Luminescence Properties Of Complexes Research Articles

Structural diversities and related properties of four coordination polymers synthesized from original ligand of 3,3',5,5'-azobenzenetetracarboxylic acid.

Four new coordination polymers, namely [Co(H2O2abtc)(bibp)]n (), {[Mn1.5(Oabtc)(H2O)2]·(H2bmib)0.5·H2O}n (), {[Cd1.5(O2abtc)]·(H2bmib)0.5·2H2O}n (), and {[Cd(nip)(bibp)]·0.5H2O}n (),were constructed under solvothermal conditions in the presence of two bis(imidazole) bridging linkers (bimb = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene, bibp = 4,4'-bis(imidazol-1-yl)biphenyl). The unstable azo ligand of 3,3',5,5'-azobenzenetetracarboxylic acid (H4abtc) could be oxidized and resulted in three oxidized derivatives of H4Oabtc (one N atom was oxidized), H4O2abtc (two N atoms were oxidized), and H2nip (one H4abtc was oxidized to two 5-nitroisophthalic acids). Their structures were determined by single-crystal X-ray diffraction and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complex exhibited an interestingly 2D + 2D → 3D parallel entangled network based on 4-connected (4(4)·6(2))-sql sheets. Complex was found to be a {Mn3(COO)6} trinuclear SBU based 2D (3,6)-connected (4(3))2(4(6)·6(6)·8(3))-kgd sheet. While complex displays a {Cd3(COO)8} trinuclear SBUs based 3D (4,8)-connected (4(6))2(4(12)·6(12)·8(4))-flu network. Complex can be regard as a {Cd2(COO)2} binuclear SBUs based 6-connected (4(4)·6(11))-6T8 framework. In addition, the magnetic property of complexes , and the luminescence properties of complexes , were investigated.

Syntheses, structures and properties of three transition metal coordination polymers based on semi-rigid 3-pyridylnicotinamide and S/N-containing dicarboxylate mixed ligands

Three new coordination complexes, [Co(L)(ADTZ)]·H2O(1), [Cd(L)(ADTZ)]·H2O(2) and [Zn(L)(ADTZ)]·H2O(3)[L=3-pyridylnicotinamide, H2ADTZ=2,5-(s-acetic acid)dimercapto-1,3,4-thiadiazole], were synthesized under hydrothermal conditions. These complexes were structurally characterized by single-crystal X-ray diffraction analysis and further characterized by infrared spectroscopy(IR), powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). Complexes 1–3 exhibit the similar 2D double-layer networks based on 1D [M-L] n zigzag chains and 1D [M-ADTZ]2n double-chains with different distances between metal ions and with various conformations of ADTZ anions. In complexes 1 and 3, the 2D sheets are extended into a 3D supramolecular frameworks by hydrogen bonding interactions. The subtle effects of the central metal atoms on the structures of the title coordination polymers were discussed. The electrochemical properties of complex 1 and luminescent properties of complexes 2 and 3 were investigated. In addition, complexes 1–3 exhibit photocatalytic activity for dye methylene blue degradation under UV light and show good stability toward photocatalysis.

Syntheses, Crystal Structures, and Luminescent Properties of Two Cadmium(II) Complexes with CdS Network and (3,4)‐Connected Topology

AbstractTwo cadmium(II) complexes with different dicarboxylate ligands, [Cd(ADC)(bib)0.5] (1) and [Cd(HIDC)(bib)0.5]n (2) [H2ADC = 1,3‐adamantanedicarboxylic acid, H3IDC = 4,5‐imidazoledicarboxylate and bib = 1,4‐bis(1‐imidazolyl) benzene] were obtained. Complexes 1 and 2 were characterized by single‐crystal and powder X‐ray diffraction, FT‐IR spectroscopy, and elemental analysis. The complexes showed different topological nets. Furthermore, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.

