Crafting mono- and novel bis-methylated pyrroloquinoxaline derivatives from a shared precursor and its application in the total synthesis of marinoquinoline A.

The synthesis of mono- and novel bis-methylated pyrrolo[1,2-a]quinoxalines through the addition of unstable methyl radicals to aryl isocyanides is described contingent upon the reaction conditions employed. The strategy has been effectively employed in the total synthesis of the natural product marinoquinoline A.

Engineering of Microcage Carbon Nanotube Architectures with Decoupled Multimodal Porosity and Amplified Catalytic Performance.

New approaches for the engineering of the 3D microstructure, pore modality, and chemical functionality of hierarchically porous nanocarbon assemblies are key to develop the next generation of functional aerogel and membrane materials. Here, interfacially driven assembly of carbon nanotubes (CNT) is exploited to fabricate structurally directed aerogels with highly controlled internal architectures, composed of pseudo-monolayer, CNT microcages. CNT Pickering emulsions enable engineering at fundamentally different length scales, whereby the microporosity, mesoporosity, and macroporosity are decoupled and individually controlled through CNT type, CNT number density, and process energy, respectively. In addition, metal nanocatalysts (Cu, Pd, and Ru) are embedded within the architectures through an elegant sublimation and shock-decomposition approach; introducing the first approach that enables through-volume functionalization of intricate, pre-designed aerogels without microstructural degradation. Catalytic structure-function relationships are explored in a pharma-important amidation reaction; providing insights on how the engineered frameworks enhance catalyst activity. A sophisticated array of advanced tomographic, spectroscopic, and microscopic techniques reveal an intricate 3D assembly of CNT building-blocks and their influence on the functional properties of the enhanced nanocatalysts. These advances set a basis to modulate structure and chemistry of functional aerogel materials independently in a controlled fashion for a variety of applications, including energy conversion and storage, smart electronics, and (electro)catalysis.

A new large species of Bitis Gray, 1842 (Serpentes: Viperidae) from the Bale Mountains of Ethiopia.

A new species of viperine viperid snake is described, Bitis harenna sp. nov. The new species is a member of the subgenus Macrocerastes based on it having three scales separating the nasal and rostral shields, and on the combination of 'divisions' of dorsal scale rows on the upper flanks and 'fusions' of rows on the lower flanks. Bitis harenna sp. nov. is distinguished from other members of the subgenus by its unique colour pattern, posterior parietal flange on the lateral wall of the braincase, and possibly by differences in scalation and head proportions. Only a single museum specimen is known, a female collected from 'Dodola' in Ethiopia probably in the late 1960s and previously identified as a possibly unusually coloured and patterned B. parviocula. A live, presumably male, specimen very closely resembling the holotype of Bitis harenna sp. nov. was photographed on the Harenna escarpment of the Bale Mountains National Park, Ethiopia in 2013, providing secure occurrence data and evidence that the holotype is not a uniquely aberrant specimen. A revised key to the species of Bitis in Ethiopia is presented. Aspects of body scalation are compared among species of the subgenus Macrocerastes and between species of Macrocerastes and Bitis, and several systematic characters are highlighted and clarified.

X-ray micro-computed tomography in willow reveals tissue patterning of reaction wood and delay in programmed cell death.

BACKGROUND: Variation in the reaction wood (RW) response has been shown to be a principle component driving differences in lignocellulosic sugar yield from the bioenergy crop willow. The phenotypic cause(s) behind these differences in sugar yield, beyond their common elicitor, however, remain unclear. Here we use X-ray micro-computed tomography (µCT) to investigate RW-associated alterations in secondary xylem tissue patterning in three dimensions (3D). RESULTS: Major architectural alterations were successfully quantified in 3D and attributed to RW induction. Whilst the frequency of vessels was reduced in tension wood tissue (TW), the total vessel volume was significantly increased. Interestingly, a delay in programmed-cell-death (PCD) associated with TW was also clearly observed and readily quantified by µCT. CONCLUSIONS: The surprising degree to which the volume of vessels was increased illustrates the substantial xylem tissue remodelling involved in reaction wood formation. The remodelling suggests an important physiological compromise between structural and hydraulic architecture necessary for extensive alteration of biomass and helps to demonstrate the power of improving our perspective of cell and tissue architecture. The precise observation of xylem tissue development and quantification of the extent of delay in PCD provides a valuable and exciting insight into this bioenergy crop trait.

