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Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve a carbon-neutral energy cycle. However, it remains a great challenge to controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation of targeted products, especially the multicarbon (C2+) products. Herein we report the coordination environment engineering of metal centers in coordination polymers for efficient electroreduction of CO2 to C2+ products under neutral conditions. Significantly, the Cu coordination polymer with Cu-N2S2 coordination configuration (Cu-N-S) demonstrates superior Faradaic efficiencies of 61.2% and 82.2% for ethylene and C2+ products, respectively, compared to the selective formic acid generation on an analogous polymer with the Cu-I2S2 coordination mode (Cu-I-S). In situ studies reveal the balanced formation of atop and bridge *CO intermediates on Cu-N-S, promoting C-C coupling for C2+ production. Theoretical calculations suggest that coordination environment engineering can induce electronic modulations in Cu active sites, where the d-band center of Cu is upshifted in Cu-N-S with stronger selectivity to the C2+ products. Consequently, Cu-N-S displays a stronger reaction trend toward the generation of C2+ products, while Cu-I-S favors the formation of formic acid due to the suppression of C-C couplings for C2+ pathways with large energy barriers. © 2024 American Chemical Society

A series of lead(II) complexes incorporating benzoate derivative ligands was prepared: [Pb(2MeOBz)2]n (1), [Pb(2MeOBz)2(H2O)]n (2), [Pb2(1,4Bzdiox)4(DMSO)]n (3), [Pb(1,4Bzdiox)2(H2O)]n (4), [Pb(Pip)2(H2O)]n (5), and [Pb(Ac)(Pip)2(MeOH)]n (6) (2MeOBz: 2-methoxybenzoate; 1,4Bzdiox: 1,4-benzodioxan-5-carboxylate; DMSO: dimethylsulfoxide; Ac: acetate; Pip: piperonylate; MeOH: methanol). All compounds were characterized via elemental analysis, ATR-FTIR spectroscopy, and powder XRD. In addition, the crystal structures of some compounds were elucidated. Compounds 1 and 2, involving 2-methoxybenzoate, were closely related, only differing in the presence of one extra aqua ligand found for the latter. However, this implies key changes in the studied properties, e.g., 2 shows solid-state luminescence that displays a different color as a function of the crystal orientation, while 1 does not. The crystal structure of 2 revealed a 1D coordination polymer. A similar relationship was found between compounds 3 and 4, incorporating 1,4-benzodioxan-5-carboxylate. In this pair, only 4, with aqua ligands, displayed a greenish-yellow-color solid-state luminescence. Furthermore, two new lead(II) piperonylate complexes, 5 and 6, were obtained from the reaction between lead(II) acetate and piperonylic acid. In water, all acetate ligands in the metal precursor were displaced and [Pb(Pip)2(H2O)]n (5) was isolated, while in methanol, a mixed acetate–piperonylate complex, [Pb(Ac)(Pip)2(MeOH)]n (6), was precipitated. Considering only conventional Pb-O bonds, the crystal structure of 6 was described as a 1D coordination polymer, although, additionally, the chains were associated via tetrel bonds, defining an extended 2D architecture.

Luminescent lanthanide coordination polymer crystals (LCPCs) represent an area of growing interest in materials chemistry owing to their unique and tailorable functional properties. The LCPCs provide a high level of structural tunability, including size- and morphology-dependent properties; therefore, they are promising materials for next-generation phosphors in a wide range of applications such as light emitting diodes. Here, by controlling the morphology of thermostable europium coordination polymer crystals, [Eu(hfa)(3)(dpbp)](n), hfa: hexafluoroacetylacetonate and dpbp:4,4'-bis(diphenyl phosphoryl) biphenyl), we realized a novel red phosphor with narrow linewidth emission (FWHM = 7.8 nm). The obtained luminescent LCPCs with unique structures were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and thermogravimetric analysis. Among, them, size tunable crystalline polymer spheres were found to have high internal quantum efficiency (ex., IQE = 79%) and highly thermostability (>300 degrees C), and to exhibit dispersibility in PMMA media. The obtained results on the structural tunability of these materials can be used for the development of synthesis techniques for nanoscale materials based on crystalline lanthanide-based coordination phosphors. [GRAPHICS] .

Luminescent lanthanide coordination polymer crystals (LCPCs) represent an area of growing interest in materials chemistry owing to their unique and tailorable functional properties. The LCPCs provide a high level of structural tunability, including size- and morphology-dependent properties; therefore, they are promising materials for next-generation phosphors in a wide range of applications such as light emitting diodes. Here, by controlling the morphology of thermostable europium coordination polymer crystals, [Eu(hfa)(3)(dpbp)](n), hfa: hexafluoroacetylacetonate and dpbp:4,4'-bis(diphenyl phosphoryl) biphenyl), we realized a novel red phosphor with narrow linewidth emission (FWHM = 7.8 nm). The obtained luminescent LCPCs with unique structures were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and thermogravimetric analysis. Among, them, size tunable crystalline polymer spheres were found to have high internal quantum efficiency (ex., IQE = 79%) and highly thermostability (>300 degrees C), and to exhibit dispersibility in PMMA media. The obtained results on the structural tunability of these materials can be used for the development of synthesis techniques for nanoscale materials based on crystalline lanthanide-based coordination phosphors. [GRAPHICS] .

