Environmental influence on the functional ecological structure of benthic macrofaunal communities of the northwest Iberian coast.

Evaluating the functional structure of benthic macrofaunal communities provides insights into how environmental drivers shape the ecosystem and establishes a baseline knowledge of the communities' dynamics and functioning. This understanding allows the prediction of responses to environmental changes and the implementation of efficient conservation and management strategies. Here we examine the structures and functions of benthic macrofaunal communities on the Northwest Iberian coast concerning environmental factors such as depth, hydrodynamic energy, and bottom type.

Unveiling the role of taxonomic sufficiency for enhanced ecosystem monitoring.

The use of Artificial substrates (AS) as sampling devices addresses challenges in macrofaunal quantitative sampling. While effectively capturing biodiversity patterns, the time-intensitive identification process at the species level remains a substantial challenge. The Taxonomic Sufficiency approach (TS), where only taxa above species level are identified, arises as a potential solution to be tested across different environmental monitoring scenarios.

Assessing the Seasonal and Spatial Dynamics of Zooplankton through DNA Metabarcoding in a Temperate Estuary.

Zooplankton are key components of estuarine trophic networks. However, routine monitoring is hindered by the difficulty of morphology-based identification. DNA-based methods allow us to circumvent some of these hurdles, providing precise species identifications regardless of the taxonomic expertise of the investigator or the developmental stage of the specimens.

New copper(I) complexes of bulky 5-substituted-2-iminopyrrolyl ligands as catalysts for azide-alkyne cycloaddition.

Five dinuclear copper(I) complexes of the type [Cu{κ,κ'-5-R-NCH-2-C(H)N(2,6-iPrCH)}] (1a-e; R = 2,4,6-iPrCH (a), R = 2,6-MeCH (b), R = 3,5-(CF)CH (c), R = 2,6-(OMe)CH (d), R = CPh (e)) were prepared by the reaction of the respective 5-R-2-iminopyrrolyl potassium salts KLa-e and [Cu(NCMe)]BF in moderate yields. These new copper(I) complexes were characterized by NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X-ray diffraction and their structural and electronic features further analyzed by DFT calculations and cyclic voltammetry, respectively. X-ray diffraction studies reveal dimeric Cu structures assembled by 2-iminopyrrolyl bridging ligands adopting a transoid conformation (complexes 1a and 1d), while complexes 1c and 1e displayed a cisoid conformation of those moieties, with respect to the Cu(I) centers.

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of F- and Cl-substituted 8-quinolinolato ligands: synthesis, molecular and electronic structures, fluorescence and application in OLED devices.

Six new four-coordinate tetrahedral boron complexes, containing 9-borafluoren-9-yl and diphenylboron cores attached to orthogonal fluorine- and chlorine-substituted 8-quinolinolato ligand chromophores, have been synthesised, characterised, and applied as emitters in organic light-emitting diodes (OLEDs). An extensive steady-state and time-resolved photophysical study, in solution and in the solid state, resulted in the first-time report of delayed fluorescence (DF) in solid films of 8-quinolinolato boron complexes. The DF intensity dependence on excitation dose suggests that this emission originates from triplet-triplet annihilation (TTA).

Enhancing SIM behaviour in a mononuclear tetrahedral [Co(,'-2-iminopyrrolyl)] complex.

A new homoleptic Co(II) complex bearing two highly sterically congested 2-formiminopyrrolyl ,'-chelating ligands is reported, displaying slow relaxation of the magnetisation at zero static (DC) field. This compound shows a large value for the zero-field splitting (ZFS) parameter of -42.6(4) cm leading to a spin-reversal energy barrier of 85 cm.

Hydrosilylation of Aldehydes and Ketones Catalyzed by a 2-Iminopyrrolyl Alkyl-Manganese(II) Complex.