Combined two-photon excitation and d→f energy transfer in a water-soluble Ir(III)/Eu(III) dyad: two luminescence components from one molecule for cellular imaging.

The first example of cell imaging using two independent emission components from a dinuclear d/f complex is reported. A water-stable, cell-permeable Ir(III) /Eu(III) dyad undergoes partial Ir→Eu energy transfer following two-photon excitation of the Ir unit at 780 nm. Excitation in the near-IR region generated simultaneously green Ir-based emission and red Eu-based emission from the same probe. The orders-of-magnitude difference in their timescales (Ir ca. µs; Eu ca. 0.5 ms) allowed them to be identified by time-gated detection. Phosphorescence lifetime imaging microscopy (PLIM) allowed the lifetime of the Ir-based emission to be measured in different parts of the cell. At the same time, the cells are simultaneously imaged by using the Eu-based emission component at longer timescales. This new approach to cellular imaging by using dual d/f emitters should therefore enable autofluorescence-free sensing of two different analytes, independently, simultaneously and in the same regions of a cell.

Sensitisation of Eu(III)- and Tb(III)-based luminescence by Ir(III) units in Ir/lanthanide dyads: evidence for parallel energy-transfer and electron-transfer based mechanisms.

A series of blue-luminescent Ir(III) complexes with a pendant binding site for lanthanide(III) ions has been synthesized and used to prepare Ir(III)/Ln(III) dyads (Ln = Eu, Tb, Gd). Photophysical studies were used to establish mechanisms of Ir→Ln (Ln = Tb, Eu) energy-transfer. In the Ir/Gd dyads, where direct Ir→Gd energy-transfer is not possible, significant quenching of Ir-based luminescence nonetheless occurred; this can be ascribed to photoinduced electron-transfer from the photo-excited Ir unit (*Ir, (3)MLCT/(3)LC excited state) to the pendant pyrazolyl-pyridine site which becomes a good electron-acceptor when coordinated to an electropositive Gd(III) centre. This electron transfer quenches the Ir-based luminescence, leading to formation of a charge-separated {Ir(4+)}˙-(pyrazolyl-pyridine)˙(-) state, which is short-lived possibly due to fast back electron-transfer (<20 ns). In the Ir/Tb and Ir/Eu dyads this electron-transfer pathway is again operative and leads to sensitisation of Eu-based and Tb-based emission using the energy liberated from the back electron-transfer process. In addition direct Dexter-type Ir→Ln (Ln = Tb, Eu) energy-transfer occurs on a similar timescale, meaning that there are two parallel mechanisms by which excitation energy can be transferred from *Ir to the Eu/Tb centre. Time-resolved luminescence measurements on the sensitised Eu-based emission showed both fast and slow rise-time components, associated with the PET-based and Dexter-based energy-transfer mechanisms respectively. In the Ir/Tb dyads, the Ir→Tb energy-transfer is only just thermodynamically favourable, leading to rapid Tb→Ir thermally-activated back energy-transfer and non-radiative deactivation to an extent that depends on the precise energy gap between the *Ir and Tb-based (5)D4 states. Thus, the sensitised Tb(iii)-based emission is weak and unusually short-lived due to back energy transfer, but nonetheless represents rare examples of Tb(III) sensitisation by a energy donor that could be excited using visible light as opposed to the usually required UV excitation.

Using remote substituents to control solution structure and anion binding in lanthanide complexes.

A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space. Peripheral modifications to a binuclear lanthanide motif derived from α,α'-bis(DO3 Ayl)-m-xylene are shown to result in dramatic changes to the binding constant for isophthalate. In this system, the parent compound displays considerable conformational flexibility, yet can be assumed to bind to isophthalate through a well-defined conformer. Addition of steric bulk remote from the binding site restricts conformational mobility, giving rise to an increase in binding constant on entropic grounds as long as the ideal binding conformation is not excluded from the available range of conformers.

d→f energy transfer in Ir(III)/Eu(III) dyads: use of a naphthyl spacer as a spatial and energetic "stepping stone".