Synthesis, Structures, and Photoluminescent Properties of Three Coordination Polymers based on an Asymmetric Semi‐rigid V‐shaped Tricarboxylate Ligand

AbstractThree coordination polymers, [Zn(HL)(phen)(H2O)]n (1), [Zn1.5(L)(4, 4′‐bpy)1.5]n·4nH2O (2), and [Zn2(HL)2(bib)2]n·2nH2O (3), were assembled from the asymmetric semi‐rigid V‐shaped tricarboxylate ligand 4‐(2‐carboxy‐phenoxy)‐isophthalic acid (H3L) with 1, 10‐phenanthroline (phen), 4, 4′‐bipyridine(4, 4′‐bpy) and 1, 4‐bis (imidazol‐1‐yl) benzene (bib) as auxiliary ligands. Complex 1 features a one‐dimensional (1D) double‐looped chain, which is further extended into a 2D supramolecular layer via two kinds of hydrogen‐bonding interactions. Complex 2 exhibits a complicated 3D framework, which can be rationalized as a (3, 4,4)‐connected trinodal net with a unique (4·8·10) (4·8·10·123) (82·122·14·16) topology. Complex 3 has a two‐dimensional (2D) (4, 4) layer formed by the {Zn2} dinuclear SUBs and the bib ligands. The structural and topological differences of the three complexes indicate that the N‐containing auxiliary ligands play important roles in the formation of the final framework structures. In addition, complexes 1–3 were characterized by elemental analysis, IR spectroscopy, and X‐ray powder diffraction. The thermal behaviors and luminescent properties of complexes 1–3 were also investigated in detail.

Synthesis, structure and luminescence properties of lanthanide coordination polymers using in situ decarboxylation of a H3cppdc ligand

The hydrothermal reaction of Ln(NO3)3·6H2O, 3-(4-carboxyphenyl)-2,6-pyridinedicarboxylic acid (H3cppdc) and N,N-dimethylformamide (DMF) gave a series of lanthanide coordination polymers n[NH2(CH3)2]·[Ln(cppc)2(H2O)2]n (where: Ln=Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9) and Er (10); and H2cppc=5-(4-carboxyphenyl)-2-pyridinecarboxylic acid). The H2cppc ligand was formed in situ via decarboxylation of the initial H3cppdc ligand under the hydrothermal reaction conditions. Complexes 1–10 that crystallized in the same C2/c space group, exhibited similar 2D layered structures and assemble into 3D supramolecular networks via hydrogen bonding and π–π stacking interactions. In addition, the luminescence properties of complexes 4, 5, 7 and 8 were investigated.

Synthesis, crystal structures, luminescence and catalytic properties of three silver(I) coordination polymers with bis(imidazole) and benzenedicarboxylic acid ligands

Three new silver coordination compounds with empirical formula [Ag2(L1)2·(ntp)·(H2O)3.25]n (1), [Ag1.5(L1)1.5·(H0.5bdc)·(H2O)4]n (2) and [Ag(L2)(Hmip)]n (3) (L1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L2 = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole, H2ntp = 2-nitroterephthalic acid, H2bdc = 1,3-benzenedicarboxylic acid, H2mip = 5-methylisophthalic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and physico-chemical spectroscopic methods. The silver centers display different environments with a linear geometry in 1 and 2 and distorted T-shaped geometry in 3. In 1–3, the bidentate N-donor ligands (L1 and L2) bridge neighboring silver centers to form 1D infinite chain structures. Complexes 2 and 3 are extended into 2D layers, and 1 is packed into a 3D 3,4,4,6-connected supermolecular network via classical O–H···O hydrogen bonds, while 3 is further extended into 3D framework through π–π interactions. The luminescence properties of complexes 1, 2 and 3 were investigated in the solid state. These coordination polymers possess a remarkable activity for degradation of methyl orange by persulfate in a Fenton-like process.

