as PowerPoint slide

•Axial-coordinated self-assemblies based on a novel zinc porphyrin (ZnP).•Isonicotinic acid analogues (A1, A2, A3 and A4) act as anchoring molecules.•Their performance in dye sensitized solar cells was tested.•All the assembly based cells have certain capabilities to export photocurrent.•Improved photocurrent generation of ZnP–A2 with a cyano-acrylic acid group.A novel zinc porphyrin ZnP bearing a 1,3,5-triazine-2,4-diamine unit has been designed and synthesized in good yields to construct axial-coordinated assemblies (denoted as ZnP–Ai, i = 1, 2, 3 and 4) with different isonicotinic acid analogues (assigned as A1, A2, A3 and A4) through zinc-to-ligand axial coordination approach. Then these assemblies were grafted onto TiO2 electrode surface to build dye sensitized solar cells. The performance of these cells also was examined. Photoelectrochemical measurements illustrate that all the assembly based cells have certain capabilities to export photocurrent. Especially, the ZnP–A2 assembly with a cyanoacrylic acid group based solar cell has the highest conversion efficiency of 0.81% with a JSC of 3.0 mA/cm2, a VOC of 0.38 V, and a FF of 0.71 among these assembly based solar cells. Additionally, the UV–vis absorption, fluorescence spectra, density functional theory (DFT) calculations, transmission electron microscopy (TEM) and electrochemical impedance spectra (EIS) were performed to determine the photoelectric behavior as well as morphological structure on the TiO2 surface modified by these assemblies.A novel zinc porphyrin ZnP bearing a 1,3,5-triazine-2,4-diamine unit has been designed and synthesized to construct axial-coordinated assemblies with different anchoring groups. Then these assemblies were grafted onto TiO2 electrode surface and their corresponding solar cells were successfully fabricated. The performance of these devices were studied and discussed.

•π-conjugated semirigid tricarboxylate ligands with naphthalene rings(H3L) were rationally designed.•Four Zn/Cd coordination polymers based on H3L have been successfully synthesized by solvothermal reaction.•Compound 3 is a promising luminescent probe for selectively sensing Cr3+ with high sensitivity in aqueous solutions.A novel series of Zn/Cd coordination polymers based on H3L, namely, [Zn2(HL)2(bipy)2(H2O)6]n (1), [Zn(HL)(phen)]n (2), [Cd3L2(bbi)3]n (3), [Zn3L2(bbi)3]n (4) [(H3L =4-[(1-carboxynaphthalen-2-yl)oxy]phthalic acid, bipy =4,4′-bipyridine, phen =1,10-phenanthroline, bbi =1,1′-(1,4-butanediyl)bis(imidazole] have been successfully synthesized by solvothermal reaction. Compound 1 possesses two diverse 1D chains constructed by different bipy coligands, which were further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. Compound 2 possesses a complicated 1D chain based on secondary building unit (SBU) with binuclear Zn cluster. Compounds 3 and 4 exhibit similar 2D→3D framework, which can be rationalized as (3,4,4)-connected 3D net with a Schläfli symbol of (63.8.102)2(63)2(64.8.10). In particular, compound 3 exhibited a high sensitivity for Cr3+ in aqueous solutions, which suggest that compound 3 is a promising luminescent probe for selectively sensing Cr3+.A series of novel Zn/Cd coordination polymers have been successfully synthesized by solvothermal reaction. The unique 3D Cd2+ polymer containing bbi as second ligand demonstrates high sensitivity for detection of toxic Cr3+ in aqueous solutions.

