Dimensional Supramolecular Framework Research Articles

Exploring the synthesis, structure, and properties of two 2D transition metal polymers based on 4, 4’-bistriazole 3, 3’-biphenyldicarboxylic acid

Two coordination polymers {[Zn(BTBPA)(H2O)2]·0·5H2O}n (Zn-1), and {[Mn(BTBPA)(H2O)2]·0·5H2O}n (Mn-2) were synthesized solvothermally by the combination of organic linker 4,4′-bistriazole 3,3′-biphenyldicarboxylic acid (H2BTBPA) and Zn(NO3)2·6H2O or MnCl2·4H2O. Both of the polymers 1–2 are as 4,4-linked two-dimensional layered structures, which constitute into three dimensional supramolecular frameworks with porous channels via O − H⋅⋅⋅O hydrogen bonds. Zn-1 exhibits recognition abilities to antibiotics (PCL, NFT and NFZ) with high sensitivity via luminescence “turn-off” mechanism. In addition, the static magnetic performance of Mn-2 was investigated.

Polymorphism-dependent thermally activated delayed fluorescence materials with diverse three dimensional supramolecular frameworks

Multifunctional organic luminescent materials have attracted intensive interests. Nevertheless, the mechanisms behind them are still to be explored. In this work, we reported four multifunctional emitters with thermally activated delayed fluorescence (TADF), aggregation-induced emission (AIE), multicolor mechanochromic luminescence (MCL) and polymorphism. We also demonstrated their applications in acid/base-responsive on/off chemosensors, ink-free rewritable paper and organic light-emitting diodes (OLEDs). By deeply analyzing their three dimensional supramolecular frameworks with ordered micro pores and different intermolecular interactions in crystal structures, we revealed the underlying mechanisms of polymorph-dependent TADF and multicolor MCL simultaneously.

Sonochemical synthesis and structural characterization of an organic-inorganic nanohybrid based on a copper-dithiocarbamate complex and PMo12O403- polyanion as a novel sonocatalyst.

A new organic-inorganic nanohybrid compound, ([Cu{(HOCH2CH2)2NCS2}2]3[PMo12O40] (1)), has been prepared by sonochemical technique using copper(II) dithiocarbamate complex and a Keggin-type polyoxomolybdate in this research. FT-IR, XRD, FE-SEM, TEM, EDX, UV-Vis, TGA, BET, and single crystal XRD analyses were applied to describe the properties of the composition of the nanohybrid. Compound (1) is composed of [PMo12O40]3- building blocks and [Cu{(HOCH2CH2)2NCS2}2]1+ cationic moieties, and electrostatic forces and substantial hydrogen-bonding interactions were applied to pack them; and consequently, a three dimensional supramolecular framework was made based on single-crystal X-ray diffraction patterns. FE-SEM and TEM images approved the morphology of the nanohybrid sample to be extremely penetrable. Very good sonocatalytic performance is shown by this supramolecular nanohybrid in the degradation of Rhodamine B (RhB), which is a cationic organic dye. The results showed complete degradation of cationic RhB (25 mg/L) within 70 min with the rate constant of 0.039min-1 in the presence of nanohybrid (1) and H2O2 (4 mmol/L). Also, sonocatalytic activity of the nanohybrid (1) was higher than H3PMo12O40, showing that the combining Cu(DEDTC)2 complex with H3PMo12O40 could be an excellent choice to improve its sonocatalytic activity. The used nanohybrid (1) can be recycled after easily removing from the reaction media by centrifuging, and there was no considerable loss of catalytic activity and retention of the structure.

Two new Ni(II) supramolecular complexes based on ethyl isonicotinate and ethyl nicotinate for removal of acid blue 92 dye

Two new luminescent supramolecular complexes (SC); [Ni(EIN)4(NCS)2] SC1 and [Ni2(EN)8(NCS)4] SC2, (EIN = ethyl isonicotinate, EN = ethyl nicotinate), have been synthesized by self-assembly method and structurally characterized by X-ray single crystal, FT-IR and UV-Vis spectra, PXRD, elemental and thermogravimetric analyses. Both SC1 and SC2 are monoclinic crystals however, they have different asymmetric units. Ni(II) atoms in both SC are isostructural and have similar hexa-coordinate environment. The structures of SC1 and SC2 consist of parallel polymeric 1D-chains, extended in two and three dimensional supramolecular frameworks by intermolecular hydrogen bonding interactions. SC1 and SC2 are luminescent materials which can be used in applications as molecular sensing systems. SC1 and SC2 were used as heterogeneous catalysts for degradation of acid blue 92 (AB-92) under sun light irradiation. The fluorescence measurements of terephthalic acid technique as a probe molecule were used to determine the •OH radicals. Also the radicals trapping experiments using isopropanol alcohol (IPA) as radical scavenger were discussed. In addition a mechanism of degradation was proposed and discussed.

