Iron(II) spin-transition complexes with dendritic ligands, part II

The dendritic triazole-based complexes \[Fe(G1-BOC)3](triflate) 2·xH2O (1; G1-BOC = tert-butyl {3-\[3-(3-tert- butoxycarbonylaminopropyl)-5-(\[1,2,4]triazol-4-ylcarbamoyl)-phenyl]propyl} carbamate, triflate = CF3SO3-), \[Fe(G1-BOC) 3]-(tosylate)2·xH2O(2;tosylate = p-CH3PhSO3-),\[Fe(G1-DPBE)3]-(triflate) 2·xH2O {3; G1-DPBE = 3,5-bis(3,5- didodecaoxybenzyloxy)-N-\[1,2,4]triazol-4-ylbenzamide}, \[Fe(G1-DPBE) 3]-(tosylate)2·xH2O (4) and \[Fe(G1-DPBE)3](BF4)2·xH2O (5) were designed and synthesized. Magnetic and thermal properties of these novel complexes were characterized by magnetic susceptibility measurements, 57Fe Mössbauer spectroscopy and thermogravimetric analysis or differential scanning calorimetry, respectively. All dendritic complexes under study show different spin-transition behaviour with respect to the nature of different dendritic ligands and counteranions. Complexes 1 and 2 have pronounced effects of a spin-state change during the first heating process and gradual spintransition properties for further temperature treatments, whereas 3 and 4 exhibited a very sharp spin-state change in the first heating procedures. Complex 5 showed a gradual spin-transition curve. In this paper, we report how the magnetic properties of these complexes are correlated with noncoordinated water molecules and their effects on spin states.

Rodlike bimetallic ruthenium and osmium complexes bridged by phenylene spacers. Synthesis, electrochemistry, and photophysics

In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2′-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 Å for the shortest and longest complex, respectively. For one of the ruthenium precursors, [RUbpy-ph2-Si(CH3) 3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed.

Disturbed microtubule function and induction of micronuclei by chelate complexes of mercury(II)

Interactions of mercury(II) with the microtubule network of cells may lead to genotoxicity. Complexation of mercury(II) with EDTA is currently being discussed for its employment in detoxification processes of polluted sites. This prompted us to re-evaluate the effects of such complexing agents on certain aspects of mercury toxicity, by examining the influences of mercury(II) complexes on tubulin assembly and kinesin-driven motility of microtubules. The genotoxic effects were studied using the micronucleus assay in V79 Chinese hamster fibroblasts. Mercury(II) complexes with EDTA and related chelators interfered dose-dependently with tubulin assembly and microtubule motility in vitro. The no-effect-concentration for assembly inhibition was 1 μM of complexed Hg(II), and for inhibition of motility it was 0.05 μM, respectively. These findings are supported on the genotoxicity level by the results of the micronucleus assay, with micronuclei being induced dose-dependently starting at concentrations of about 0.05 μM of complexed Hg(II). Generally, the no-effect-concentrations for complexed mercury(II) found in the cell-free systems and in cellular assays (including the micronucleus test) were identical with or similar to results for mercury tested in the absence of chelators. This indicates that mercury(II) has a much higher affinity to sulfhydryls of cytoskeletal proteins than to this type of complexing agents. Therefore, the suitability of EDTA and related compounds for remediation of environmental mercury contamination or for other detoxification purposes involving mercury has to be questioned.

Hybrid CuTCNQ/AgTCNQ metal-organic charge transfer complexes via galvanic replacement vs. corrosion recrystallization

This study reports a hybrid of two metal-organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8-tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion-recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal-organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal-organic semiconductors that will expand the scope of TCNQ-based charge transfer complexes for improved catalysis, sensing, electronics and biological applications.

Influences of molecular structure on co-crystallization of polypyridyl metal complexes.