Three coordination polymers based on the new ligand oxamide N,N-bis(4-phthalic acid), namely [Zn(L)0.5-(2,2′-bpy)]n(1), [Ni2(2,2′-bpy)4(µ2-Ox)]L·3H2O (2) and [Cd(L)(1,10-phen)] (3) [L = oxamide N,N-bis(4-phthalic acid)], (2,2′-bpy = 2,2′-bipyridine), (1,10-phen = 1,10-phenanthroline), have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction: compound 1 is one-dimensional ladder-like coordination polymer, compound 2 exhibits a three-dimensional structure resulting in extensive hydrogen bonds built with the help of lattice water molecules, compound 3 also exhibits a three-dimensional supramolecular structure. All compounds were also characterized by elemental analysis, IR spectra and thermogravimetric analysis; furthermore, the magnetic measurements for 2 reveal antiferromagnetic coupling between the nickel(II) ions.

Mn(III) and Cu(II) complexes based on bis(N-(3-methoxy-salicylidene)-4-amino-phenyl)ether (H2L) have been successfully synthesized and characterized systematically by IR spectra, elemental analyses and X-ray single crystal diffraction. The antioxidant activity of the ligand and its metal complexes have been determined by DPPH, superoxide, hydroxyl and ABTS radical scavenging methods in vitro, suggesting that the Cu(II) complex exhibits greater antioxidant activity against DPPH, superoxide, hydroxyl and ABTS radicals than those of the ligand and the Mn(III) complex. Furthermore, the antimicrobial effects of the tested compounds have been tested against the growth of bacteria in vitro to assess their bactericidal properties. It has been found that the Cu(II) complex has lower MIC values and exhibits better antimicrobial effects than the free ligand and the Mn(III) complex.Mn(III) and Cu(II) complexes based on bis(N-(3-methoxy-salicylidene)-4-amino-phenyl)ether (H2L) have been synthesized and characterized. The antioxidant activity and antimicrobial effects of the ligand and its Mn(III) and Cu(II) complexes have been determined. The antioxidant activity and antimicrobial effects of the Cu(II) complex are stronger than the ligand and the Mn(III) complex.

Four complexes based on H3L, namely, [Zn2(L)(dib)1.5(μ2-O)]n (1), {[Zn(HL)(dib)]·H2O}n (2), [Zn(HL)(dib)]n (3), [Zn3(L)2(dib)3]n (4) [4-[(3-carboxynaphthalen-2-yl)oxy]phthalic acid (H3L) and 1,4-di(1H-imidazol-1-yl) benzene (dib)] have been synthesized by solvothermal reactions. Complex 1 displays (3,5)-connected gra-type topology with a Schläfli symbol of (63)(69.8), the two-dimensional (2D) structure was extended to a three-dimensional (3D) framework by dib ligand, showing an enhanced luminescence intensity. Complex 2 possesses a 2D 4-connected sql-type topology with a Schläfli symbol of (44.62), which are further stacked with each other by C–H⋯π and C–H⋯O interactions to form a 3D supramolecular framework. Complex 3 features a novel 4-connected topology with a Schläfli symbol of (33.42.5), the driving forces in 3D supramolecular​ frameworks are C–H⋯O, C–H⋯π, and π⋯π stacking interactions in 3. Complex 4 has a 3D (3,4,4)-connected net with a Schläfli symbol of (63.8.102)2(63)2(64.8.10), representing a new topological prototype. In addition, complexes 1–4 exhibit non-interpenetrated structures owing to the steric hindrance of the naphthalene ring. It is also noteworthy that dib Ligand may not only affect the coordination mode of polycarboxylate acid but also subtly adjust the pH value of reaction solvent as well as N,N′-dimethylformamide (DMF). Additionally, the luminescent properties were investigated in the solid state at room temperature for 1–4.Four coordination polymers based on a semirigid tricarboxylic acid together with dib ligand have been synthesized by solvothermal reactions. Their syntheses, 3D supramolecular​ frameworks, topological structures, and luminescent properties are discussed in detail.