Luminescent lanthanide coordination polymer crystals (LCPCs) represent an area of growing interest in materials chemistry owing to their unique and tailorable functional properties. The LCPCs provide a high level of structural tunability, including size- and morphology-dependent properties; therefore, they are promising materials for next-generation phosphors in a wide range of applications such as light emitting diodes. Here, by controlling the morphology of thermostable europium coordination polymer crystals, [Eu(hfa)(3)(dpbp)](n), hfa: hexafluoroacetylacetonate and dpbp:4,4'-bis(diphenyl phosphoryl) biphenyl), we realized a novel red phosphor with narrow linewidth emission (FWHM = 7.8 nm). The obtained luminescent LCPCs with unique structures were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and thermogravimetric analysis. Among, them, size tunable crystalline polymer spheres were found to have high internal quantum efficiency (ex., IQE = 79%) and highly thermostability (>300 degrees C), and to exhibit dispersibility in PMMA media. The obtained results on the structural tunability of these materials can be used for the development of synthesis techniques for nanoscale materials based on crystalline lanthanide-based coordination phosphors. [GRAPHICS] .

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4′-bipy)2 (H2 O)] (4,4′-bipy=4,4′-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid–methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal–organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4′-bipy)2 (H2 O)] (4,4′-bipy=4,4′-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid–methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal–organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.

A chiral Eu(III) coordination polymer with phase-transition behavior, [Eu(+tfc)3(m-dpeb)]n, (+tfc: (+)-3-trifluoroacetylcamphorato, m-dpeb: 1,3-bis(diphenylphosphorylethynyl)benzene) was reported for understanding the effect of polymer chain arrangement (orientation effect) on the circularly polarized luminescence (CPL) in a solid system. The phase-transition behavior of the transformable Eu(III) coordination polymer was characterized using differential scanning calorimetry and powder X-ray diffraction. The Eu(III) coordination polymer exhibited phase transition at approximately 180 degrees C. The magnitude of the CPL intensity was drastically changed because of the phase transition, without coordination geometrical change around the Eu(III) ion. In this study, the orientation effect of a chiral Eu(III) coordination polymer on the CPL properties in crystalline solid is demonstrated.

Exploiting redox activity in supramolecular frameworks such as coordination polymers, metal-organic frameworks and related nanostructures is of paramount importance both at the molecular level and for their technological applications, since the modulation of their redox states is an emerging strategy to enhance their physical properties. In the plethora of organic linkers, quinone derivatives are excellent redox-active ligands, widely used for various applications such as electrode materials, flow batteries, pseudocapacitors, etc. Benzoquinones undergo a one-electron reversible reduction to form a semiquinone radical species that can be further reduced to form hydroquinone. Remarkably, the quinoid ring can be functionalized with various functional groups making these systems excellent linkers to construct supramolecular frameworks as well as challenging platforms to tune the redox potential and therefore the stability of radical anions and electrochemical performances of the obtained materials. The recent advances on benzoquinone-based 2D CPs/MOFs and related nanostructures are reported, highlighting the extreme versatility of this class of redox-active linkers in tailoring the physical properties of the obtained materials. The current/future potential of these materials in electrochemical and technologically relevant applications will also be envisioned., QC 20221027

A chiral Eu(III) coordination polymer with phase-transition behavior, [Eu(+tfc)3(m-dpeb)]n, (+tfc: (+)-3-trifluoroacetylcamphorato, m-dpeb: 1,3-bis(diphenylphosphorylethynyl)benzene) was reported for understanding the effect of polymer chain arrangement (orientation effect) on the circularly polarized luminescence (CPL) in a solid system. The phase-transition behavior of the transformable Eu(III) coordination polymer was characterized using differential scanning calorimetry and powder X-ray diffraction. The Eu(III) coordination polymer exhibited phase transition at approximately 180 degrees C. The magnitude of the CPL intensity was drastically changed because of the phase transition, without coordination geometrical change around the Eu(III) ion. In this study, the orientation effect of a chiral Eu(III) coordination polymer on the CPL properties in crystalline solid is demonstrated.

This work contributes to enlightening the opportunities of the anisotropic scheme of non-covalent interactions present in supramolecular materials. It provides a top-down approach based on their selective disruption that herein has been employed to process a conventional microcrystalline material to a nanofibrillar porous material. The developed bulk microcrystalline material contains uracil-1-propionic acid (UPrOH) nucleobase as a molecular recognition capable building block. Its crystal structure consists of discrete [Cu(UPrO)2 (4,4′-bipy)2 (H2 O)] (4,4′-bipy=4,4′-bipyridine) entities held together through a highly anisotropic scheme of non-covalent interactions in which strong hydrogen bonds involving coordinated water molecules provide 1D supramolecular chains interacting between them by weaker interactions. The sonication of this microcrystalline material and heating at 45 °C in acetic acid–methanol allows partial reversible solubilization/recrystallization processes that promote the cross-linking of particles into an interlocked platelet-like micro-particles metal–organic gel, but during CO2 supercritical drying, the microcrystalline particles undergo a complete morphological change towards highly anisotropic nanofibers. This unprecedented top-down microstructural conversion provides a nanofibrillar material bearing the same crystal structure but with a highly increased surface area. Its usefulness has been tested for HPLC separation purposes observing the expected nucleobase complementarity-based separation.

Herein, we describe and study a new family of isostructural multifunctional metal-organic frameworks (MOFs) with the formula {[Ln(5)L(6)(OH)(3)(DMF)(3)]center dot 5H(2)O} n (where (H2L) is 3-amino-4-hydroxybenzoic acid ligand) for magnetism and photoluminescence. Interestingly, three of the materials (Dy-, Er-, and Yb-based MOFs) present singlemolecule magnet (SMM) behavior derived from the magnetic anisotropy of the lanthanide ions as a consequence of the adequate electronic distribution of the coordination environment. Additionally, photoluminescence properties of the ligand in combination with Eu and Tb counterparts were studied, including the heterometallic Eu-Tb mixed MOF that shows potential as ratiometric luminescent thermometers. Finally, the porous nature of the framework allowed showing the CO2 sorption capacity.