Accesses to electronic structures and the excited states of iridium complexes containing pyrazolyl or benzimidazoly ligands: A DFT/TDDFT exploitation

The ground state, 3MLCT and 3MC excited states of two Ir complexes Ir(dfbpzb)(ppy)Cl (1) and Ir(Mebib)(ppy)Cl (2) where dfbpzb=1,5-difluore-2,4-bis(3-methylpyrazolyl)benzene, ppy=2-phenylpyridine, and Mebib=bis(N-methylbenzimidazoly)benzene, have been investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The substitution from dfbpzb ligand to Mebib ligand induces a significant change on the luminescent properties of complexes 1 and 2. The complex 1 does not emit at room temperature, while complex 2 does. The UV–Vis absorption spectra of both complexes are well reproduced by TD-DFT calculations. Importantly, the triplet metal-to-ligand charge transfer (3MLCT) and metal-centered (3MC) states were discussed in detail by excited state calculations, and the 3MLCT→3MC deactivation pathway was demonstrated as an important factor for the lack of emission for the investigated complex 1.

Synthesis, Characterization and Property of Nano Rare Earth Terbium Complex with Gatifloxacin

Rare earth metal complexes have special characteristics, such as extremely narrow emission bands and high internal quantum efficiencies, which are suitable to be used as the emission materials, chemistry and biological technology. Ternary nano complex of terbium gatifloxacin phenanthroline was synthesized.The composition and structure of ternary complex were characterized by element analysis, Mass Spectrometry (MS), UltraViolet Absorption Spectrometry (UV) and fluorescence spectra(FS). The influences of solubility, thermal stability and luminescent properties of complex as well as addition of phenanthroline secondary ligands on the fluorescence spectra of the ternary complexes were studied. The results of fluorescence spectra analysis showed that partial energy was transferred from Characterization to terbium ions by intramolecular energy transfer processes, meanwhile, the addition of phenanthroline can effectively increase the luminescence intensity of terbium icons. The complex possessed well luminescence and showed characteristic emission peaks of Tb3+ under UV light excitation and emitted strong green fluorescence. Moreover, in an ITO/PVK/Tb(GFLX)3Phen/Al device, Tb3+ ion can be excited by intramolecular ligand-to-metal energy transfer process. The main peak of emission at 545 nm is attributed to 5D0→7F2 transition of the Tb3+ ion, and this process results in the enhancing green emission. Biological actrivity properties of the rare earth complex was well studied.

Syntheses, Structure, and Properties of Mixed Cp–Amidinate Rare-Earth-Metal(III) Complexes

A family of mixed Cp–amidinate rare-earth-metal(III) complexes [Cp2L1LnPhCN] (Ln = Y (1), La (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7); L1 = PhC(NSiMe3)2), [Cp2L1Ln] (Ln = Er (8), Yb (9)), and [Cp2L2Ln] (Ln = Y (10), Eu (11), Gd (12), Tb (13), Dy (14), Er (15); L2 = N(t-Bu)C(Ph)N(SiMe3)) were synthesized by treatment of Cp3Ln with lithium amidinates. The phase transition has been observed for compounds 5 and 9 at low temperature (200 K). Single-crystal structural analyses reveal that compounds 1, 3, 4, 5b, 6, 7, 9b, and 10–15 contain two staggered Cp rings. In contrast, two eclipsed Cp rings were observed in compounds 2, 5a, 8, and 9a. Moreover, the luminescent properties of complex 6 and magnetic properties of complex 7 were also investigated.

A Novel Charged Iridium (III) Complex for Amine Sensor Application

A new phosphorescent iridium metal with cyclometalated and dimethyl carboxylate bipyridine ligands complex 1 was synthesized and characterized. The ester functional were designed and connected as amine recognition group. The UVVis absorption and luminescence properties of complex 1 were investigated with amine. The result show that complex 1 exhibited high selectivity and efficient signaling behavior n-butylamine in acid catalyst.