Five CoII complexes based on H3L1 and H3L2, namely, [Co3(L1)2(4,4′-bipy)(H2O)3]n (1), [Co3(L1)2(4,4′-bipy)3(H2O)4]n (2), {[Co2(L1)(4,4′-bibp)(μ3-OH)(H2O)]·H2O}n (3), {[Co3(L2)2(dib)3]·2H2O}n (4), and [Co3(L2)2(4,4′-bibp)3]n (5) [(H3L1 = 4-[(3-carboxynaphthalen-2-yl)oxy]phthalic acid, H3L2 = 3-[(3-carboxynaphthalen-2-yl)oxy]phthalic acid, 4,4′-bipy = 4,4′-bipyridine, dib = 1,4-di(1H-imidazol-1-yl) benzene, and 4,4′-bibp = 4,4′-bis(imidazol)-biphenyl] have been synthesized by solvothermal reactions. Complex 1 displays a (4,4,6)-connected topology with a Schläfli symbol of (4.104.12)(411.64)(45.6)2, and the two-dimensional (2D) structure was assembled to form a three-dimensional (3D) framework by C–H···π interactions of internaphthalene rings, showing the dominant antiferromagnetic exchanges in a triangular {Co3} cluster. Complex 2 presents a 2D (3,4,4)-connected network with a Schläfli symbol of (5.62)2(52.63.7)2(54.82) and weakly antiferromagnetic behavior. Complex 3 features a novel (4,4,8)-connected topology with a Schläfli symbol of (32.4.52.6)2(32.42.52)2(34.46.58.67.72.8). In addition, complex 3 based on a parallelogram-shaped [Co4(μ3-OH)2]6+ secondary building unit provides antiferromagnetic interactions mediated by μ3-OH and syn-syn-COO– groups. The driving forces in 3D supramolecular frameworks are C–H···O, C–H···π, and π···π stacking interactions for 2–3. Complexes 4–5 have an identical (4,4,5)-connected 2D network with a Schläfli symbol of (4.64.8)(42.67.8)2(44.62)2. Additionally, the C–H···O hydrogen bonds between naphthalene rings and uncoordinated carboxy oxygen atoms extend 2D networks into 3D supramolecular frameworks. Magnetic investigations reveal that 4 and 5 exhibit antiferromagnetic interactions in the linear {Co3} unit.

Seven new complexes based on H4L1 and H4L2, namely, [Cd2(L1)(H2O)5]n (1), {[Cu5(L1)2(μ3-OH)2(H2O)4]·2H2O}n (2), {[Cd2(L1)(4,4′-bipy)2(H2O)3]·2H2O}n (3), [Zn2(L1)(4,4′-bipy)(H2O)3]n (4), {[Ni7(L1)4(4,4′-bipy)12(H2O)12]·2H2O}n (5), {[Ni1.5(L2)(4,4′-bipy)1.5(H2O)4]·H2O}n (6), and {[Ni9(L2)6(dib)12(H2O)18]·18H2O}n (7) [(H4L1 = 4-(3′,5′-dicarboxylphenoxy)phthalic acid, H4L2 = 3-(3′,5′-dicarboxylphenoxy)phthalic acid, 4,4′-bipy = 4,4′-bipyridine, dib = 1,4-di(1H-imidazol-1-yl)benzene], have been synthesized by solvothermal reactions. Complex 1 possesses a 4-connected chiral three-dimensional (3D) structure with a Schläfli symbol of (4.63.82). Complex 2 presents a (4,6)-connected porous architecture based on a chair-shaped [Cu4(μ3-OH)2]6+ secondary building unit (SBU) with a Schläfli symbol of (43.63)2(46.66.83), revealing unusual ferromagnetic behavior. Complex 3 exhibits a 2D → 3D framework through H-bonding interactions, which is a (3,3,4)-connected 2-fold interpenetrated structure with a Schläfli symbol of (6.82)2(63.83). Complex 4 shows a (3,4,6)-connected (4.64.8)2(62.8)2(42.66.86.10) topology. Complex 5 displays a rare (3,4)-connected polycatenation structure, possessing identical topologies with a Schläfli symbol of (63)(65.8) and weakly ferromagnetic behavior. Complex 6 features a (3,4)-connected 3D framework with a Schläfli symbol of (4 × 102)2(42.103.12). Complex 7 can be regarded as a (4,4)-connected (63.83)2(85.10) topology. Moreover, diverse structural topologies have not been documented hitherto. The magnetic properties of 2 and 5 are discussed in detail. The fluorescence properties have also been analyzed with density functional theory calculations, indicating that the emissions can be ascribed to intraligand charge transfer for 1 and ligand-to-ligand charge transfer for 3–4.