Heteroleptic complexes of the type \[RuL2L′](PF6)2 (L, L′ = combinations of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy)) were found to cocrystallize with \[Ni(phen)3](PF6)2 to produce cocrystals of \[Ni(phen)3]x\[RuL2L′]1–x(PF6)2. In this report we show that the ability of the complexes to cocrystallize is influenced by the number of common ligands between complexes in solution. Supramolecular selection is a phenomenon caused by molecular recognition through which cocrystals can grow from the same solution but contain different ratios of the molecular components. It was found that systems where L = phen displayed less supramolecular selection than systems where L = bipy. With increasing supramolecular selection, the composition of cocrystals was found to vary significantly from the initial relative concentration in the cocrystallizing solution, and therefore it was increasingly difficult to control the final composition of the resultant cocrystals. Consequently, modulation of concentration-dependent properties such as phase was also found to be less predictable with increasing supramolecular selection. Notwithstanding the complication afforded by the presence of supramolecular selection, our results reaffirm the robustness of the \[M(phen)3](PF6)2 structure because it was maintained even when ca. 90% of the complexes in the cocrystals were \[Ru(phen)(bipy)2](PF6)2, which in its pure form is not isomorphous with \[M(phen)3](PF6)2. Experiments between complexes without common ligands, i.e., \[Ru(bipy)3](PF6)2 cocrystallized with \[Ni(phen)3](PF6)2, were found to approach the limit to which molecular recognition processes can be confused into cocrystallizing different molecules to form single cocrystals. For these systems the result was the formation of block-shaped crystals skewered by a needle-shaped crystals.

Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands : synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F8), diphenylaminofluorenyl (NPh2- F8), or naphthalimidylfluorenyl (NI-F8) motifs on the bipyridyl or acetylide ligands (Pt-4−Pt-8), (i.e., {4,4′-bis[7-R1-F8-(≡)n-]bpy}Pt(7- R2-F8- ≡ -)2, where F8 = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′- bipyridine, Pt-4: R1 = R2 = BTZ, n = 0; Pt-5: R1 = BTZ, R2 = NI, n = 0; Pt-6: R1 = R2 = BTZ, n = 1; Pt-7: R1 = BTZ, R2 = NPh2, n = 1; Pt- 8: R1 = NPh2, R2 = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly 1π,π* transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially 1MLCT (metal-to-ligand charge transfer)/ 1LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some 1ILCT (intraligand charge transfer) transition for Pt-4−Pt-7, and predominantly 1ILCT transition admixing with minor 1MLCT/1LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the 1π,π* and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized 1π,π* fluorescence and 3MLCT/3LLCT phosphorescence in CH2Cl2, while Pt-5 manifests 1ILCT fluorescence and 3ILCT phosphorescence. However, only 1LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4−Pt-8 in CH3CN. Except for Pt-7 that contains NPh2 at the acetylide ligands, Pt-4−Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh2 on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.

The molecular structure of kaolinite–potassium acetate intercalation complexes: A combined experimental and molecular dynamic simulation study

The kaolinite (Kaol) intercalated with potassium acetate (Ac) was prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetry. Molecular dynamic simulation was performed to investigate the structure of Kaol–Ac intercalation complex and the hydrogen bonds between Kaol and intercalated Ac andwater using INTERFACE forcefield. The acetate anions andwater arranged in a bilayer structure in the interlayer space of Kaol. The potassium cations distributed in the interlayer space and strongly coordinated with acetate anions aswell aswater rather than keyed into the ditrigonal holes of tetrahedral surface of Kaol. Strong hydrogen bonds formed between the hydrogen atoms of hydroxyl on the octahedral surface and oxygen atoms of both acetate anions and water. The acetate anions andwater also weakly bonded hydrogen to the silica tetrahedral surface through their hydrogen atoms with the oxygen atoms of silica tetrahedral surface.

New insights into the molecular structure of kaolinite–methanol intercalation complexes

A series of kaolinite–methanol complexes with different basal spacings were synthesized using guest displacement reactions of the intercalation precursors kaolinite–N-methyformamide (Kaol–NMF), kaolinite–urea (Kaol–U), or kaolinite–dimethylsulfoxide (Kaol–DMSO), with methanol (Me). The interaction of methanol with kaolinite was examined using X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Kaolinite (Kaol) initially intercalated with N-methyformamide (NMF), urea (U), or dimethylsulfoxide (DMSO) before subsequent reaction with Me formed final kaolinite–methanol (Kaol–Me) complexes characterized by basal spacing ranging between 8.6 Å and 9.6 Å, depending on the pre-intercalated reagent. Based on a comparative analysis of the three Kaol–Me displacement intercalation complexes, three types of Me intercalation products were suggested to have been present in the interlayer space of Kaol: (1) molecules grafted onto a kaolinite octahedral sheet in the form of a methoxy group (Al-O-C bond); (2) mobile Me and/or water molecules kept in the interlayer space via hydrogen bonds that could be partially removed during drying; and (3) a mixture of types 1 and 2, with the methoxy group (Al-O-C bond) grafted onto the Kaol sheet and mobile Me and/or water molecules coexisted in the system after the displacement reaction by Me. Various structural models that reflected four possible complexes of Kaol–Me were constructed for use in a complimentary computational study. Results from the calculation of the methanol kaolinite interaction indicate that the hydroxyl oxygen atom of methanol plays the dominant role in the stabilization and localization of the molecule intercalated in the interlayer space, and that water existing in the intercalated Kaol layer is inevitable.