Self-assembly, crystal structure, and spectroscopy properties of two new complexes with 1,10-phenanthroline-5,6-dione and SCN ligands

Two new complexes [Co(Pdon)(SCN)2(H2O)2] (I) and [Hg(Pdon)2Br2] (II) (Pdon = 1,10-phenanthroline-5,6-dione) have been synthesized and characterized by element analysis, IR and single crystal X-ray diffraction (CIF files CCDC nos. 793904 (I) and 783209 (II)). Compounds I and II are mononuclear complexes obtained by the self-assembly of Pdon, SCN− and metal ion Co2+ and Hg2+, which are further in close contacted forming a two dimensional supramolecular framework via O-H⁣⋯S and O-H⋯O hydrogen bonding interactions interactions between adjacent molecules.

A Novel Two-Fold Interpenetrating Two-Dimensional CdII Coordination Polymer Based on a Bis(imidazole) Ligand and 4,4′-Oxydibenzoic Acid: Synthesis, Structure and Physical Properties

A two-fold interpenetrating two-dimensional CdII coordination polymer, [Cd(oba)(mmmb)·H2O]n (1) (mmmb = 5-methyl-1,3-bis(1-imidazolyl)benzene, H2oba = 4,4′-oxydibenzoic acid) has been prepared and characterized through IR, elemental analysis, thermal analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that complex 1 is a two-fold interpenetrating (4,4)-connected network. These layers are linked by O–H⋯O and C–H⋯O hydrogen bonds to form a three dimensional supramolecular framework. The framework is reinforced by π–π interactions. In addition, complex 1 exhibits strong fluorescent emissions in the solid state at room temperature.

Synthesis, Crystal Structure and Physicochemical Proprieties of a Cytosine Selenomolybdate Based on Strandberg-Type [Se2Mo5O21]4− Polyanion

We have synthesized and crystallized a cytosine-selenomolybdate compound, (C4H6N3O)4[Se2Mo5O21]·(C4H5N3O)4·6H2O (1). Single-crystal X-ray analysis was carried out, compound (1) crystallizes in the triclinic system, space group P1, with a = 8.416(3) A, b = 13.163(8) A, c = 15.601(2) A, α = 106.49(3)°, β = 102.74(2)°, γ = 99.88(4)° and Z = 1. The data were characterized by elemental analysis, IR spectrum, UV–Vis spectra, photoluminescence, thermogravimetric analyses and cyclic voltammetry measurements. The heteropolyanion is composed of five distorted MoO6 octahedra by sharing vertices and edges with two capped SeO3 pyramids on each side. The organic molecules can be regarded as a dimer of a cytosine–cytosinium, linked by hydrogen bonds. The [Se2Mo5O21]4− cluster anions in compounds (1) are further inter-linked by water molecules and the organic groups through hydrogen bonds to form a three dimensional supramolecular framework. Hybrid compound (C4H6N3O)4[Se2Mo5O21]·(C4H5N3O)4·6H2O constructed by Strandberg-type polyoxoanion and cytosine–cytosinium dimer.

Synthesis, Crystal Structure, and Properties of a Tetranuclear Copper(II) Complex With α-Naphthylacetic Acid

A tetranuclear copper(II) complex, Cu4(NAA)8(CH3CN)2 (1) (HNAA = α-naphthylacetic acid), has been prepared and structurally characterized by IR, elemental analysis, TGA, and single-crystal X-ray diffraction. Complex 1 features a tetranuclear cluster based on two bridged binuclear units, which is further interlinked into a higher dimensional supramolecular framework by intermolecular weak interactions. The weak antiferromagnetic behavior in 1 can be observed.

Synthesis and Crystal Structure of a New Dinuclear Iron(III) Complex: [Fe2O(PhCO2)2(2,2′‐bpy)2(N3)2]·H2O

AbstractBy using a precursor complex [Fe3O(PhCO2)6(H2O)3]NO3 as starting material and 2,2′‐bpy (= 2,2′‐bipyridine) as rigid chelating ligand, the new dinuclear iron‐oxido complex [Fe2O(PhCO2)2(2,2′‐bpy)2(N3)2]·H2O (1) was synthesized and structurally characterized. The reaction of [Fe3O(PhCO2)6(H2O)3]NO3 with 2,2′‐bpy and sodium azide in 1:3:3 ratio gave the dinuclear complex 1, whereas a 1:6:3 ratio reaction system only gave the complex [Fe(2,2′‐bpy)3]3+, which indicated that 2,2′‐bipyridine plays a crucial function in the nuclear forming procedure. Meanwhile, the N3– ligands take up the chelating domain of oxygen and reduce the nucleation. Different π–π interactions exist in 1, which extend its structure to a three dimensional supramolecular framework.