In this work, a metal-mediated assembling strategy has been used to organize a series of new assemblies based on tetrapyridylporphyrin (ZnP) on nanostructured TiO2 electrode surfaces, wherein the metal ions (M, M = Zn2+, Cd2+, Hg2+ and Mn2+) bridge the pyridyl units of ZnP and (E)-4-[(pyridin-4-ylmethylene)-amino]benzoic acid (A), resulting in a ZnP–M–A assembled mode. The assembled structures were characterized by transmission electron microscopy (TEM), computational calculations, energy-dispersive X-ray spectroscopy (EDX), IR, UV-vis absorption and fluorescence spectra. The performances of the assembly-sensitized solar cells were also measured under an irradiance of 100 mW cm−2 AM 1.5G sunlight. Photoelectrochemical results reveal a relatively large photocurrent of the ZnP–Mn–A device. Simultaneously, a large open-circuit photovoltage and a significantly improved conversion efficiency of the ZnP–Zn–A device are also observed. These findings may serve as another good testing ground for the fabrication of supramolecular solar cells in future.

•The metal-mediated assembling strategy for organizing zinc porphyrin.•A series of differently bivalent metal ions were prepared.•A series of differently anchoring groups were also prepared.•Significant improvement in solar-to-electrical conversation efficiency.•Well-arrays of zinc porphyrins on the TiO2 electrode surfaces were reflected.In this work, employing the metal-mediated assembling strategy for organizing acetohydrazide zinc porphyrin (ZnP) and different organic acid (Ai) ligands on the nanostructured TiO2 electrode surfaces have been prepared, wherein the ZnP and Ai units are bound by a series of differently bivalent metal ions (M, M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+), resulting in a ZnP–M–Ai assembled approach. The photovoltaic performances of these assemblies-sensitized solar cells were performed under irradiance of 100 mW cm−2 AM 1.5G sunlight. A significantly improved conversion efficiency of ZnP–Mn–A5 and ZnP–Cd–A5 devices occurs, indicating well-ordered arrangements of ZnP molecules on the TiO2 electrode surfaces for ZnP–Mn–A5 and ZnP–Cd–A5, where A5 is a pyridine–monocarboxylic acid ligand bearing longer arm. The results were also verified by the HOMO–LUMO gaps, UV–vis and fluorescence spectra.Graphical abstractNanostructured TiO2 electrode surface grafted novel assembly with acetohydrazide zinc porphyrin (ZnP) has been successfully organized by the metal ion (M, M = Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+) to bind the ZnP and different organic acid (Ai) ligands, in which Ai serves as anchoring group to functionalize the TiO2 electrode surface.

•A homochiral Cu(II) coordination polymer has been synthesized and characterized.•This chiral complex was constructed by two achiral V−shaped ligands.•The topology of this 3D complex represents a simple yet unreported 75∙8 topology.By using a V-shaped N-containing ligand and a V-shaped carboxylate ligand, we have successfully synthesized a 3D novel copper homochiral coordination polymer, namely [Cu(OPY)(1,3-bdc)]n (complex 1), [1,3-H2bdc = isophthalic acid, OPY = 4,4′-(oxybis(4,1-phenylene))dipyridine]. The compound has been solvothermally synthesized and characterized by IR, elemental analysis, single crystal X-ray diffraction, XRD, UV–vis, and TG analysis. The complex 1 crystallizes in the chiral space group P65 and possesses an unprecedented uninodal 3D 75∙ 8 topology. However, the complex was synthesized by achiral materials. The complex 1 displays a moderate SHG response and its SHG efficiency is about 0.3 times that of urea. In addition, the compound shows high thermal stability.A 3D non-interpenetrated chiral coordination polymer [Cu(OPY)(1,3-bdc)]n has been solvothermally synthesized by using V-shaped N-containing and multi-carboxylate ligands simultaneously without any chiral precursors. The structure of the complex is composed by the exclusively left-handed helical chains and each single chain is generated around the crystallographic 65 axis with a long pitch of 27.99 Å.