We report the synthesis of multi-Mo-substituted Preyssler-type phosphotungstates, [P5W30-xMoxO110Na(H2O)]14−, with different amounts of incorporated Mo via the hydrothermal reactions of H3PO4, Na2WO4, and Na2MoO4; and characterization by 31P nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR), elemental analysis, electrospray ionization-mass spectrometry (ESI-MS), and cyclic voltammetry. The number of substituted Mo increases by increasing the amount of Na2MoO4 in the reaction mixture, and in the [P5W30-xMoxO110Na(H2O)]14−, up to penta-Mo-substituted species can be produced as mixtures of isomers with different Mo numbers and Mo positions. Single crystal X-ray structure analysis and density functional theory calculation indicate that the most suitable substitution position is the belt position.

Pancreatic cancer is a usually fatal disease that needs innovative therapeutic approaches since the current treatments are poorly effective. In this study, based on cell lines, triazole-based coordination trimers made with soluble Fe(II) in an aqueous media were explored for the first time as adjuvant agents for the treatment of this condition. These coordination complexes were effective at relatively high concentrations and led to an increase in reactive oxygen species (ROS) in two pancreatic cancer cell lines, PANC-1 and BXPC-3, and this effect was accompanied by a significant reduction in cell viability in the presence of gemcitabine (GEM). Importantly, the tested compounds enhanced the effect of GEM, an approved drug for pancreatic cancer, through apoptosis induction and downregulation of the mTOR pathway. Although further evaluation in animal-based models of pancreatic cancer is needed, these results open novel avenues for exploring these iron-based materials in biomedicine in general and in pancreatic cancer treatment., Asociación Española Contra el Cáncer, IMDEA Nanociencia, Comunidad de Madrid, Ministerio de Economía y Competitividad (España), Depto. de Bioquímica y Biología Molecular, Fac. de Ciencias Biológicas, TRUE, pub

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. The supplementary ifnormation contains: Selected hydrogen-bond parameters for 3, solid-state optical absorption spectra for crystalline samples of 1–4, plots of concentration ratios against irradiation time for 1–4 and Degussa P25, the changes in photodegradation percentage of MB9 after three successive cycles for 4, IR spectra of pristine and CP 4 after the third cycle and UV–vis spectra for the MB9 solution in the presence of 4 and quenchers. CCDC numbers are 2068533–2068536 for compounds 1–4, respectively.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Coordination polymer frameworks (CPFs) have broad applications due to their excellent features, including stable structure, intrinsic porosity, and others. However, preparation of thin-film CPFs for energy storage and conversion remains a challenge because of poor compatibility between conductive substrates and CPFs and crucial conditions for thin-film preparation. In this work, a CPF film was prepared by the coordination of the anisotropic four-armed ligand and CuII at the liquid–liquid interface. Such film-based micro-supercapacitors (MSCs) are fabricated through high-energy scribing and electrolytes soaking. As-fabricated MSCs displayed high volumetric specific capacitance of 121.45 F cm−3. Besides, the volumetric energy density of MSCs reached 52.6 mWh cm−3, which exceeds the electrochemical performance of most reported CPF-based MSCs. Especially, the device exhibited alternating current (AC) line filtering performance (−84.2° at 120 Hz) and a short resistance capacitance (RC) constant of 0.08 ms. This work not only provides a new CPF for MSCs with AC line filtering performance but also paves the way for thin-film CPFs preparation with versatile applications., QC 20211221

Energiförbrukning är ett hett ämne i världen idag, eftersom världens befolkning fortsätter att växa. Som ett resultat ökar också den globala energiförbrukningen snabbt och utsläppen av koldioxid därmed, vilket påverkar global uppvärmning och klimatförändringar. Således kommer utvecklingen av förnybara energikällor att bli en av nödvändighet. Solenergi utgör en förnybar energikälla och uppvisar en enorm potential för att tillgodose det globala energibehovet. En solcell är kan användas för att omvandla solljus till elektricitet. Många typer av solceller har utvecklats under det senaste decenniet, och forskning för att förbättra effektiviteten kommer att fortsätta i framtiden. Material baserade på kopparhalogenidkomplex har uppvisat intressanta optiska och elektrokemiska egenskaper på grund av flera laddningsöverföringsexciterade tillstånd. Genom att kombinera kopparhalogenidsystem med organiska ligander med två bindningsgrupper, kommer komplexet att kunna bilda nätverksstrukturer i flera dimensioner och därmed effektivt kunna leda ström. Eftersom kopparhalogenidkomplex uppvisar unika optiska och elektriska egenskaper, är det värt att undersöka dem för användning i solceller. Syftet med examensarbete har varit att undersöka kopparhalogenidkomplex med optiska och elektrokemiska egenskaper. Kopparhalogenidkomplex med bidentatligander har syntetiserats och applicera som tunna filmer undersöktes. I kapitel 1 och 2 av uppsatsen presenteras bakgrunden och en introduktion av denna studie, samt de experimentella metoderna. I kapitel 3 beskrivs syntesen av kopparjodid-4,4'-bipyridinkomplex och karakteriseringen av detsamma. Applicering av det resulterande materialet på glassubstrat diskuteras också. I kapitel 4 beskrivs syntesen av kopparhalogenid-N-oxid-4,4'-bipyridinkomplex med efterföljande karakterisering. I kapitel 5 undersöks metoder för att applicera kopparjodidpyridin på koppar-folie och FTO-belagda glassubstrat., Energy consumption is presently a hot topic in the world since the world’s population continues to grow. As a result, global energy consumption is increasing rapidly and the emission of carbon dioxide is also increasing, which causes global warming and climate change. Thus, the development of renewable energy sources will be one of the solutions. Solar energy is one of the renewable energy sources and has a huge potential to satisfy the global energy demand. A solar cell harvests light and converts it to electricity. Many kinds of solar cells have been developed in the past decades, and investigation for the improvement of the efficiency will be continued in the future. Copper halide organic complex materials have some potential for optical and electrochemical properties due to several charge transfer states inside the structure. By combining copper halide with bidentate organic ligands, the complex will form high dimensional network structure and will have electrical property due to the formation of electron conducting paths. Since copper halide complex has potential for unique optical and electrical properties, it is worth investigating for the further photovoltaic application. The aim of the thesis is to investigate copper halide complex material showing optical and electrochemical property. Copper halide complex with bidentate ligands were synthesized and the way to apply copper halide complex to films were also investigated in this thesis. In chapter 1 and 2, the background and the introduction of this study and the experimental methods are presented. In chapter 3, the synthesis of copper iodide 4,4’-bipyridine complex and the characterization of the complex sample are presented. The application of the complex to glass substrate is also discussed. In chapter 4, the synthesis of copper halide N-oxide-4,4’-bipyridine complex and the characterization are discussed. In chapter 5, the way to apply copper iodide pyridine to copper foil and FTO-coated glass substrate