Two-dimensional coordination polymeric structures in caesium complexes with ring-substituted phenoxyacetic acids

The two-dimensional polymeric structures of the caesium complexes with the phenoxyacetic acid analogues (4-fluorophenoxy)acetic acid, (3-chloro-2-methylphenoxy)acetic acid and the herbicidally active (2,4-dichlorophen­oxy)acetic acid (2,4-D), namely poly[[5-(4-fluorophenoxy)acetato][4-(4-fluorophenoxy)acetato]dicaesium], [Cs2(C8H6FO3)2]n, (I), poly[aqua[5-(3-chloro-2-methylphenoxy)acetato]caesium], [Cs(C9H8ClO3)(H2O)]n, (II), and poly[[7-(2,4-di­chlorophenoxy)acetato][(2,4-dichlorphenoxy)acetic acid]caesium], [Cs(C8H5Cl2O3)(C8H6Cl2O3)]n, (III), are described. In (I), the Cs+ cations of the two individual irregular coordination polyhedra in the asymmetric unit (one CsO7 and the other CsO8) are linked by bridging carboxylate O-atom donors from the two ligand molecules, both of which are involved in bidentate chelate Ocarboxy,Ophenoxy interactions, while only one has a bidentate carboxylate O,O'-chelate inter­action. Polymeric extension is achieved through a number of carboxylate O-atom bridges, with a minimum CsCs separation of 4.3231 (9) Å, giving layers which lie parallel to (001). In hydrated complex (II), the irregular nine-coordination about the Cs+ cation comprises a single monodentate water molecule, a bidentate Ocarboxy,Ophenoxy chelate interaction and six bridging carboxylate O-atom bonding interactions, giving a CsCs separation of 4.2473 (3) Å. The water mol­ecule forms intralayer hydrogen bonds within the two-dimensional layers, which lie parallel to (100). In complex (III), the irregular centrosymmetric CsO6Cl2 coordination environment comprises two O-atom donors and two ring-substituted Cl-atom donors from two hydrogen bis[(2,4-dichlorophenoxy)acetate] ligand species in a bidentate chelate mode, and four O-atom donors from bridging carboxyl groups. The duplex ligand species lie across crystallographic inversion centres, linked through a short O-HO hydrogen bond involving the single acid H atom. Structure extension gives layers which lie parallel to (001). The present set of structures of Cs salts of phenoxyacetic acids show previously demonstrated trends among the alkali metal salts of simple benzoic acids with no stereochemically favourable interactive substituent groups for formation of two-dimensional coordination polymers.

Resolving cryptic species complexes of major tephritid pests

An FAO/IAEA Co-ordinated Research Project (CRP) on “Resolution of Cryptic Species Complexes of Tephritid Pests to Overcome Constraints to SIT Application and International Trade” was conducted from 2010 to 2015. As captured in the CRP title, the objective was to undertake targeted research into the systematics and diagnostics of taxonomically challenging fruit fly groups of economic importance. The scientific output was the accurate alignment of biological species with taxonomic names; which led to the applied outcome of assisting FAO and IAEA Member States in overcoming technical constraints to the application of the Sterile Insect Technique (SIT) against pest fruit flies and the facilitation of international agricultural trade. Close to 50 researchers from over 20 countries participated in the CRP, using coordinated, multidisciplinary research to address, within an integrative taxonomic framework, cryptic species complexes of major tephritid pests. The following progress was made for the four complexes selected and studied: Anastrepha fraterculus complex – Eight morphotypes and their geographic and ecological distributions in Latin America were defined. The morphotypes can be considered as distinct biological species on the basis of differences in karyotype, sexual incompatibility, post-mating isolation, cuticular hydrocarbon, pheromone, and molecular analyses. Discriminative taxonomic tools using linear and geometric morphometrics of both adult and larval morphology were developed for this complex. Bactrocera dorsalis complex – Based on genetic, cytogenetic, pheromonal, morphometric, and behavioural data, which showed no or only minor variation between the Asian/African pest fruit flies Bactrocera dorsalis, B. papayae, B. philippinensis and B. invadens, the latter three species were synonymized with B. dorsalis. Of the five target pest taxa studied, only B. dorsalis and B. carambolae remain as scientifically valid names. Molecular and pheromone markers are now available to distinguish B. dorsalis from B. carambolae. Ceratitis FAR Complex (C. fasciventris, C. anonae, C. rosa) – Morphology, morphometry, genetic, genomic, pheromone, cuticular hydrocarbon, ecology, behaviour, and developmental physiology data provide evidence for the existence of five different entities within this fruit fly complex from the African region. These are currently recognised as Ceratitis anonae, C. fasciventris (F1 and F2), C. rosa and a new species related to C. rosa (R2). The biological limits within C. fasciventris (i.e. F1 and F2) are not fully resolved. Microsatellites markers and morphological identification tools for the adult males of the five different FAR entities were developed based on male leg structures. Zeugodacus cucurbitae (formerly Bactrocera (Zeugodacus) cucurbitae) – Genetic variability was studied among melon fly populations throughout its geographic range in Africa and the Asia/Pacific region and found to be limited. Cross-mating studies indicated no incompatibility or sexual isolation. Host preference and genetic studies showed no evidence for the existence of host races. It was concluded that the melon fly does not represent a cryptic species complex, neither with regard to geographic distribution nor to host range. Nevertheless, the higher taxonomic classification under which this species had been placed, by the time the CRP was started, was found to be paraphyletic; as a result the subgenus Zeugodacus was elevated to genus level.