•Metal (Mn and Cd)-mediated assemblies of two acetohydrazide zinc porphyrins.•Porphyrins appended organic acid entities were immobilized on TiO2 films.•Enhanced photovoltaic behavior of Mn-mediated assembly of phenol–porphyrin.•This work affords a fertile base for supramolecular solar cells.In this work, a metal-mediated assembling strategy has been used to construct four assemblies (ZnPx–M–A) with two acetohydrazide zinc porphyrins bearing two different donor groups (ZnPx, benzimidazyl unit for ZnP1, phenol group for ZnP2) appended (E)-4-[(pyridin-4-ylmethylene)amino] benzoic acid ligands (A), in which the metal ions (M, M = Cd2+ and Mn2+) are used to bridge the ZnPx and A units, resulting in a ZnPx–M–A organized mode. Further, these assemblies were immobilized on the semiconducting TiO2 electrode surfaces by the carboxylic groups of A units, and their photovoltaic performances were performed under irradiance of 100 mW cm−2 AM 1.5G sunlight. The assembled structures were characterized by transmission electron microscopy (TEM), computational calculations and energy-dispersive X-ray spectroscopy (EDX). Photoelectrochemical studies reveal a significantly improved photovoltaic performance for ZnP2–Mn–A compared to other assemblies, which are also reflected by their corresponding UV–Vis absorption, fluorescence spectra and HOMO–LUMO energy gaps.Graphical abstractWe have successfully organized four metal-mediated assemblies (ZnPx–M–A) based on two acetohydrazide zinc porphyrin bearing two different donor groups (ZnPx, benzimidazyl unit for ZnP1, phenol group for ZnP2) and (E)-4-[(pyridin-4-ylmethylene)amino] benzoic acid ligand (A), wherein the metal ions (M, M = Cd2+ and Mn2+) were used to bridge the ZnPx and A units to attach on the nanostructured TiO2 electrode surfaces. Photoelectrochemical studies reveal significantly improved photovoltaic performance for the assembly ZnP2–Mn–A.

•A novel assembly with acetohydrazide porphyrin coordination polymer.•The assembly based on porphyrin is prepared as parallel sample.•Coordination polymer-based assembly shows enhanced photoelectronic behavior.•A series of different organic acid ligands as anchoring groups are prepared.In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO2 electrode surface in supramolecular solar cells.An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells.

To probe the coordination approach of pyridazine and pyrazine ligands, five new complexes of [CuII2L2Cl2] (1), [CuII(L-H)(NO3)(H2O)2](NO3)(H2O) (2), {[CuII(L-H)(H2O)](ClO4)2(H2O)}n (3), [CuII2L2(OH)](NO3)(H2O)2 (4), [CuII2L2(OH)](ClO4) (5) based on Schiff base ligand (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine (HL) bearing pyridazinyl and pyrazinyl groups have been synthesized and characterized by IR spectra, elemental analyses, the bond valence sum (BVS) analyses, powder X-ray diffraction (PXRD) analyses, X-ray single crystal diffraction and density function theory calculations. The structures of 1, 2 and 3 suggest that the second nitrogen donors of the pyrazinyl unit can link with other metal ions to construct a higher dimensional architecture by the reaction of HL with Cu(ClO4)2 [CuCl2 for 1, Cu(NO3)2 for 2 and Cu(ClO4)2 for 3]. The structures of 4 and 5 indicate that additional donor units of the pyridazinyl chromophore can bind multiple metal ions to form a multi-metallic cluster, when the protons of the hydrazone backbones are abstracted in the presence of triethylamine to strengthen the coordination behavior of the second nitrogen atom. However, for 1, the protons of the hydrazone backbone are lost with or without triethylamine and the additional nitrogen atoms of the pyrazinyl and pyridazinyl groups are not found to connect to other metal ions, which can probably be assigned to the strong coupling effect of chlorine ions. Magnetic measurements display weak antiferromagnetic coupling between the copper(II) ions in 1 and 5, and ferromagnetic coupling in 3. In addition, the antioxidant activities of HL and 1–5 were also studied.

