Iodine-Rich Supramolecular Complexes of Chlorobismuthates(III): Unusual Lone Pair Activity and Features of Halogen Bonding in Crystals.

The first chrorobismuthate(III) supramolecular hybrids with halogen-bond-linked I2, (Py(CH2)2Py){[BiCl5](I2)} (1) and (Py(CH2)3Py){[BiCl5](I2)0.5} (2), were synthesized via the reaction between Bi2O3, I2, and salts of the corresponding cations in HCl. The compounds featured one- and two-dimensional (2D) supramolecular motifs built by I···Cl contacts; in the case of 1, Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I2 pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.

Molecular Recognition on the Multisite Binding Surface of the Keplerate {Mo72Fe30} Giving Supramolecular Texturing and Modulating the Function of Guest Molecules.

Molecular recognition underlies structure formation in supramolecular architectures either in materials or in living systems. Here, we used the nanoscale nontoxic Keplerate-type polyoxometalate (POM) {Mo72Fe30} as a template for the recognition of two different guest molecules [tetracycline (TC) and doxorubicin (DOX)] on the textured surface. By means of single crystal X-ray analysis and X-ray photoelectron spectroscopy (XPS), we revised the key features of the {Mo72Fe30} structure, showcasing the guest dimolybdenum units' {Mo2} location under the hexagonal pores and dynamic exchange of these units during dissolution in an aqueous medium. Based on the clarified POM structure, we demonstrated how the small differences between the TC and the DOX molecules can be recognized by the Keplerate surface, revealing the nature of the binding sites─{Mo6}/{FeO6} for TC and {FeO6} for DOX. Furthermore, using the Monte-Carlo method, we calculated the statistical distribution of the guest molecules in the stoichiometric compounds {Mo72Fe30}@TC12 and {Mo72Fe30}@DOX12, displaying the supramolecular ordering of the DOX species and randomization of the TC as a result of different coordinations to the POM surface. The produced {Mo72Fe30}@TC12 and {Mo72Fe30}@DOX12 associates were evaluated for bioactivity, showing how their interaction with POM can modulate the biological function of guest molecules.

Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties.

Seven heterometallic iodoantimonates with the general formula (Cat)2{[Sb2M2I10]} (M = Cu(I) (1-6), Ag(I) (7)) were prepared. X-ray diffraction data indicate that these compounds are the first Sb(III) representatives of the structural type previously known only for heterometallic iodobismuthates(III). In 3 and 4, halogen-substituted cations form halogen bonds with the heterometallic halometalate chain. 1-7 show prominent thermal stability. The estimated optical band gaps lie between 2.16 and 2.40 eV. As in heterometallic iodobismuthates, incorporation of Cu+ rather than Ag+ provides a much lower band gap.

Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies.

We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

Octahedral Tantalum Bromide Clusters as Catalysts for Light-Driven Hydrogen Evolution.

The development of an efficient hydrogen generation strategy from aqueous protons using sunlight is a current challenge aimed at the production of low-cost, easily accessible, renewable molecular hydrogen. For achieving this goal, non-noble metal containing and highly active catalysts for the hydrogen evolution reaction (HER) are desirable. Octahedral tantalum halide clusters {Ta6(µ-X)12}2+ (X = halogen) represent an emerging class of such HER photocatalysts. In this work, the photocatalytic properties of octahedral aqua tantalum bromide clusters toward HER and in acid and homogeneous aqueous conditions were investigated. The [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner ligand; a = apical ligand) compound is revealed to be an efficient precatalyst in acid (HBr) conditions and with methanol as the sacrificial agent. A response surface methodology (RSM) study was applied for the optimization of the HER conditions, considering the concentrations of both additives (methanol and HBr) as independent variables. An optimal H2 production of 11 mmol·g-1 (TON = 25) was achieved, which displays exceptional catalytic properties compared to regular Ta-based materials. The aqua tantalum bromide clusters assist in the photocatalytic hydrogen generation in agreement with energy-conversion schemes, and plausible active catalytic species and a reaction mechanism were proposed from computational and experimental perspectives.

Noncovalent Self-Assembly of Single-Layer MoS2 Nanosheets and Zinc Porphyrin into Stable SURMOF Nanohybrids with Multimodal Photocatalytic Properties.