A series of luminescent complexes based on {Ir(phpy)2} (phpy = cyclometallating anion of 2-phenylpyridine) or {Ir(F2phpy)2} [F2phpy = cyclometallating anion of 2-(2',4'-difluorophenyl)pyridine] units, with an additional 3-(2-pyridyl)-pyrazole (pypz) ligand, have been prepared; fluorination of the phenylpyridine ligands results in a blue-shift of the usual (3)MLCT/(3)LC luminescence of the Ir unit from 477 to 455 nm. These complexes have pendant from the coordinated pyrazolyl ring an additional chelating 3-(2-pyridyl)-pyrazole unit, separated via a flexible chain containing a naphthalene-1,4-diyl or naphthalene-1,5-diyl spacer. Crystal structures show that the flexibility of the pendant chain allows the naphthyl group to lie close to the Ir core and participate in a π-stacking interaction with a coordinated phpy or F2phpy ligand. Luminescence spectra show that, whereas the {Ir(phpy)2(pypz)} complexes show typical Ir-based emission--albeit with lengthened lifetimes because of interaction with the stacked naphthyl group--the {Ir(F2phpy)2(pypz)} complexes are nearly quenched. This is because the higher energy of the Ir-based (3)MLCT/(3)LC excited state can now be quenched by the adjacent naphthyl group to form a long-lived naphthyl-centered triplet ((3)nap) state which is detectable by transient absorption. Coordination of an {Eu(hfac)3} unit (hfac = 1,1,1,5,5,5-hexafluoro-pentane-2,4-dionate) to the pendant pypz binding site affords Ir-naphthyl-Eu triads. For the triads containing a {Ir(phpy)2} core, the unavailability of the (3)nap state (not populated by the Ir-based excited state which is too low in energy) means that direct Ir→Eu energy-transfer occurs in the same way as in other flexible Ir/Eu complexes. However for the triads based on the{Ir(F2phpy)2} core, the initial Ir→(3)nap energy-transfer step is followed by a second, slower, (3)nap→Eu energy-transfer step: transient absorption measurements clearly show the (3)nap state being sensitized by the Ir center (synchronous Ir-based decay and (3)nap rise-time) and then transferring its energy to the Eu center (synchronous (3)nap decay and Eu-based emission rise time). Thus the (3)nap state, which is energetically intermediate in the {Ir(F2phpy)2}-naphthyl-Eu systems, can act as a "stepping stone" for two-step d→f energy-transfer.

Cu12 and Cd16 coordination cages and their Cu3 and Cd3 subcomponents, and the role of inter-ligand π-stacking in stabilising cage complexes.

The bridging ligand L(14Nap), which contains two chelating pyrazolyl-pyridine units separated by a naphthalene-1,4-diyl spacer, has been used in self-assembly of polyhedral coordination cages. The largest such cage is [Cd16(L(14Nap))24](BF4)32 which has a tetra-capped truncated tetrahedral Cd16 core with a bridging ligand spanning every edge. The complex is indefinitely stable in dilute solution, which makes it quite different from the previously-reported isostructural cage [Cd16(L(14Ph))24](BF4)32 (based on a 1,4-phenyl bridge) that forms on crystallisation but slowly rearranges to smaller cages in solution. The additional inter-ligand π-stacking between ligand fragments associated with replacement of a phenyl group by a naphthyl group allows the complex to be stable in solution, providing conclusive proof of the importance of inter-ligand π-stacking in the assembly of these cages. With Cu(II) in place of Cd(II) a smaller cage [Cu12(L(14Nap))15](ClO4)24 was formed which contains a mixture of tris-chelated (six-coordinate) and bis-chelated (four-coordinate, or five-coordinate if an additional monodentate ligand is present) Cu(II) ions; the difference between the two structures arises in part from the different stereoelectronic preferences of the two metal ions. Despite this difference both the Cd16 and Cu12 cages contain {M3(L(14Nap))3}(6+) triangular helical units as subcomponents which form the triangular faces of the polyhedra. By using a 1 : 1 ligand : metal ratio in the synthesis examples of these can be isolated and characterised; the structures of the trinuclear cyclic helicates [Cd3(L(14Nap))3(BF4)4(EtOAc)2](BF4)2 and [Cu3(L(14Nap))3(BF4)(MeCN)2](BF4)5 have also been determined.

Combined two-photon excitation and d → f energy-transfer in Ir/lanthanide dyads with time-gated selection from a two-component emission spectrum.

In a pair of Ir/Eu and Ir/Tb dyads, two-photon excitation of the Ir-phenylpyridine chromophore at 780 nm is followed by partial d → f energy-transfer to give a combination of short-lived Ir-based (blue) and long-lived lanthanide-based (red or green) emission; these components can be selected separately by time-gated detection.

d → f energy transfer in a series of Ir(III)/Eu(III) dyads: energy-transfer mechanisms and white-light emission.