Hofmann-type organometallic frameworks are well known for their porous crystal structure, exhibiting interesting electronic, optical, and magnetic properties, and are therefore considered as promising materials for various technological applications. Here, using density functional theory+U (DFT+U) calculations, we investigate the spin-state transition in a newly synthesized Hofmann clathrate, namely the Fe{OS(CH3)(2)}(2){Ag(CN)(2)}(2) complex, by applying hydrostatic pressure as an external perturbation. Our study reveals that under a relatively low isotropic hydrostatic pressure, the complex exhibits a reversible spin switching, whereas it undergoes a structural phase transition when the pressure is larger and anisotropic. The spin state of the Fe atom in the Hofmann clathrate complex transforms from high spin to intermediate spin state under anisotropic compression of the lattice parameters. The coordination polymer complex remains a magnetic semiconductor after the pressure-driven structural transformation.

The present thesis aims to provide suitable information on the fundamentals about the controlled manipulation and targeted application of nanoscale porous materials. The research interests in this work are focused on the controlled colloidal synthesis and functionalization of two specific porous materials based on porous coordination polymers (PCPs) and calcium carbonate polymeric nanoparticles (CCPNs), as nanocarriers for intended biological and catalytic applications.

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu(L)(DMF)}, where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(HO)]·HO} (complex 2). On the other hand, ultrasound is required to induce the nanostructuration. Remarkably, different morphologies are obtained using different solvents and interconversion from one morphology to another seems to occur upon solvent exchange. Both complexes 1 and 2, as well as the corresponding nanostructures, have been fully characterized by different means such as infrared spectroscopy, x-ray diffraction and microscopy.

Bisphosphonates (BPs) constitute a class of drugs used for the treatment of calcium-and bone-related disorders, including osteoporosis, Paget’s disease, etc. The presence of the anionic phosphonate groups endows them with the ability to act as ligands to metal ions. As a result, the synthesis of complexes or coordination polymers of various structural motifs can be accomplished. In this work, the 3rd generation BP drug risedronate (RIS) was combined with biologically acceptable alkaline earth metal ions (e.g., Ca and Sr) in an effort to synthesize new materials. These metal– RIS compounds can operate as controlled delivery systems (CDSs) when exposed to appropriate experimental conditions, such as the low pH of the human stomach. CDS networks containing Ca or Sr and RIS were physicochemically and structurally characterized and were evaluated for their ability to release the free RIS drug during an acid-driven hydrolysis process. Due to the low solubility of RIS at low pH, cationic additives (linear polyethyleneimine and amine-terminated polyaminoamide dendrimer) were utilized as drug solubilizers. Based on the drug release results of this study, there was an attempt to correlate the drug release efficiency with the structural features of these CDSs.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. The supplementary ifnormation contains: Selected hydrogen-bond parameters for 3, solid-state optical absorption spectra for crystalline samples of 1–4, plots of concentration ratios against irradiation time for 1–4 and Degussa P25, the changes in photodegradation percentage of MB9 after three successive cycles for 4, IR spectra of pristine and CP 4 after the third cycle and UV–vis spectra for the MB9 solution in the presence of 4 and quenchers. CCDC numbers are 2068533–2068536 for compounds 1–4, respectively.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Four silver-based coordination polymers, {[Ag(L1)2]NO3}∞ (1), {[Ag(L1)2]ClO4}∞ (2), {[Ag(L2)2]NO3·H2O}∞ (3) and {[Ag(L2)2]ClO4}∞ (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(I) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min−1. The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

We present a new heteroditopic ligand (3pyCCMoid) that contains the typical skeleton of a curcuminoid (CCMoid) decorated with two 3-pyridyl groups. The coordination of 3pyCCMoid with ZnII centres results in a set of novel coordination polymers (CPs) that display different architectures and dimensionalities (from 1D to 3D). Our work analyses how synthetic methods and slight changes in the reaction conditions affect the formation of the final materials. Great efforts have been devoted toward understanding the coordination entities that provide high dimensional systems, with emphasis on the characterization of 2D materials, including analyses of different types of substrates, stability and exfoliation in water. Here, we foresee the great use of CCMoids in the field of CPs and emphasize 3pyCCMoid as a new-born linker.