A noncovalent integration of nanosheets of molybdenum disulfide (MoS2) and the zinc porphyrin complex Zn(II) 5,10,15,20-tetrakis(4-carboxyphenyl)porphine (ZnTCPP) through coordination bonding with metal clusters of zinc acetate (Zn[OAc]2) was applied for synthesis of stable hybrid nanomaterial avoiding surface prefunctionalization. The X-ray powder diffraction in combination with the BET nitrogen adsorption method confirms formation of a ZnTCPP-based surface-attached metal-organic framework (SURMOF) with micropores of 1.63 nm on the MoS2 nanosheets. Fluorescence spectroscopy confirmed Forster resonance energy transfer (FRET) between MoS2 and ZnTCPP without contact quenching. Fluorescent trapping with terephthalic acid for hydroxyl radicals and Sensor Green for singlet oxygen was applied for studying the pathways of photodegradation of model organic pollutant 1,5-dihydroxynaphthalene (DHN) in the presence of SURMOF/MoS2. Visible light initiates sensitization through the excitation of ZnTCPP generating singlet oxygen, whereas UV-light promotes either aerobic FRET-mediated "Z scheme" or anaerobic "Type II heterojunction" mechanisms. Owing to its multimodal photochemistry, the SURMOF/MoS2 hybrid showed comparatively high photocatalytic activity in UV-assisted degradation of DHN (keffUV = 4.0 × 10-2 min-1) as well as the antibacterial activity confirmed by E. coli survival test under visible light. Noncovalent self-assembly utilizing coordination bonding in SURMOFs as supramolecular adhesive to avoid surface premodification provides a basis for new types of multicomponent nanosystems with switchable functionalities by combining different 2D materials and chromophores in one hybrid structure.

Not So Similar: Different Ways of Nb(V) and Ta(V) Catecholate Complexation.

The reactions between catechol (H2cat) and niobium(V) or tantalum(V) precursors in basic aqueous solutions lead to the formation of catecholate complexes of different natures. The following complexes were isolated and characterized by single-crystal X-ray diffraction (SCXRD): (1) (NH4)3[NbO(cat)3]∙4H2O; (2) K2[Nb(cat)3(Hcat)]·2H2cat·2H2O; (3) Cs3[NbO(cat)3]·H2O; (4) (NH4)4[Ta2O(cat)6]·3H2O; (5) Cs2[Ta(cat)3(Hcat)]·H2cat; (6) Cs4[Ta2O(cat)6]·7H2O. The isolated crystalline products were characterized by elemental analysis, X-ray powder diffraction (XRPD), FTIR, and TGA. The structural features of these complexes, such as {Ta2O} unit geometry, Cs-π interactions, and crystal packing effects, are discussed.

Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (1), [Ir(cod)(NO)(dpp-bian)](BF4)2 (2) and [Ir(cod)(dpp-bian)](BF4) (3), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of 1-3 feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for 1) or a NO group (for 2) to complete a square-pyramidal geometry. In the nitrosyl complex 2, the Ir-N-O group has a bent geometry (the angle is 125°). The CV data for 1 and 3 show two reversible waves between 0 and -1.6 V (vs. Ag/AgCl). Reversible oxidation was also found at E1/2 = 0.60 V for 1. Magnetochemical measurements for 2 in a range from 1.77 to 300 K revealed an increase in the magnetic moment with increasing temperature up to 1.2 µB (at 300 K). Nitrosyl complex 2 is unstable in solution and loses its NO group to yield [Ir(cod)(dpp-bian)](BF4) (3). A paramagnetic complex, [Ir(cod)(dpp-bian)](BF4)2 (4), was also detected in the solution of 2 as a result of its decomposition. The EPR spectrum of 4 in CH2Cl2 is described by the spin Hamiltonian H = gßHS with S = 1/2 and gxx = gyy = 2.393 and gzz = 1.88, which are characteristic of the low-spin 5d7-Ir(II) state. DFT calculations were carried out in order to rationalize the experimental results.

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior.

Nine heterometallic iodobismuthates with the general formula Cat2{[Bi2M2I10}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {Bi2I10} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C. Optical band gaps (Eg), estimated at room temperature via diffuse reflectance measurements, range from 1.81 to 2.03 eV. Thermally induced changes in optical behavior (thermochromism) for compounds 1-9 were recorded, and general correlations were established. The thermal dependence of Eg appears to be close to linear for all studied compounds.

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions.

Solution behavior of K;5[(Mn(H2O))PW11O39]·7H2O (1), Na3.66(NH4)4.74H3.1[(MnII(H2O))2.75(WO(H2O))0.25(α-B-SbW9O33)2]·27H2O (2), and Na4.6H3.4[(MnII(H2O)3)2(WO2)2(ß-B-TeW9O33)2]·19H2O (3) was studied with NMR-relaxometry and HPLC-ICP-AES (High Performance Liquid Chromatography coupled with Inductively Coupled Plasma Atomic Emission Spectroscopy). According to the data, the [(Mn(H2O))PW11O39]5- Keggin-type anion is the most stable in water among the tested complexes, even in the presence of ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Aqueous solutions of 2 and 3 anions are less stable and contain other species resulting from dissociation of Mn2+. Quantum chemical calculations show the change in Mn2+ electronic state between [Mn(H2O)6]2+ and [(Mn(H2O))PW11O39]5-.