Two new self-assemblies based on two zinc porphyrins substituted at the meso-positions with different donor units (denoted as ZnP1 and ZnP2) and isonicotinic acid (A) by metal–ligand axial coordination have been designed and immobilized on the double-layer nanostructured TiO2 film-coated highly transparent FTO conducting glass electrode in a photosynthesis device. These cells were also measured under irradiance of 100 mW cm−2 AM 1.5G sunlight. The results reveal that the performance of ZnP2-A outperforms that of ZnP1-A. The UV–vis absorption spectra, fluorescence spectra, molecular orbital (MO) patterns, and HOMO–LUMO energy gaps of these assemblies were also investigated to further demonstrate the photovoltaic behavior of these cells.Two new self-assemblies based on two zinc porphyrins bound to isonicotinic acid by metal–ligand axial coordination. The UV–vis absorption spectra, fluorescence spectra, and the photovoltaic performance of these photosynthesis devices are also described. Our results reveal that these photosynthesis devices enable attainment of impressive improvement in photocurrent response, especially for the assembly based on the substituent of phenol over the assembly substituted with benzimidazyl. Additionally, the molecular orbital (MO) patterns and HOMO–LUMO energy gaps of these assemblies are also studied to further demonstrate these experimental products.Figure optionsDownload full-size imageDownload as PowerPoint slide

•Four Mn(II), Ni(II) and Zn (II) complexes have been synthesized.•Zn(II) complex exhibits a semideprotonated behavior.•Weak antiferromagnetic coupling of a Mn(II) complex is also observed.•The antioxidant activities are also described.Four new complexes, [Mn2(L-H)2Cl4]·CH3CN (1), [Mn(L-H)(NO3)2·CH3OH] (2), [Ni(L-H)2](NO3)2·2H2O (3) and [Zn(L-H)L](NO3) (4) have been synthesized by the reaction of (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine (HL) with MnCl2, Mn(NO3)2, Ni(NO3)2 and Zn(NO3)2. Noteworthy, complex 4 is a semi-deprotonated compound. The results signify that the feature of metal salt, such as the size, shape, coordination ability and coordination mode, has significant effects in determining the resulting structure. The magnetic property of 1 and antioxidant activities of HL and 1–4 were also studied.Three protonated complexes [Mn2(L-H)2Cl4]·CH3CN (1), [Mn(L-H)(NO3)2 · CH3OH] (2), [Ni(L-H)2](NO3)2 · 2H2O (3) and one semi-deprotonated complex [Zn(L-H)L](NO3) (4) derived from a schiff base ligand (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine, have been synthesized and evidenced by X-ray single diffraction and elemental analyses. The magnetic property of 1 and antioxidant activities of HL and 1–4 were also studied.

The complexes [Fe(bpz*mpy)2](ClO4)2 (1a), [Cu(bpz*mpy)2](ClO4)2 (1b) and [Ag(bpz*mpy)(Ph3P)](ClO4) · H2O (2) (bpz*mpy = pyridin-2-yl-bis(3,5-dimethylpyrazol-1-yl)methane) have been synthesized and characterized by physicochemical and spectroscopic methods. X-ray crystallographic analysis reveals that the central FeII and CuII ions in complexes 1a and 1b are located on a twofold rotation axis and have a distorted octahedral coordination sphere, while the AgI center in complex 2 is tetrahedrally coordinated. The electrochemical properties of complex 1b have been investigated. Furthermore, a variable temperature magnetic susceptibility study of complex 1a has also been performed over the measured temperature range 2–300 K.