Constructing Two MnII Coordination Polymers with 1,4‐Bis(1‐imidazol‐yl)‐2,5‐dimethyl Benzene and Different Dicarboxylate Ligands: Syntheses, Crystal Structures, and Luminescent Properties

AbstractTwo new coordination polymers, [Mn(tda)(bimb)0.5]n (1) and [Mn(obb)(bimb)]n (2) [H2tda = 2,5‐thiophenedicarboxylic acid, H2obb = 4,4′‐oxybis(benzoic acid) and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were hydrothermally synthesized by reactions of MnII salt with a rigid ligand 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene and dicarboxylate ligands. Complex 1 exhibits an unusual binodal (3,7)‐connected three‐dimensional (3D) architecture with point symbol (44.617).(63). Complex 2 is a three‐dimensional structure with pcu topology. Furthermore, the luminescent properties of complexes 1 and 2 are investigated.

Self-assembly and structures of new lanthanide coordination polymers with 1,3-phenylenebis(oxy)diacetic acid

Seven Ln(III) coordination polymers, namely [Ln(PODA)(FA)(H2O)]n [Ln=La(1), Ce(2), Pr(3), Nd(4), Eu(5)] and [Ln(PODA)1.5(phen)]n [Ln=La(6), Pr(7)] (H2PODA=1,3-phenylenebis(oxy)diacetic acid, HFA=formic acid, phen=1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, single crystal X-ray crystallography, UV–Vis spectroscopy and powder X-ray diffraction analysis (PXRD). Structural analysis reveals that 1–5 are isostructural and exhibit 3-D frameworks with a (32.42.52)2(38.420.524.614) topology, which comprise single- and quadruple-strand helical chains; while 6 and 7 show similar layer structures with a (44.62) topology, however, they only consist of one kind of single-strand helical chain. In addition, the thermal stabilities of complexes 3 and 7 and the luminescent properties of complex 5 have been briefly investigated.

A series of flexible bis(imidazole)-based coordination polymers tuned by central metal ions and dicarboxylates: Diverse structures and properties

Seven new coordination polymers, namely, [Ni(L)1.5(2-CMSN)(H2O)]·2H2O 1, [Co2(L)2(2-CMSN)2(H2O)]·H2O 2, [Cd(L)(2-CMSN)(H2O)] 3 [Zn(L)(2-CMSN)]·2H2O 4, [Cd(ADTZ)(H2O)] 5, [Cd(L)(ADTZ)(H2O)] 6, and [Zn(L)(ADTZ)]·H2O 7 [where 2-H2CMSN=2-carboxymethylsulfanyl nicotinic acid, H2ADTZ=2,5-(s-acetic acid) dimercapto-1,3,4-thiadiazole, L=1,4-bis(imidazol-1-ylmethyl)benzene] have been synthesized under hydrothermal conditions. The complexes were structurally characterized by single crystal X-ray diffraction analyses, infrared spectroscopy (IR), elemental analyses, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 features a 1D ladder-like double chain. Complexes 2 and 3 exhibit the similar 2D networks based on six-nuclear metallic rings. Complex 4 is a 2D sheet. Complex 5 exhibits a 3D (4,6)-connected (43·53)(45·53·67) topology. Complex 6 shows a 2D undulated network with the Schläfli symbol of (3·52)(32·53·64·7). Complex 7 is a 3D 4-fold interpenetrated dia network. Structural comparison of these polymers suggests that different central metals and dicarboxylates play important roles in the construction of 1–7. The luminescent properties of complexes 3, 4, 6, 7 and the electrochemical properties of complexes 1, 2 have been investigated. Furthermore, the complexes 2–4, 6 and 7 exhibit photocatalytic activities for dye methylene blue degradation under UV light and show good stability toward photocatalysis.

Synthesis, Crystal Structures and Properties of Two Heterometallic Complexes [Cu2M] (M = Cd, Mn) with a Novel Oxamato-bridged Ligand

Two novel trinuclear oxamato-bridged thiosemicarbazone complexes, [Cu(obte)]2Cd(DMF)2 (2) and [Cu(obte)]2Mn(DMF)2 (3) (H2obte = N-(2-benzaldehyde) oxamic acid ethyl ester thiosemicarbazone (1); DMF=dimethylformamide), have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Complexes 2 and 3 are isostructural, displaying a trinuclear structure. The luminescence properties of complexes 2 and 3 were investigated in the solid state at room temperature. The ligand 1 and its complex 2 have been evaluated for their antitumor activities against K562 cells.