Nanoscale coordination polymers (NCPs) have fascinated researchers over the last years. Their intrinsic theranostic properties of metal ions and organic ligands, the encapsulation of several drugs/biomolecules with excellent yields and the surface functionalisation, enhancing their biocompatibility and targeting, have remarkably impacted in prospective drug delivery alternatives in medicine. Moreover, the properties and characteristics of these nanoparticles (NPs) can be fine-tuned thanks to the synthetic flexibility of coordination chemistry. For all these reasons, the number of examples published has grown exponentially over the last years, embracing different disciplines such as molecular electronics, sensors or nanomedicine, among others. Specifically, significant advances in antitumoural applications are reported, one of the areas where this novel family of NPs has experienced a considerable advance. NCPs have accomplished a high sophistication degree and efficiency as theranostic nanoplatforms (i.e., drug delivery carriers and bioimaging probes) with long residence time in the bloodstream, targeting capacities and remarkable cellular internalisation. In this review, an introduction emphasizing the advantages of NPs for cancer treatment is included. Later on, the most representative examples of NCPs for antitumoural applications are described grouped into six mean representative areas: i) encapsulation approaches, ii) stimuli-responsive NCPs, iii) metal chemotherapy, iv) photodynamic therapy (PDT), v) unconventional therapeutic approaches and vi) theranostics. Particular emphasis is given to understand the encapsulation/release properties of these particles at the nanoscale and their interaction with biological environments, highlighting any limitation and challenges that these systems are facing from a clinical translation perspective and envisioning possible future trends and areas that will deserve further attention for the following years.

Energiförbrukning är ett hett ämne i världen idag, eftersom världens befolkning fortsätter att växa. Som ett resultat ökar också den globala energiförbrukningen snabbt och utsläppen av koldioxid därmed, vilket påverkar global uppvärmning och klimatförändringar. Således kommer utvecklingen av förnybara energikällor att bli en av nödvändighet. Solenergi utgör en förnybar energikälla och uppvisar en enorm potential för att tillgodose det globala energibehovet. En solcell är kan användas för att omvandla solljus till elektricitet. Många typer av solceller har utvecklats under det senaste decenniet, och forskning för att förbättra effektiviteten kommer att fortsätta i framtiden. Material baserade på kopparhalogenidkomplex har uppvisat intressanta optiska och elektrokemiska egenskaper på grund av flera laddningsöverföringsexciterade tillstånd. Genom att kombinera kopparhalogenidsystem med organiska ligander med två bindningsgrupper, kommer komplexet att kunna bilda nätverksstrukturer i flera dimensioner och därmed effektivt kunna leda ström. Eftersom kopparhalogenidkomplex uppvisar unika optiska och elektriska egenskaper, är det värt att undersöka dem för användning i solceller. Syftet med examensarbete har varit att undersöka kopparhalogenidkomplex med optiska och elektrokemiska egenskaper. Kopparhalogenidkomplex med bidentatligander har syntetiserats och applicera som tunna filmer undersöktes. I kapitel 1 och 2 av uppsatsen presenteras bakgrunden och en introduktion av denna studie, samt de experimentella metoderna. I kapitel 3 beskrivs syntesen av kopparjodid-4,4'-bipyridinkomplex och karakteriseringen av detsamma. Applicering av det resulterande materialet på glassubstrat diskuteras också. I kapitel 4 beskrivs syntesen av kopparhalogenid-N-oxid-4,4'-bipyridinkomplex med efterföljande karakterisering. I kapitel 5 undersöks metoder för att applicera kopparjodidpyridin på koppar-folie och FTO-belagda glassubstrat., Energy consumption is presently a hot topic in the world since the world’s population continues to grow. As a result, global energy consumption is increasing rapidly and the emission of carbon dioxide is also increasing, which causes global warming and climate change. Thus, the development of renewable energy sources will be one of the solutions. Solar energy is one of the renewable energy sources and has a huge potential to satisfy the global energy demand. A solar cell harvests light and converts it to electricity. Many kinds of solar cells have been developed in the past decades, and investigation for the improvement of the efficiency will be continued in the future. Copper halide organic complex materials have some potential for optical and electrochemical properties due to several charge transfer states inside the structure. By combining copper halide with bidentate organic ligands, the complex will form high dimensional network structure and will have electrical property due to the formation of electron conducting paths. Since copper halide complex has potential for unique optical and electrical properties, it is worth investigating for the further photovoltaic application. The aim of the thesis is to investigate copper halide complex material showing optical and electrochemical property. Copper halide complex with bidentate ligands were synthesized and the way to apply copper halide complex to films were also investigated in this thesis. In chapter 1 and 2, the background and the introduction of this study and the experimental methods are presented. In chapter 3, the synthesis of copper iodide 4,4’-bipyridine complex and the characterization of the complex sample are presented. The application of the complex to glass substrate is also discussed. In chapter 4, the synthesis of copper halide N-oxide-4,4’-bipyridine complex and the characterization are discussed. In chapter 5, the way to apply copper iodide pyridine to copper foil and FTO-coated glass substrate