A new Ag(I) complex [AgL]n (HL = 1H-1,2,4-triazole-1-methylene-1H-benzimidazole-1-acetic acid) was synthesized, and characterized by elemental analysis, IR spectra. The X-ray crystal structure of the complex was determined. The complex crystallizes in the Monoclinic system, space group p2(1)/n with a = 10.418(4) Å, b = 8.526(3) Å, c = 14.319(5) Å, β = 105.700(5)°, V = 1224.3(8) Å3, Z = 4. The complex has two-dimensional motif. The complex and free ligand display photoluminescence at room temperature. A quasi-reversible redox couple for the complex is observed.

In this work, a metal-mediated assembling strategy has been used to organize a series of new assemblies based on tetrapyridylporphyrin (ZnP) on nanostructured TiO2 electrode surfaces, wherein the metal ions (M, M = Zn2+, Cd2+, Hg2+ and Mn2+) bridge the pyridyl units of ZnP and (E)-4-[(pyridin-4-ylmethylene)-amino]benzoic acid (A), resulting in a ZnP–M–A assembled mode. The assembled structures were characterized by transmission electron microscopy (TEM), computational calculations, energy-dispersive X-ray spectroscopy (EDX), IR, UV-vis absorption and fluorescence spectra. The performances of the assembly-sensitized solar cells were also measured under an irradiance of 100 mW cm−2 AM 1.5G sunlight. Photoelectrochemical results reveal a relatively large photocurrent of the ZnP–Mn–A device. Simultaneously, a large open-circuit photovoltage and a significantly improved conversion efficiency of the ZnP–Zn–A device are also observed. These findings may serve as another good testing ground for the fabrication of supramolecular solar cells in future.

We prepared in this work an anchoring porphyrin and a series of hat-porphyrins. The zinc atom of the hat-porphyrins can be coordinated axially with the pyridine moiety of the anchoring porphyrin which is anchored on the titania surface by a carboxyl group. The structures of the assemblies were confirmed using computational calculations, transmission electron microscopy (TEM) and energy dispersive spectrometry (EDS). Solar cell devices of the monomer anchoring porphyrin and its assemblies were fabricated and the photovoltaic performances were measured under standard AM 1.5 sunlight irradiance. We found that the assembly devices showed higher JSC and lower VOC than that of the monomer anchoring porphyrin device. However, the comprehensive influence of JSC and VOC led to an enhancement in the solar-to-electric power-conversion efficiency (PCE) of the assemblies. We also studied the variation of JSC and VOC using electronic absorption and emission spectroscopy, charge extraction measurements, transient photovoltage decay measurements and electrochemical impedance spectroscopy.

An acylhydrazone zinc porphyrin P1 and its coordination polymers (CPs, denoted as P1M, M = Mn, Co, Ni, Cu, Zn) with different metal ions (Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) were synthesized. Then these coordination polymers were assembled into bilayer structured supramolecular chromophores through axially coordinating with anchoring porphyrin AP, and their performance in dye sensitized solar cells was investigated. Our results reveal that the bilayer structured supramolecular chromophore based solar cells show significantly improved photocurrent conversion efficiency. Particularly, P1Mn and P1Zn based solar cells showed a relatively higher short circuit current density (JSC) due to their broad absorption bands and remarkable light harvesting abilities. Meanwhile, the VOC values of the cells fabricated with the bilayered chromophores slightly decreased. Electrochemical impedance spectroscopy (EIS) in combination with charge extraction (CE) and transient photovoltage decay (TPD) measurements indicates that the decreased VOC resulted from the vigorous electron recombination and the downward shifted conduction band edge (ECB) of titania.