Supramolecular hybrids based on Ru(II) porphyrin and octahedral Mo(II) iodide cluster.

The coordination-driven design and synthesis of new stable supramolecular cluster-porphyrin (CP) hybrids based on an A2-type ruthenium porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]ruthenium(carbonyl)(aqua) [RuDTolP(CO)H2O] and an octahedral molybdenum(II) iodide cluster with six terminal isonicotinate ligands (Bu4N)2[{Mo6I8}(OOC-C5H4N)6] (PyMoC) are reported. The stepwise supramolecular assembly of the PyMoC "superoctahedron" with RuDTolP(CO)H2O has been studied by 1H NMR and 2D 1H-1H COSY, 1H-15N HMBC and DOSY techniques, as well as by UV-vis spectroscopy and HR-ESI mass spectrometry. The formation of discrete cluster-porphyrin CPn adducts with different numbers of coordinated porphyrins (n = 1-6), including the geometrical isomers of CP2, CP3 and CP4, has been observed. Using a double equivalent amount of RuDTolP(CO)H2O relative to the cluster (C : P ratio 1 : 12) affords a mixture of CP5 and CP6 species in solution, while only the CP6 complex is crystallized from this system. Fine tuning of crystallization conditions leads to the formation of a more complex architecture CP6+2, where the CP6 assembly incorporates two additional porphyrin molecules bound to the cluster core by hydrogen bonds. Thus, the coordination-based supramolecular approach provides new stable cluster-multiporphyrin 3D arrays based on two types of photosensitizers, which can be promising for the design of photoactive materials.

One-Step Interfacial Integration of Graphene Oxide and Organic Chromophores into Multicomponent Nanohybrids with Photoelectric Properties.

A one-step protocol for interfacial self-assembly of graphene oxide (GO), glutamine-substituted perylene diimide (PDI-glu), 10,12-pentacosadiynoic acid (PCDA), and zinc acetate into three- and four-component hybrid nanofilms through hydrogen and coordination bonding was developed. The hybrids deposited onto solid supports were studied after polymerization of PCDA by UV-vis absorption, fluorescence, and Raman spectroscopies, scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results of spectroscopic studies suggest that the hybrids assembled through H-bonds can maintain the light-induced Förster energy transfer from the PDI-glu chromophore to the conjugated polymer and then to GO leading to fluorescence quenching. In the hybrids assembled through coordination bonding with zinc clusters, the energy transfer proceeds from PDI-glu to the PDA polymer, whereas the transfer from PDA to GO is quenched completely. Another important characteristic of these ultrathin hybrids is their stability with respect to photobleaching of chromophores due to the acceptor properties of GO. The as-assembled hybrid nanofilms were integrated with conventional photovoltaic planar architectures to study their photoelectric properties. The zinc-containing hybrids integrated with a hole transport layer exhibited photovoltaic properties. The cell with the integrated four-component hybrid comprising both PDI-glu and PDA showed a photocurrent/dark current ratio almost an order higher than that of the three-component hybrid assembled with PDA only. The supramolecular method based on the interfacial self-assembly can be extended to a wide variety of organic chromophores and polymerizable surfactants for integrating them into multicomponent functional GO-based nanohybrids with targeted properties for organic electronics.

Proton Affinity in the Chemistry of Beta-Octamolybdate: HPLC-ICP-AES, NMR and Structural Studies.

The affinity of [ß-Mo8O26]4- toward different proton sources has been studied in various conditions. The proposed sites for proton coordination were highlighted with single crystal X-ray diffraction (SCXRD) analysis of (Bu4N)3[ß-{Ag(py-NH2)Mo8O26]}] (1) and from analysis of reported structures. Structural rearrangement of [ß-Mo8O26]4- as a direct response to protonation was studied in solution with 95Mo NMR and HPLC-ICP-AES techniques. A new type of proton transfer reaction between (Bu4N)4[ß-Mo8O26] and (Bu4N)4H2[V10O28] in DMSO results in both polyoxometalates transformation into [V2Mo4O19]4-, which was confirmed by the 95Mo, 51V NMR and HPLC-ICP-AES techniques. The same type of reaction with [H4SiW12O40] in DMSO leads to metal redistribution with formation of [W2Mo4O19]2-.

One-Dimensional Iodoantimonate(III) and Iodobismuthate(III) Supramolecular Hybrids with Diiodine: Structural Features, Stability and Optical Properties.

Two isostructural pairs of supramolecular iodoantimonate(III) and iodobismuthate(III) complexes with I2 units "trapped" in solid state via halogen bonding-Cat3[[M2I9](I2)} (Cat = tetramethylammonium and 1-methylpyridinium, M = Sb(III) and Bi(III)) were prepared. For all compounds, values of optical band gaps were determined, together with thermal stability; the complexes were additionally characterized by Raman spectroscopy.

Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry.

Self-assembly of (Bu4N)4[ß-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[ß-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV-Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2.

Nanostructured Hybrids Based on Tantalum Bromide Octahedral Clusters and Graphene Oxide for Photocatalytic Hydrogen Evolution.

The generation of hydrogen (H2) using sunlight has become an essential energy alternative for decarbonization. The need for functional nanohybrid materials based on photo- and electroactive materials and accessible raw materials is high in the field of solar fuels. To reach this goal, single-step synthesis of {Ta6Bri12}@GO (GO = graphene oxide) nanohybrids was developed by immobilization of [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner and a = apical positions of the Ta6 octahedron) on GO nanosheets by taking the advantage of the easy ligand exchange of the apical cluster ligands with the oxygen functionalities of GO. The nanohybrids were characterized by spectroscopic, analytical, and morphological techniques. The hybrid formation enhances the yield of photocatalytic H2 from water with respect to their precursors and this is without the presence of precious metals. This enhancement is attributed to the optimal cluster loading onto the GO support and the crucial role of GO in the electron transfer from Ta6 clusters into GO sheets, thus suppressing the charge recombination. In view of the simplicity and versatility of the designed photocatalytic system, octahedral tantalum clusters are promising candidates to develop new and environmentally friendly photocatalysts for H2 evolution.

Coordination of Pt(IV) by {P8W48} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies.

Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li17(NH4)21H2[P8W48O184] with [Pt(H2O)2(OH)4] results in coordination of up to six {Pt(H2O)x(OH)4-x} fragments to the internal surface of the polyoxoanion. The product was isolated as K22(NH4)9H3[{Pt(OH)3(H2O)}6P8W48O184]·79H2O (1) and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode. The complex shows electrocatalytic activity in water oxidation.

Niobium and Tantalum Halocyanide Clusters: The Complete Family.

Synthetic procedures providing straightforward access to the whole family of Nb and Ta halide clusters with terminal cyanide ligands have been developed. Corresponding [M6X12(CN)12]4- (M = Nb, Ta; X = Cl, Br) can be accessed by ligand-exchange procedures from K4Nb6X18 (X = Cl, Br) and Bu4NCN, (Et4N)2[Ta6Cl18] and Bu4NCN and from [Ta6Br12(H2O)4Br2]·4H2O and KCN in moderate to high yields (50-80%). The products were isolated as Bu4N salts. The compounds were investigated both experimentally and by quantum chemistry, revealing correlations between structural, electrochemical, electrostatic, electronic, and topological features as a function of type of metal, halide, and charge.

Enhancement of photoactivity and cellular uptake of (Bu4N)2[Mo6I8(CH3COO)6] complex by loading on porous MCM-41 support. Photodynamic studies as an anticancer agent.

The incorporation by ionic assembly of the hexanuclear molybdenum cluster (Bu4N)2[Mo6I8(CH3CO2)6] (1) in amino-decorated mesoporous silica nanoparticles MCM-41, has yielded the new molybdenum-based hybrid photosensitizer 1@MCM-41. The new photoactive material presents a high porosity, due to the intrinsic high specific surface area of MCM-41 nanoparticles (989 m2 g-1) which is responsible for the good dispersion of the hexamolybdenum clusters on the nanoparticles surface, as observed by STEM analysis. The hybrid photosensitizer can generate efficiently singlet oxygen, which was demonstrated by using the benchmark photooxygenation reaction of 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABDA) in water. The photodynamic therapy activity has been tested using LED light as an irradiation source (λirr ~ 400-700 nm; 15.6 mW/cm2). The results show a good activity of the hybrid photosensitizer against human cervical cancer (HeLa) cells, reducing up to 70 % their viability after 20 min of irradiation, whereas low cytotoxicity is detected in the darkness. The main finding of this research is that the incorporation of molybdenum complexes at porous MCM-41 supports enhances their photoactivity and improves cellular uptake, compared to free clusters.

Selenium(IV) Polybromide Complexes: Structural Diversity Driven by Halogen and Chalcogen Bonding.

Reactions between bromoselenate(IV)-containing solutions, dibromine and salts of pyridinium-family organic cations resulted in structurally diverse, bromine-rich polybromine-bromoselenates(IV): (4-MePyH)5[Se2Br9][SeBr6](Br3)2 (1), (2-MePyH)2{[SeBr6](Br2)} (2), (PyH)2{[SeBr5]Br(Br2)2} (3), (1-MePy)2{[SeBr6](Br2)} (4). The compounds feature halogen and (in the case of 3) chalcogen bonding in solid state, resulting in formation of supramolecular architectures of different dimensionality. DFT calculations allowed estimation of the energies of non-covalent interactions in 1-4; additionally, characterization by Raman spectroscopy was performed.