Highly water-dispersible, redox-active 1D coordination polymers (CPs) have been synthesized using low-cost precursors. These CPs, containing chloranilic acid as organic ligand and a transition element, such as Fe and Mn as a metal center, form long-term stable slurries containing up to 100 g/L solid particles in aqueous media (0.5 M NaCl, 1 mg carbon nanotubes). Voltammetry studies showed that the iron-based particulate slurries exhibited three different redox stages with no metal plating. However, the suspensions with manganese-based coordination polymers experienced a metal plating process in the same potential window range as for the iron-based CPs. Moreover, the particulate suspension of iron-CPs shown longer-term stability than their isostructural analogs based on manganese. The 1D Fe-CPs were used as catholyte and anolyte in a symmetrical cell with a low-cost size exclusion cellulose membrane acting as a separator. The cell experienced a reversible capacity value of 45 mAh/g (225 mAh/L) at a current density value of 20 mA/g for 50 cycles (~12 days) at neutral pH. This study opens the possibility of using inexpensive coordination polymers as single bifunctional electrolyte material in aqueous batteries and other sustainable energy storage-related systems.

Four silver-based coordination polymers, {[Ag(L1)(2)]NO3}(infinity) (1), {[Ag(L1)(2)]ClO4}(infinity) (2), {[Ag(L2)(2)]NO3 center dot H2O}(infinity) (3) and {[Ag(L2)(2)]ClO4}(infinity) (4), were synthesized using the thiomorpholine-4-carbonitrile (L1) and piperazine-1,4-dicarbonitrile (L2) ligands. Compounds 1 and 2 are two-dimensional, while 3 and 4 are three-dimensional. L1 and L2 are 1,4-bis-monodentate ligands in all compounds, while Ag(i) ions are four-coordinated in a slightly distorted tetrahedral geometry. Topological analysis in standard representations suggests that underlying nets in 1 and 2 have an sql topology, while 3 and 4 exhibit a dia topology. Thermal analysis shows that 3 loses crystalline water at room temperature, while other compounds show good thermal stability. All compounds show good photocatalytic activity for photocatalytic degradation of the mordant blue 9 dye, with reaction rates in the range 0.029 to 0.061 min(-1). The best result was obtained for compound 4, which can be correlated to its largest lattice volume.

Large blue rectangular crystals of the 2D layered coordination polymer 1 have been obtained. The interest for this complex is two-fold. First, complex 1 is made of 2D layers packing along the (0–11) direction favored by the presence of lattice and coordinated water molecules. And second, nanostructures that could be derived by delamination are potentially suitable for catalytic purposes. Therefore it represents an excellent example to study the role of interlayer solvent molecules on the ultrasound-assisted delamination of functionally-active 2D metal-organic frameworks in water, a field of growing interest. With this aim, ultrasound-assisted delamination of the crystals was optimized with time, leading to stable nanosheet colloidal water suspensions with very homogeneous dimensions. Alternative bottom-up synthesis of related nanocrystals under ultrasound sonication yielded similar shaped crystals with much higher size dispersions. Finally, experimental results evidence that the nanostructures have higher catalytic activities in comparison to their bulk counterparts, due to larger metallic center exposition. These outcomes confirm that the combination of liquid phase exfoliation and a suitable synthetic design of 2D coordination polymers represents a very fruitful approach for the synthesis of functional nanosheets with an enhancement of catalytic active sites, and in general, with boosted functional properties.

Cellulose-based hydrogels are promising sustainable materials for a variety of applications, including tissue engineering, water treatment, and drug delivery. However, the tailoring of diverse properties by efficient green chemistry methods is an ongoing challenge. Here, composite hydrogels of consistent spheroidal structure, incorporating TEMPO-oxidized cellulose nanofibrils and nanofibrous chiral Cu(II) aspartate coordination polymer, are presented. The hydrogels are prepared by a single-step procedure in aqueous media at ambient temperature and pressure, adhering to the principles of green chemistry. With a view to adapting this method for a variety of alternative coordination polymers (to tailor functional properties), the following critical factors for formation of robust composite hydrogel spheroids are identified: rheological properties of the primary matrix used for spheroidal hydrogel formation and coordination polymer self-assembly rate. © 2020 The Authors. Published by Wiley-VCH GmbH, QC 20201202

Two new scandium-containing coordination polymers, with the formulae {(CH3)2NH2}[Sc(BPDC)2] (1) and [Sc(OH) (BPyDC)] (2) were solvothermally synthesized by using the linear linker molecules biphenyl-4,4′-dicarboxylic acid (H2BPDC) and 2,2′-bipyridine-5,5′-dicarboxylic acid (H2BPyDC). Crystal structures were determined from single-crystal and powder Xray diffraction data, respectively. The crystal structures of 1 and 2 contain isolated ScO6 or chains of trans corner-sharing ScO6 octahedra as the inorganic building unit (IBU), which are connected by the linker molecules to a 3D framework or a layered structure, respectively. The compounds were characterized by IR-spectroscopy, elemental analysis, thermogravimetric analysis and photoluminescence spectroscopy. 1 shows blue emission at 400 nm, while 2 exhibits intense green emission at 550 nm with a high quantum yield (QY) of 69 %.

Table S1. Crystallographic data and refinement parameters for SQUEEZED 3 with general formula {[Ag2(H2BTEC)(L)2]}∞; Table S2. Pairwise interaction energies in the crystal structure of 1 based on B3LYP/ DGDZVP energy mode; Table S3. Pairwise interaction energies in the crystal structure of 2 based on B3LYP/ DGDZVP energy mode; Table S4. Pairwise interaction energies in the crystal structure of 3 based on B3LYP/ DGDZVP energy model; Table S5. Pairwise interaction energies in the crystal structure of 4 based on B3LYP/ DGDZVP energy model; Powder X-ray diffraction analysis: All samples correspond to the single-phase X-ray powder patterns (Figure S1) in accordance with the structural model obtained by the single-crystal X-ray diffraction. It should be noted that the best overlap of peaks in the powder pattern for 3 was obtained using SQUEEZED cif single crystal data. According to the results of powder X-ray structural analysis, as well as thermogravimetric analysis, 3 readily loses solvent water molecules without change of the structure. For 1, 2 and 4, given the absence of any secondary phases, it can be concluded that all of the samples are stable in air under conditions of manual pulverization required to create powder samples from single crystals.