A well-defined and very active single-component manganese(II) catalyst system for the hydrosilylation of aldehydes and ketones is presented. First, the reaction of 5-(2,4,6-PrCH)-2-[-(2,6-PrCH)formimino]pyrrolyl potassium () and [MnCl(Py)] afforded the binuclear 2-iminopyrrolyl manganese(II) pyridine chloride complex [Mn{κ,-5-(2,4,6-PrCH)-NCH-2-C(H)═N(2,6-PrCH)}(Py)(μ-Cl)] . Subsequently, the alkylation reaction of complex with LiCHSiMe afforded the respective (trimethylsilyl)methyl-Mn(II) complex [Mn{κ,-5-(2,4,6-PrCH)-NCH-2-C(H)═N(2,6-PrCH)}(Py)CHSiMe] in a good yield.

Two better than one: The complementary of different types of artificial substrates on benthic marine macrofauna studies.

Non-destructive methodologies based on the use of artificial substrates (AS) for quantitative sampling of macrofauna have been used to solve sampling problems in complex benthic environment, such as rocky reefs. The macrofauna assemblages of two different types of AS (dendritic and crevice), at two different locations were studied. The main goal was to evaluate the complementarity of dendritic and crevice AS when sampling the macrofauna associated with rocky environments, in two scenarios: within the same location and between locations.

Luminescent halogen-substituted 2-(N-arylimino)pyrrolyl boron complexes: the internal heavy-atom effect.

A group of new boron complexes [BPh{κN,N'-NCH-2-C(H)[double bond, length as m-dash]N-CHX}] (X = 4-Cl 4c, 4-Br 4d, 4-I 4e, 3-Br 4f, 2-Br 4g, 2-I 4h) containing different halogens as substituents in the N-aryl ring have been synthesized and characterized in terms of their molecular properties. Their photophysical characteristics have been thoroughly studied in order to understand whether these complexes exhibit an internal heavy-atom effect. Phosphorescence emission was found for some of the synthesized halogen-substituted boron molecules, particularly for 4g and 4h.

Boron complexes of aromatic 5-substituted iminopyrrolyl ligands: synthesis, structure, and luminescence properties.

A group of new mononuclear boron chelate compounds [BPh{κN,N'-5-R-NCH-2-C(H)[double bond, length as m-dash]N-Ar}] (R = Ar = CH7; R = CH, Ar = 2,6-iPrCH8; R = Anthracen-9-yl (Anthr), Ar = CH9; R = Anthr, Ar = 2,6-iPrCH10) were synthesized via the reaction of B(CH) with the corresponding 5-substituted 2-(N-arylformimino)pyrrole ligand precursors 3-6. These complexes were prepared in order to evaluate the luminescence potential derived from the substitution of the position 5 of the pyrrolyl ring with an aromatic group. Compounds 7-10 were photophysically characterized in solution and in the solid state.

Synthesis and Characterization of Isosorbide-Based Polyurethanes Exhibiting Low Cytotoxicity Towards HaCaT Human Skin Cells.

The synthesis of four samples of new polyurethanes was evaluated by changing the ratio of the diol monomers used, poly(propylene glycol) (PPG) and D-isosorbide, in the presence of aliphatic isocyanates such as the isophorone diisocyanate (IPDI) and 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI). The thermal properties of the four polymers obtained were determined by DSC, exhibiting values in the range 55⁻70 °C, and their molecular structure characterized by FTIR, ¹H, and C NMR spectroscopies. The diffusion coefficients of these polymers in solution were measured by the Pulse Gradient Spin Echo (PGSE) NMR method, enabling the calculation of the corresponding hydrodynamic radii in diluted solution (1.

Cobalt(I) Complexes of 5-Aryl-2-iminopyrrolyl Ligands: Synthesis, Spin Isomerism, and Application in Catalytic Hydroboration.

This work reports the first successful isolation and full characterization of cobalt(I) complexes of 5-aryl-2-iminopyrrolyl ligands. In one approach, when [Co{κ N,N'-5-(2,4,6-R-CH)-NCH-2-C(H)═N(2,6-Pr-CH)}(Py)Cl] (R = Pr, 1a; R = Ph, 1b) were reacted with K(HBEt) or Na(Hg) in toluene, the Co(I) arene complexes [Co{κ N,N'-5-(2,4,6-Pr-CH)-NCH-2-C(H)═N(2,6-Pr-CH)}(η-CHCH)] (2a) and [ Co{κ N,N'-5-[2'-(κ:η- CH)-CH-4',6'-Ph]-NCH-2-C(H)═N(2,6-Pr-CH)}] (2b) were formed. The reaction of complex 1a with KC in EtO yielded the [Co{κ N,N'-5-(2,4,6-Pr-CH)-NCH-2-C(H)═N(2,6-Pr-CH)}] (3).