An extensive series of blue-luminescent iridium(III) complexes has been prepared containing two phenylpyridine-type ligands and one ligand containing two pyrazolylpyridine units, of which one is bound to Ir(III) and the second is pendant. Attachment of {Ln(hfac)(3)} (Ln = Eu, Gd; hfac = anion of 1,1,1,5,5,5,-hexafluoropentanedione) to the second coordination site affords Ir(III)/Ln(III) dyads. Crystallographic analysis of several mononuclear iridium(III) complexes and one Ir(III)/Eu(III) dyad reveals that in most cases the complexes can adopt a folded conformation involving aromatic π stacking between a phenylpyridine ligand and the bis(pyrazolylpyridine) ligand, but in one series, based on CF(3)-substituted phenylpyridine ligands coordinated to Ir(III), the steric bulk of the CF(3) group prevents this and a quite different and more open conformation arises. Quantum mechanical calculations well reproduce these two types of "folded" and "open" conformations. In the Ir(III)/Eu(III) dyads, Ir → Eu energy transfer occurs with varying degrees of efficiency, resulting in partial quenching of the Ir(III)-based blue emission and the appearance of a sensitized red emission from Eu(III). Calculations based on consideration of spectroscopic overlap integrals rule out any significant contribution from Förster (dipole-dipole) energy transfer over the distances involved but indicate that Dexter-type (exchange) energy transfer is possible if there is a small electronic coupling that would arise, in part, through π stacking between components. In some cases, an initial photoinduced electron-transfer step could also contribute to Ir → Eu energy transfer, as shown by studies on isostructural iridium/gadolinium model complexes. A balance between the blue (Ir-based) and red (Eu-based) emission components can generate white light.

Lanthanide complexes of DOTA monoamide derivatives bearing an isophthalate pendent arm.

An isophthalate-bearing DOTA monoamide derivative has been synthesised and used to prepare a family of lanthanide complexes. Luminescence and NMR studies in solution show that the predominant form of the complexes in solution is a mono-capped square antiprism about the lanthanide centre, in which a solvent molecule occupies the ninth coordination site. The crystal structure of the terbium complex is presented and is in close agreement with the solution state data.

Visible-light sensitisation of Tb(III) luminescence using a blue-emitting Ir(III) complex as energy-donor.

In Ir(III)/Tb(III) dyads in which the excited state energy of the Ir(III) unit lies above 22,000 cm(-1), visible-light excitation of the Ir(III) chromophore results in sensitised emission from Tb(III) following Ir → Tb energy-transfer.

Iridium(III) luminophores as energy donors for sensitised emission from lanthanides in the visible and near-infrared regions.

Luminescent iridium(iii) complex units bearing pendant 2,2'-bipyridyl-type binding sites can be used to generate Ir/Ln dyads in which the Ir(iii) luminophore acts as an energy donor to the lanthanide by the Dexter mechanism, generating sensitised emission in the visible (from Eu) or near-infrared (Nd, Yb) regions.

Synthesis and spectroscopic studies on azo-dye derivatives of polymetallic lanthanide complexes: using diazotization to link metal complexes together.

Heteronuclear tetrametallic lanthanide complexes have been synthesized from stable complexes by diazotization and azo-compound formation. Luminescence spectroscopy has been used to show that the complexes used as building blocks are stable under the reaction conditions.

Sensitised luminescence in lanthanide containing arrays and d-f hybrids.

Sensitised luminescence from lanthanide complexes offers many potential advantages in imaging and assay, particularly when coupled with time-gating protocols that can be used to gate out background signal. In this perspective, we discuss the routes by which lanthanide arrays and polymetallic d-f hybrids can be prepared by conventional synthesis and self-assembly, and discuss and evaluate the possibilities for exploiting and evaluating the intermediates in the sensitisation process, with particular emphasis on the mechanisms of energy transfer.

[Ru(bipy)(3)](2+) and [Os(bipy)(3)](2+) chromophores as sensitisers for near-infrared luminescence from Yb(iii) and Nd(iii) in d/f dyads: contributions from Förster, Dexter, and redox-based energy-transfer mechanisms.