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.

Die in drei Dimensionen verknüpften und porösen Metall-Organischen Gerüstverbindungen (metal-organic frameworks: MOFs) bieten interessante Ansatzpunkte für verschiedene Anwendungen, wie Sensorik oder Separation. Ihre in nur einer Dimension verknüpften Gegenstücke, die linearen Koordinationspolymere (linear coordination polymers: LCPs), können als vereinfachte Modellsysteme für MOFs betrachtet werden. In einer explorativ ausgerichteten Untersuchung zu LCPs wurde die Grundlage für ein Modellsystem aufgebaut, welches für die Synthese von LCPs mit einer definierten Abfolge unterschiedlicher Bausteine genutzt werden kann. Wie in ähnlichen biologischen Systemen, wie z.B. DNA/RNA bietet das die Möglichkeit, Informationen zu codieren. Der zweite Schwerpunkt der Arbeit lag auf der Untersuchung von Synthesen von Zr-MOFs in Dimethylformamid (DMF) mittels Kernresonanzspektroskopie, um mögliche Nebenreaktionen aufzuklären. Als Basis für die Synthese neuer LCPs dienten Silber(I)-Kationen und N Donor Linkermoleküle sowie 18 Krone 6 als zusätzlicher Ligand, welcher das Silberatom gegen störende Einflüsse aus der Reaktionslösung abschirmt. Es konnten verschiedene neue LCPs synthetisiert werden, deren struktureller Aufbau mithilfe von Einkristalldiffraktometrie aufgeklärt wurde. Neben der Synthese dieser LCPs wurden Versuche durchgeführt, um die Eignung anderer Metallatome für eine mögliche Erweiterung des Reaktionssystems zu überprüfen. Dafür wurden Molekülkomplexe synthetisiert, bei denen die bidentaten Linkermoleküle durch entsprechende monodentate Liganden ersetzt wurden. Hier wurden Verbindungen mit Eisen(II), Mangan(II), Kupfer(II) und Quecksilber(II) erhalten und ihre Kristallstrukturen röntgenographisch aufgeklärt. Eine Bestimmung der Bindungsvalenzen anhand der Atomabstände in der Koordinationssphäre des jeweiligen Zentralatoms wurde genutzt, um die gefundenen Koordinationsumgebungen im Hinblick auf ihre Eignung für ein solches Modellsystem zu beurteilen. Für die Untersuchun, Because of their modular composition coordination polymers form a group of compounds that is vast in numbers and versatile in their properties. On the one hand, the three-dimensionally connected metal organic frameworks (MOFs) offer interesting potential applications, like sensing or separation. On the other hand, the one-dimensionally connected linear coordination polymers (LCPs) can be regarded as simplified model systems for MOFs. In an explorative investigation into LCPs with a strong connection between the metal atom and linker molecule, it was the goal to set up a model system that allows the formation of LCPs with a defined sequence of different building blocks. Similar to biological systems like DNA/RNA, this can be used to encode information. The second focus of the thesis lay on nuclear magnetic resonance investigations on Zr MOF syntheses in the solvent dimethylformamide (DMF), which were carried out in order to identify possible side reactions. The synthesis of new LCPs was based on silver(I) cations and N donor linker molecules, as well as on 18 crown 6 as an additional ligand to protect the silver atom against interfering influences from the reaction solution. The structures of newly-found compounds were determined via single-crystal X-ray diffraction. Besides the experiments carried out to form these LCPs, experiments with iron(II), manganese(II), copper(II) and mercury(II) cations were conducted to find other fitting combinations of metal cations and linker molecules. For this, molecular complexes were synthesized in which the bidentate linker molecules were changed to monodentate ligands. The bond-lengths to the neighboring atoms of the central atoms of these complexes were used to calculate the respective bond valences. These valences served as a basis to evaluate the suitability of the coordination spheres found in these complexes to form LCPs relevant for this model system. The investigation of side reactions in DMF-based Zr-MOF syntheses was per

Table S1. Crystallographic data and refinement parameters for SQUEEZED 3 with general formula {[Ag2(H2BTEC)(L)2]}∞; Table S2. Pairwise interaction energies in the crystal structure of 1 based on B3LYP/ DGDZVP energy mode; Table S3. Pairwise interaction energies in the crystal structure of 2 based on B3LYP/ DGDZVP energy mode; Table S4. Pairwise interaction energies in the crystal structure of 3 based on B3LYP/ DGDZVP energy model; Table S5. Pairwise interaction energies in the crystal structure of 4 based on B3LYP/ DGDZVP energy model; Powder X-ray diffraction analysis: All samples correspond to the single-phase X-ray powder patterns (Figure S1) in accordance with the structural model obtained by the single-crystal X-ray diffraction. It should be noted that the best overlap of peaks in the powder pattern for 3 was obtained using SQUEEZED cif single crystal data. According to the results of powder X-ray structural analysis, as well as thermogravimetric analysis, 3 readily loses solvent water molecules without change of the structure. For 1, 2 and 4, given the absence of any secondary phases, it can be concluded that all of the samples are stable in air under conditions of manual pulverization required to create powder samples from single crystals.