Synthesis and characterization of two new metal-organic materials based on In III/btec

Two new metal-organic materials, In(2,2′-bipy)(btec) 0.5Cl ( 1) and In 2(phen) 4(Hbtec) 2 ( 2) (btec = 1,2,4,5-benzenetetracarboxylate, 2,2′-bipy = 2,2′-bipyridyl, phen = 1,10-phenanthroline) have been synthesized under mild hydrothermal condition. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction, thermogravimetric analysis, IR, fluorescence spectroscopy, inductively coupled plasma (ICP) and elemental analysis. The structural analysis reveals that compound 1 exhibits a novel wavelike 2D layer with unusual contorted rhombic grids, while compound 2 possesses dinuclear In 2(phen) 4(Hbtec) 2 complex molecules. It is noteworthy that their structures finally extend to the higher dimensional supramolecular framework structures through the π–π stacking interactions of N-donor ligands. Additionally, these two compounds show strong fluorescence in the solid state at room temperature.

Synthesis and X‐ray structure of two conformational isomers of [Zn(medpt)(SCN)2], medpt = bis (3 – aminopropyl)methylamine

AbstractTwo conformational isomers of [Zn (medpt)(NCS)2], medpt=bis(3‐aminopropyl) methylamine, (1) and (2) have been synthesised and the crystal structures are determined using single crystal X‐ray diffraction. The structures of the complexes have been solved by Patterson method and refined by full‐matrix least‐ squares techniques to R1 = 0.0524 for (1) and R1 = 0.0506 for (2), respectively. The geometry around the Zn(II) centre in both isomers is distorted trigonal bipyramidal. The two pendent thiocyanate moieties in (1), with Zn–N–C angles 167.9(4)–173.9(4)º, coordinate the mental centre almost linearly while the corresponding coordinations in (2) are significantly bent [Zn–N–C angles 150.8(3)–153.1(2)°]. Intermolecular N–H…S hydrogen bonds stabilise the crystal packing in the complexes forming infinite chains parallel to the [100] direction. The combinations of molecular chains generate three/two dimensional supramolecular framework in complexes (1) and (2). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Silver(I) Saccharinato Complexes with Ethylenediamine andN,N-Dimethylethylenediamine - [Ag2(sac)2(en)(H2O)]n and [Ag2(sac)2(dmen)2

Two new silver(I)-saccharinato (sac) complexes with ethylenediamine (en) and N,N-dimethylethylenediamine (dmen) were synthesized and characterized by elemental analysis, FT–IR spectroscopy, thermal analysis and single crystal X-ray diffraction. The [Ag2(sac)2(en)(H2O)]n complex, 1, is a coordination polymer in which[Ag(sac)2(H2O)]− and [Ag(en)2]+ ions are bridged by one of the sac ligands and Ag–Ag bonds [2.9920(3) A], resulting in [Ag2(sac)2(en)(H2O)] building blocks which are also linked into one-dimensional helical chains by bridging en ligands. Each silver(I) atom is three-coordinate with a distorted T–shaped coordination of AgN2O. The individual chains of 1 are further stacked by π–π; interactions, OW–H···O and N–H···O hydrogen bonds to form a three–dimensional supramolecular framework. The [Ag2(sac)2(en)2] complex, 2, has two molecules in its asymmetric unit, and each dimer is formed by bridging of two monomeric [Ag(sac)(dmen)] units by Ag–Ag bonds. The silver(I) atoms exhibit a distorted T–shaped coordination of AgN3 with an N–bonded sac and bidentate dmen ligands. The Ag···Ag separations in the pair of dimers are 3.2725(9) and 3.3127(9) A. The dimeric molecules of 2 are connected to one-dimensional hydrogen bonded chains by N–H···O hydrogen bonds.

Bis–(5,5′–diethylbarbiturato) Copper(II) and Cadmium(II) Complexes with Ethylenediamine. Synthesis, Crystal Structures, Spectroscopic and Thermal Characterization of cis–[Cu(barb)2(en)] and {[Cd(barb)2(μ–en)]·2H2O}n

AbstractTwo new bis(5,5′–diethylbarbiturato) (barb) complexes of copper(II) and cadmium(II) with ethylenediamine (en) were synthesized and characterized by elemental analysis, FT–IR spectroscopy and thermal analysis. In addition, their solid–state structures were determined by single crystal X–ray diffraction studies. cis–[Cu(barb)2(en)] (1) crystallizes in the monoclinic space group of C2/c and consists of neutral monomeric units, in which the copper(II) ion exhibit a highly distorted octahedral coordination by two barb anions and a neutral chelating en ligand. The individual molecules of 1 are held together by N–H···O hydrogen bonds, forming a three–dimensional network. {[Cd(barb)2(μ–en)]·2H2O}n (2) is a one–dimensional coordination polymer and also crystallizes in the monoclinic crystal system (P21/c). In 2, [Cd(barb)2(en)] building blocks are connected into a chain by bridging NH2 groups of en, and the individual chains are further stacked by O–H···O and N–H···O hydrogen bonds to form a three–dimensional supramolecular framework. The barb ligands in both complexes act as a bidentate ligands via the negatively charged imino N atom and one of the carbonyl O atoms adjacent to the imino N atom. The M–O bond distances in both complexes are much longer than M–N bond distances, indicating a weak interaction of the carbonyl group of barb.