New phenyl-nickel complexes of bulky 2-iminopyrrolyl chelates: synthesis, characterisation and application as aluminium-free catalysts for the production of hyperbranched polyethylene.

A family of mono(2-iminopyrrolyl) complexes with the general formula [Ni{κ2N,N'-5-(aryl)-NC4H2-2-C(H)[double bond, length as m-dash]N-2,6-(aryl)}(C6H5)(PPh3)] were obtained from the reaction of the sodium salts of the newly synthesised 5-aryl-2-(N-arylformimino)pyrroles with the square planar complex trans-[Ni(C6H5)(PPh3)2Cl]. These new iminopyrrole ligand precursors, designed with increasing bulkiness and different electronic properties, and their corresponding nickel(ii) complexes were characterised by NMR spectroscopy and elemental analysis, and their structural features were analysed by single crystal X-ray diffraction. The nickel complexes were tested as aluminium-free catalysts for the polymerisation of ethylene, at low to moderate pressures and different temperatures and in the absence or presence of the phosphine scavenger [Ni(COD)2], giving rise to catalytic activities in the range of 3.

Hydroboration of Terminal Olefins with Pinacolborane Catalyzed by New Mono(2-Iminopyrrolyl) Cobalt(II) Complexes.

The 5-substituted 2-aryliminopyrrolyl ligand precursors of the type 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]-1 H-pyrrole (R = 2,6-Me-CH (1a), 2,4,6-Pr-CH (1b), 2,4,6-Ph-CH (1c; reported in this work), anthracen-9-yl (1d), CPh (1e; reported in this work)) were treated with K[N(SiMe)] in toluene to yield the respective 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]pyrrolyl potassium salts 2a-e in high yields. The paramagnetic 15-electron Co(II) complexes of the type [Co{κ N,N'-5-R-NCH-2-C(H)═N(2,6-Pr-CH)}(Py)Cl] (3a-e; Py = pyridine) were prepared by salt metathesis of CoCl(Py) with the respective potassium salts 2a-e in moderate to good yields. When the CoCl(THF) precursor was combined with the in situ prepared sodium salt of ligand precursor 1b, the trinuclear complex [Co{κ N, N'-5-(2,4,6-Pr-CH)-NCH-2-C(H)═N(2,6-Pr-CH)}(μ-Cl)][(μ-Cl)Co(THF)] (4) was obtained in high yields.

ILs through the looking glass: electrostatics and structure probed using charge-inverted ionic liquid pairs.

Ionic liquids combining potassium cations with 1-alkyl-3-methylcyclopentadienyl anions, K[CCCp] (n = 4, 6) have been synthesized. Differential scanning calorimetry measurements have shown that K[CCCp] and K[CCCp] melt without decomposition at around 90 °C. These two ionic liquids are the charge-inverted counterparts of [CCIm]Cl and [CCIm]Cl, two common ionic liquids.

Boron complexes of aromatic ring fused iminopyrrolyl ligands: synthesis, structure, and luminescence properties.

The condensation reactions of 2-formylindole (1) or 2-formylphenanthro[9,10-c]pyrrole (2) with various aromatic amines afforded the corresponding phenyl or phenanthrene ring fused mono-/bis-iminopyrrole ligand precursors 3-8, which, upon reaction with BPh in an appropriate molar ratio, led to the new mono- and diboron chelate compounds PhB[NCHC(H)[double bond, length as m-dash]N-2,6-Ar] (Ar = 2,6-iPrCH9; CH10), PhB[(NCHC(H)[double bond, length as m-dash]N)-1,4-CH]BPh11, PhB(NCHC(H)[double bond, length as m-dash]N-Ar) (Ar = 2,6-iPrCH12; CH13), and PhB[(NCHC(H)[double bond, length as m-dash]N)-1,4-CH]BPh14, respectively. Boron complexes 12-14, containing a phenanthrene fragment fused to the pyrrolyl C3-C4 bond, are highly fluorescent in solution, with quantum efficiencies of 37%, 61% and 58% (in THF), respectively, their emission colours ranging from blue to orange depending on the extension of π-conjugation. Complexes 9-11, containing a benzene fragment fused to the pyrrolyl C4-C5 bond, are much weaker emitters, exhibiting quantum efficiencies of 10%, 7% and 6%, respectively.