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.

Four silver-based coordination polymers, {[Ag(L)2](BF4)}∞ (1), {[Ag(H2BTC)(L)]·(H3BTC)}∞ (2), {[Ag2(H2BTEC)(L)2]·3.33H2O}∞ (3), and [Ag(H25SSA)(L)]∞ (4), were synthesized using thiomorpholine-4-carbonitrile (L) as the primary ligand and three aromatic polyoxoacids as coligands: trimesic (H3BTC), pyromellitic (H4BTEC), and 5-sulfosalicylic acid (H35SSA). Compounds 1 and 3 are two-dimensional, while 2 and 4 are one-dimensional. L acts as a bis-monodentate ligand, while the Ag(I) ion is three-coordinated in 2 and four-coordinated in all of the other compounds. The tetrahedral coordination of Ag(I) in 3 leads to an almost complete absence of intermolecular interactions with the metal center. All compounds show reasonable photocatalytic activity for photocatalytic degradation of mordant blue 9 dye, with reaction rates in the 0.036–0.056 min–1 range. Changes in the reaction rates can be correlated with the type and coordination of the coligand. Complex 3 exhibits photoluminescence at 77 K, while 4 exhibits photoluminescence at both room temperature and 77 K. Luminescence lifetimes indicate electronic transitions of singlet parentage, where transitions are allowed. A TD-DFT study determined the contributions of individual singlet–singlet electronic excitations to the fluorescence, indicating that metal– intraligand transitions are responsible for luminescence in both complexes.

Five new coordination polymers (CPs) constructed of aminopyridine-2-carboxylate (ampy) ligand have been synthesized and fully characterized. Three of them correspond to metal-organic chains built from the coordination of ampy to sodium and lanthanides with formulae [MNa(ampy)4]n (M = terbium (2), erbium (1) and ytterbium (3)) resembling a previously reported dysprosium material which shows anticancer activity. On another level, the reaction of Hampy with cobalt and copper ions ({[CoK(ampy)3(H2O)3](H2O)3}n (4) and [Cu(ampy)2]n (5)) lead to CPs with variable dimensionalities, which gives the opportunity of analyzing the structural properties of this new family. Lanthanide materials display solid state intense photoluminescent emissions in both the visible and near-infrared region and exhibit slow relaxation of magnetization with frequency dependence of the out-of-phase susceptibility. More interestingly, in our search for multifunctional materials, we have carried out antitumor measurements of these compounds. These multidisciplinary studies of metal complexes open up the possibility for further exploring the applications in the fields of metal-based drugs.

Soft crystallization routes for the controlled growth of oneand two-dimensional Cu(II)-coordination polymers of the type [(Cu- (hfa)2)x(3-tpt)]n (hfa = hexafluoroacetylacetonate, 3-tpt = 2,4,6-tris(3- pyridyl)-1,3,5-triazine) are described. Three volatile solvents with different protic/aprotic characteristics were chosen as the reaction media, e.g., supercritical CO2, chloroform, and ethanol. Five (1−5) new compounds were crystallized, with different structures and Cu(II)/3-tpt ratios. The structures of 3-tpt and five new coordination polymers were elucidated by single-crystal synchrotron X-ray diffraction. A description of the crystallization pathways followed for the synthesis of the individual compounds is given based on the protic or aprotic character of the used solvents and reagents’ solubility constraints. The main novelty of the work relies in establishing the foundations of 3-tpt isomeric control during crystallization through solvent selection. From the five precipitated new compounds, 3 displays a significant framework flexibility, associated with N2 adsorption at low temperature, presenting a stepwise adsorption isotherm. The N2 adsorption process was followed by in situ synchrotron X-ray powder diffraction

This article introduces a new family of coordination polymers (CPs) that contains a natural biocompatible curcumin derivative, the bisdemethoxycurcumin (BDMC), coordinated to Zn(II) centers. The reaction between BDMC and zinc acetate, performed under mild conditions in ethanol, provides a new 1D phase termed BDMCZn-1. In addition, dimensionality and porosity of this network have been expanded by studying the reaction occurring between three species, the BDMC, the Zn(II) and a ditopic co-linker: 1,2-bis(4-pyridyl)ethylene, 1,3-bis(4- pyridyl)propane or 4,4'-bipyridine. In total, seven new CPs are presented, named as BDMCZnx. The structures of five of them could be elucidated by single crystal X-ray diffraction. Moreover, we show that the combination of the latest technique with solid-state 13C nuclear magnetic resonance is a powerful tool set to analyze the coordination modes of the BDMC, providing insight into the two unresolved structures. In the achievement of the new CPs, we further discuss the coordination capacity of BDMC, the relevance of solvents and supramolecular interactions.

A coordination polymer formulated as [Sr(H2BTEC)(H2O)]n (H4BTEC = benzene-1,2,4,5-tetra­carb­oxy­lic acid, C10H6O8), was synthesized hydro­thermally and characterized by single-crystal and powder X-ray diffraction, scanning electron microscopy and thermal analysis. Its crystal structure is made up of a zigzag inorganic chain formed by edge-sharing of [SrO8] polyhedra running along [001]. Adjacent chains are connected to each other via the carboxyl­ate groups of the ligand, resulting in a double-layered network extending parallel to (100). O—H...O hydrogen bonds of medium-to-weak strength between the layers consolidate the three-dimensional structure. One of the carb­oxy­lic OH functions was found to be disordered over two sets of sites with half-occupancy.