Resolution of Cryptic Species Complexes of Tephritid Pests to Enhance SIT Application and Facilitate International Trade

Tephritid fruit flies (Diptera: Tephritidae) are considered by far the most important group of horticultural pests worldwide. Female fruit flies lay eggs directly into ripening fruit, where the maggots feed causing fruit loss. Each and every continent is plagued by a number of fruit fly pests, both indigenous as well as invasive ones, causing tremendous economic losses. In addition to the direct losses through damage, they can negatively impact commodity trade through restrictions to market access. The quarantine and regulatory controls put in place to manage them are expensive, while the on-farm control costs and loss of crop affect the general well-being of growers. These constraints can have huge implications on loss in revenues and limitations to developing fruit and vegetable-based agroindustries in developing, emergent and developed nations. Because fruit flies are a global problem, the study of their biology and management requires significant international attention to overcome the hurdles they pose. The Joint Food and Agriculture Organisation / International Atomic Energy Agency (FAO/IAEA) Programme on Nuclear Techniques in Food and Agriculture has been on the foreground in assisting Member States in developing and validating environment-friendly fruit fly suppression systems to support viable fresh fruit and vegetable production and export industries. Such international attention has resulted in the successful development and validation of a Sterile Insect Technique (SIT) package for the Mediterranean fruit fly. Although demands for R&D support with respect to Mediterranean fruit fly are diminishing due to successful integration of this package into sustainable control programmes against this pest in many countries, there were increasing demands from Member States in Africa, Asia and Latin America, to address other major fruit fly pests and a related, but sometimes neglected issue of tephritid species complexes of economic importance. Any research, whether it is basic or applied, requires a taxonomic framework that provides reliable and universally recognized entities and names. Among the currently recognized major fruit fly pests, there are groups of species whose morphology is very similar or identical, but biologically they are distinct species. As such, some insect populations that are grouped taxonomically within the same pest species, display different biological and genetic traits and show reproductive isolation which suggest that they are different species. On the other hand, different species may have been taxonomically described, but there may be doubt as to whether they actually represent distinct biological species or merely geographical variants of the same species. This uncertain taxonomic status has practical implications on the effective development and use of the SIT against such complexes, particularly at the time of determining which species to mass-rear, and significantly affects international movement of fruit and vegetables through the establishment of trade barriers to important agricultural commodities which are hosts to these pest tephritid species...

Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

Plumbing systems of shallow level intrusive complexes

We have come a long way from simple straw and balloon models of magma plumbing systems to a more detailed picture of shallow level intrusive complexes. In this chapter, the sub-volcanic plumbing system is considered in terms of how we can define the types and styles of magma networks from the deep to the shallow subsurface. We look at the plumbing system from large igneous provinces, through rifted systems to polygenetic volcanoes, with a view to characterising some of the key conceptual models. There is a focus on how ancient magmatic centres can help us better understand magmatic plumbing. New innovative ways to consider and quantify magma plumbing are also highlighted including 3D seismic, and using the crystal cargo to help fingerprint key magma plumbing events. Conclusions are drawn to our understanding of the 3D plumbing system and how these recent advances can be helpful when exploring the other chapters of this contribution.