Two 3D CdIIand ZnIIComplexes Based on Flexible Dicarboxylate Ligand and Nitrogen-containing Pillar: Synthesis, Structure, and Luminescent Properties

Two 3D isomorphous and isostructural complexes, namely, (1) and (2); (BDOA = Benzene-1,4-dioxyacetic acid, bpy = 4,4'-bipyridine) were synthesized under hydrothermal conditions and characterized by means of elemental analyses, thermogravimetric (TG), infrared spectrometry, and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic system, space group P-1 and each metal ion in the complexes are six-coordinated with the same coordination environment. In the as-synthesized complexes, anions link central metal ions to form a 1D zigzag chain , whereas bpy pillars connect metal ions to generate a 1D linear chain . Both infinite chains are interweaved into 2D grid-like layers which are further constructed into a 3D open framework, where hydrogen bonds play as the bridges between the adjacent 2D layers. Luminescent properties of complex 1 showed selectivity for ion.

Four Complexes derived from a Benzimidazole‐thioether Derivative Ligand: Syntheses, Crystal Structures and Luminescent Properties

Abstract Four complexes based on a benzimidazole‐thioether derivative ligand 2‐[(4‐pyridine)sulfydryl]‐ethyl‐1H‐benzimidazole (pteHb), namely, {[CdCl2(pteHb)2]2·2DMF}n (1), [CdI2(pteHb)]2 (2), {[CoCl2(pteHb)]2·DMF} (3), and {[ZnCl2(pteHb)]2·DMF} (4), were prepared under solvothermal and solvent evaporation conditions. X‐ray diffraction analysis reveals that the Cl– ions of complex 1 act as μ2 bridge to connect the CdII ions resulting in a dinuclear unit. The units are bridged by the ligand pteHb to give a 1D double‐looped chain. Complexes 2–4 are dinuclear and further assembled into a 3D supramolecular architecture via π–π interactions, hydrogen bonding interactions, and intermolecular forces. Complexes 1–4 were characterized by elemental analyses and IR spectroscopy. Furthermore, solid‐state luminescent properties of complexes 1, 4, and ligand pteHb were also investigated.

Construction of several new s-/p-block complexes containing binuclear metal–terpyridine building blocks: dependence of structural diversity on the number of coordinated water molecules

Five new coordination polymers, [Mg(DSPT)(H2O)2]·2H2O (H2DSPT = 4′-(2,4-disulfophenyl)-2,2′:6′2′′-terpyridine) (1), {[Ca(DSPT)(H2O)2]·1.5H2O}n (2), {[Pb(DSPT)(H2O)]·2H2O}n (3), {[Pb(DSPT)]·0.5H2O}n (4), and {[Pb3(DSPT)3(H2O)]·8H2O}n (5), were prepared under hydrothermal conditions. They are all complexes containing similar M2L2 binuclear metal–terpyridine building units. Complex 1 is a discrete binuclear molecule that extends to 2D layers via O–H⋯O hydrogen bonds between coordinated water and a sulfo group on H2DSPT. Complexes 2 and 3 are 1D coordination chains based on [M2(DSPT)2] ring subunits but are connected by different M–O bonds, and the 1D chains are also further connected by O–H⋯O hydrogen bonds between coordinated water and a sulfo group on H2DSPT to a 2D layer. Complex 4 exhibits a 2D coordination network also based on the [M2(DSPT)2] ring subunits. Complex 5 is a by-product of the synthesis of complex 4 that displays a 1D coordination chain structure containing the same [M2(DSPT)2] ring subunits. Interestingly, the 2D layers described above show identical skeletons when the bond types between [M2(DSPT)2] ring subunits are neglected. The 2D layers in complexes 1–3 can be derived from replacing selected coordination bonds in complex 4 with hydrogen bonds, and such structural diversity is largely dependent on the number of coordinated water molecules around the metal center. Thermogravimetric analyses of 1–4 showed that they were stable at temperatures higher than 500 °C. The luminescent properties of complexes 1–4 were also investigated.