The complexes and contain [M(bipy)(3)](2+) chromophores with a pendant aza-18-crown-6 macrocycle for binding of lanthanide(iii) ions. The photophysical properties of the adducts . and ., prepared by addition of excess Ln(NO(3))(3) (Ln = Nd, Yb) to solutions of and in MeCN, were examined using time-resolved and steady-state luminescence methods. Whereas does not act as an energy-donor to Yb(iii), it will transfer energy to (and generate sensitised near-infrared luminescence from) Nd(iii) with a Ru(ii)-->Nd(iii) energy-transfer rate constant of 6.8 x 10(6) s(-1). In contrast, is quenched by both Yb(iii) and Nd(iii), but with faster energy-transfer to Yb(iii) (2.6 x 10(7) s(-1)) than to Nd(iii) (1.4 x 10(7) s(-1)). Thus d --> f energy transfer is in both cases faster for Os(ii) than for Ru(ii), but the relative ability of Nd(iii) and Yb(iii) to act as energy-acceptors is inverted from . to .. Reasons for this are discussed with reference to contributions from the Förster and Dexter mechanism for energy-transfer in . and ., using calculated spectroscopic overlap integrals coupled with molecular modelling to estimate inter-chromophore separations. The particular effectiveness of Os(ii) --> Yb(iii) energy-transfer in . is explained in terms of the Horrocks redox mechanism involving an initial *Os(ii) --> Yb(iii) photoinduced electron transfer step generating an Os(iii)/Yb(ii) state, which is shown to be marginally favourable for ., but not for . in which the [Ru(bipy)(3)](2+) unit is a poorer excited-state electron-donor by about 0.1 eV.

Using the Ugi multicomponent condensation reaction to prepare families of chromophore appended azamacrocycles and their complexes.

The Ugi reaction offers an effective method for preparing chromophore-appended DOTA-monoamide ligands, which can readily be elaborated to their lanthanide complexes.

On the mechanism of d-f energy transfer in RuII/LnIII and OsII/LnIII dyads: Dexter-type energy transfer over a distance of 20 A.

We have used time-resolved luminescence methods to study rates of photoinduced energy transfer (PEnT) from [M(bipy)3]2+ (M=Ru, Os) chromophores to Ln(III) ions with low-energy f-f states (Ln=Yb, Nd, Er) in d-f dyads in which the metal fragments are separated by a saturated -CH2CH2- spacer, a p-C6H4 spacer, or a p-(C6H4)2 spacer. The finding that d-->f PEnT is much faster across a conjugated p-C6H4 spacer than it is across a shorter CH2CH2 spacer points unequivocally to a Dexter-type energy transfer, involving electronic coupling mediated by the bridging ligand orbitals (superexchange) as the dominant mechanism. Comparison of the distance dependence of the Ru-->Nd energy-transfer rate across different conjugated spacers [p-C6H4 or p-(C6H4)2 groups] is also consistent with this mechanism. Observation of Ru-->Nd PEnT (as demonstrated by partial quenching of the RuII-based 3MLCT emission (MLCT=metal-to-ligand charge transfer), and the growth of sensitised NdIII-based emission at 1050 nm) over approximately 20 A by an exchange mechanism is a departure from the normal situation with lanthanides, in which long-range energy transfer often involves through-space Coulombic mechanisms.

Heteronuclear bipyrimidine-bridged Ru-Ln and Os-Ln dyads: low-energy 3MLCT states as energy-donors to Yb(III) and Nd(III).

The complexes [Ru((t)Bu(2)bipy)(bpym)X(2)] (X = Cl, NCS) and [M((t)Bu(2)bipy)(2)(bpym)][PF(6)](2) (M = Ru, Os) all have a low-energy LUMO arising from the presence of a 2,2'-bipyrimidine ligand, and consequently have lower-energy (1)MLCT and (3)MLCT states than analogous complexes of bipyridine. The vacant site of the bpym ligand provides a site at which [Ln(diketonate)(3)] units can bind to afford bipyrimidine-bridged dinuclear Ru-Ln and Os-Ln dyads; four such complexes have been structurally characterised. UV/Vis and luminescence spectroscopic studies show that binding of the Ln(III) fragment at the second site of the bpym ligand reduces the (3)MLCT energy of the Ru or Os fragment still further. The result is that in the dyads [Ru((t)Bu(2)bipy)X(2)(mu-bpym)Ln(diketonate)(3)] (X = Cl, NCS) and [Os((t)Bu(2)bipy)(2)(mu-bpym)Ln(diketonate)(3)][PF(6)](2) the (3)MLCT is too low to sensitise the luminescent f-f states of Nd(III) and Yb(III), but in [Ru((t)Bu(2)bipy)(2)(mu-bpym)Ln(diketonate)(3)][PF(6)](2) the (3)MLCT energy of 13,500 cm(-1) permits energy transfer to Yb(III) and Nd(III) resulting in sensitised near-infrared luminescence on the microsecond timescale.