First examples of neutral and cationic indenyl nickel(II) complexes bearing arsine or stibine ligands: highly active catalysts for the oligomerisation of styrene.

New indenyl nickel(ii) complexes bearing arsine or stibine ligands synthesised by a new methodology exhibit very high catalytic activities for the oligomerisation of styrene.

Starting a DNA barcode reference library for shallow water polychaetes from the southern European Atlantic coast.

Annelid polychaetes have been seldom the focus of dedicated DNA barcoding studies, despite their ecological relevance and often dominance, particularly in soft-bottom estuarine and coastal marine ecosystems. Here, we report the first assessment of the performance of DNA barcodes in the discrimination of shallow water polychaete species from the southern European Atlantic coast, focusing on specimens collected in estuaries and coastal ecosystems of Portugal. We analysed cytochrome oxidase I DNA barcodes (COI-5P) from 164 specimens, which were assigned to 51 morphospecies.

Luminescent Di- and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis, Characterization, and Application in OLEDs.

New bis- and tris(iminopyrrole)-functionalized linear (1,2-(HNC4 H3 -C(H)N)2 -C6 H4 (2), 1,3-(HNC4 H3 -C(H)N)2 -C6 H4 (3), 1,4-(HNC4 H3 -C(H)N)2 -C6 H4 (4), 4,4'-(HNC4 H3 -C(H)N)2 -(C6 H4 -C6 H4 ) (5), 1,5-(HNC4 H3 C-(H)N)2 -C10 H6 (6), 2,6-(HNC4 H3 C-(H)N)2 -C10 H6 (7), 2,6-(HNC4 H3 C-(H)N)2 -C14 H8 (8)) and star-shaped (1,3,5-(HNC4 H3 -C(H)N-1,4-C6 H4 )3 -C6 H3 (9)) π-conjugated molecules were synthesized by the condensation reactions of 2-formylpyrrole (1) with several aromatic di- and triamines. The corresponding linear diboron chelate complexes (Ph2 B[1,3-bis(iminopyrrolyl)-phenyl]BPh2 (10), Ph2 B[1,4-bis(iminopyrrolyl)-phenyl]BPh2 (11), Ph2 B[4,4'-bis(iminopyrrolyl)-biphenyl]BPh2 (12), Ph2 B[1,5-bis(iminopyrrolyl)-naphthyl]BPh2 (13), Ph2 B[2,6-bis(iminopyrrolyl)-naphthyl]BPh2 (14), Ph2 B[2,6-bis(iminopyrrolyl)-anthracenyl]BPh2 (15)) and the star-shaped triboron complex ([4',4'',4'''-tris(iminopyrrolyl)-1,3,5-triphenylbenzene](BPh2 )3 (16)) were obtained in moderate to good yields, by the treatment of 3-9 with B(C6 H5 )3 . The ligand precursors are non-emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π-conjugation length.

Copper(II) complexes of bis(aryl-imino)acenaphthene ligands: synthesis, structure, DFT studies and evaluation in reverse ATRP of styrene.

Two new Ar-BIAN Cu(II) complexes (where Ar-BIAN = bis(aryl-imino)acenaphthene) of formulations [CuCl2(Mes-BIAN)] (1) (Mes = 2,4,6-Me3C6H2) and [CuCl2(Dipp-BIAN)] (2) (Dipp = 2,6-iPr2C6H3) were synthesised by direct reaction of CuCl2 suspended in dichloromethane with the respective ligands Mes-BIAN (L1) and Dipp-BIAN (L2), dissolved in dichloromethane, under an argon atmosphere. Attempts to obtain these compounds by solubilising CuCl2 in methanol and adding a dichloromethane solution of the corresponding ligand, under aerobic conditions, gave also compound 1, but, in the case of L2, the Cu(I) dimer [CuCl(Dipp-BIAN)]2 (3) was obtained instead of compound 2. The compounds were fully characterised by elemental analyses, MALDI-TOF mass spectrometry, FT-IR, (1)H NMR and EPR spectroscopic techniques.