Syntheses, Crystal Structures, and Properties of Six Coordination Complexes Based on a Newly Designed Mercapto-thiadiazole Ligand

Six coordination complexes were solvothermally synthesised: a 3D framework [Cd(tmtt)2]n (1), 2D architectures [Zn(tmtt)2]n (2) and [Pb(tmtt)2]n (3), 1D chain structures [Ni(tmtt)2·(H2O)2]n (4) and [Co(tmtt)2·(H2O)2]n (5), and a mononuclear structure [Hg(tmtt)2] (6). The complexes, based on self-assembly of different metal ions with a newly designed mercapto-thiadiazole ligand tmttH (tmttH = 5-[(1H-1,2,4-triazol-1-yl)methyl]-1,3,4-thiadiazole-2(3H)-thione), were characterised by single crystal X-ray diffraction analyses. Crystal structure analyses reveal that complex 1 exhibits a four-fold interpenetrating 3D framework with {64.82} topology based on two kinds of right-handed single-helical chains, 2 displays a bilayer structure, 3 presents a crown-shaped network, 4 and 5 show 1D double–helical chain structures, and 6 is a mononuclear structure. Moreover, the thermal stabilities of crystalline samples 1–6 have been investigated, and the luminescent properties of complexes 1, 2, 3, 6, and the free ligand have been studied. The results of photoluminescent measurements illustrate that 2 and 3 may serve as excellent candidates for potential photoactive materials.

Three New Metal–Organic Polymers Based on Flexible 3-(4-(Carboxymethoxy) Phenyl) Propanoic Acid: Crystal Structures, Luminescent and Magnetic Properties

Three new metal–organic coordination complexes, [Zn2L(bpp)2Cl2] n (1), [ZnL(bipy)] n (2), [NiL(bipy)(H2O)] n (3), have been synthesized through hydrothermal reactions of flexible 3-(4-(carboxymethoxy)phenyl) propanoic acid(H2L) with different pyridyl-containing 1,3-bis(4-pyridyl)propane(bpp) or 4,4′-bipyridine(bipy) ligand, and they are characterized by elemetal analysis and single-crystal X-ray diffraction techniques. Complex 1 has a 2-D layer supramolecular network composed of 1-D distorted trapezoidal chains via C–H···π stacking interactions. Complex 2 displays a 2-D lattice-shaped layer structure. Complex 3 has three kinds of O–H···O intermolecular hydrogen bonds, exhibiting a 3-D supramolecular framework. The luminescent properties of complex 1 and 2 have indicated the mixture characteristic of intraligand and ligand-to-ligand charge transition. The magnetic property of 3 has shown the ferromagnetic coupling between Ni2+ ions.

Tuning Structural Topologies of Two Cadmium(II) Coordination Polymers via Isomeric Dipyridyl Ligands: Syntheses, Crystal Structures, and Luminescent Properties

AbstractAbstract. Two new coordination polymers {[Cd2(BDC)2(3‐bpmp)(H2O)2]·2H2O}n (1) and [Cd2(BDC)2(4‐bpmp)]n (2) [H2BDC = 5‐hydroxy‐isophthalic acid, 3‐bpmp = 1,4‐bis(3‐pyridylmethy)piperazine, and 4‐bpmp = 1,4‐bis(4‐pyridylmethy) piperazine] were synthesized via hydrothermal synthesis, and further characterized by IR spectroscopy, elemental analysis, XRD, and X‐ray crystallography. Complex 1 shows a two‐dimensional (4,4) sql topology and complex 2 features an 8‐connected hex topology. Moreover, the luminescent properties of complexes 1 and 2 were investigated in the solid state at room temperature.