Tunable fluorophores based on 2-(N-arylimino)pyrrolyl chelates of diphenylboron: synthesis, structure, photophysical characterization, and application in OLEDs.

Reactions of 2-(N-arylimino)pyrroles (HNC4H3C(H)=N-Ar) with triphenylboron (BPh3) in boiling toluene afford the respective highly emissive N,N'-boron chelate complexes, [BPh2 {κ(2)N,N'-NC4H3C(H)=N-Ar}] (Ar=C6H5 (12), 2,6-Me2-C6H3 (13), 2,6-iPr2-C6H3 (14), 4-OMe-C6H4 (15), 3,4-Me2-C6 H3 (16), 4-F-C6H4 (17), 4-NO2-C6H4 (18), 4-CN-C6H4 (19), 3,4,5-F3-C6H2 (20), and C6F5 (21)) in moderate to high yields. The photophysical properties of these new boron complexes largely depend on the substituents present on the aryl rings of their N-arylimino moieties. The complexes bearing electron-withdrawing aniline substituents 17-20 show more intense (e.

Photophysical properties of iminopyrrolyl boron complexes: a DFT interpretation.

The three compounds [BPh(2)(κ(2)N,N'-NC(4)H(3)C(H)=N-C(6)H(5))] (A), [BPh(2)(κ(2)N,N'-NC(4)H(3)C(H)=N-1,4-C(6)H(4)-N=H)C-H(3)C(4)N-N,N'κ(2))BPh(2)] (B) and [BPh(2)(κ(2)N,N'-NC(4)H(3)C(H)=N-4,4'-C(6)H(4)-C(6)H(4)-N=(H)C-H(3)C(4)N-N,N'κ(2))BPh(2)] (C) are blue to green light emitters with average to excellent quantum yields. DFT and TD-DFT calculations were performed in order to understand their behaviour. The geometry of their ground and singlet excited state was optimised, and their absorption patterns and emission were calculated.

Syntheses and photophysical properties of new iminopyrrolyl boron complexes and their application in efficient single-layer non-doped OLEDs prepared by spin coating.

Efficient non-doped OLEDs have been achieved using new binuclear tetracoordinate organoboron complexes containing 2-(N-aryl)formiminopyrrolyl ligands.

Synthesis and structural characterisation of (aryl-BIAN)copper(I) complexes and their application as catalysts for the cycloaddition of azides and alkynes.

A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine) were synthesised and characterised by (1)H and (13)C NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula [Cu(Ar-BIAN)(2)]BF(4) (where Ar = C(6)H(5) (1), 4-iPrC(6)H(4) (3), 2-iPrC(6)H(4) (4)) were prepared by reaction of [Cu(NCMe)(4)]BF(4) with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type [Cu(Ar-BIAN)L(2)]BF(4) (where Ar = 2,6-iPr(2)C(6)H(3), L = PhCN (6); Ar = 4-iPrC(6)H(4), L = PPh(3) (7)) were readily accessible by treatment of [Cu(NCR)(4)]BF(4) (R = Me, Ph) with one equivalent of the corresponding Ar-BIAN ligands in the absence or presence of two equivalents of PPh(3), in the same solvent. The structures of complexes 3, 4, 6 and 7 were obtained by single crystal X-ray diffraction, showing distorted tetrahedral geometries around the copper centres in all cases.

Iminopyrrole derivatives containing electron-withdrawing substituents: the formation of dimers and supramolecular arrangements.

The crystal structures of two p-substituted phenylformiminopyrrole derivatives, namely 2-[(4-fluorophenyl)iminomethyl]pyrrole, C(11)H(9)FN(2), (1), and 2-[(1H-pyrrol-2-ylmethylidene)amino]benzonitrile, C(12)H(9)N(3), (2), bear F and C[triple-bond]N electron-withdrawing groups, respectively. Both structures feature two independent molecules in the asymmetric unit forming dimers via N-H..