Multifunctional Dy Complexes with Triphenylmethanolates: Structural Diversity, Luminescence, and Magnetic Relaxation.

The coordination environment of magneto-luminescent Dy-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (PhCO), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear -[Dy(OCPh)(THF)][BPh]·(2,6-MeCHN) (), -Dy(OCPh)(THF) (), -Dy(OCPh)(py) () and dinuclear [(PhCO)Dy(THF){(μ-Cl)Li(THF)}μ-Cl] () complexes where the Dy ion presents five- or six-coordinate geometries.

Impact of Hydroxyapatite on Gelatin/Oxidized Alginate 3D-Printed Cryogel Scaffolds.

Fabrication of scaffolds via 3D printing is a promising approach for tissue engineering. In this study, we combined 3D printing with cryogenic crosslinking to create biocompatible gelatin/oxidized alginate (Gel/OxAlg) scaffolds with large pore sizes, beneficial for bone tissue regeneration. To enhance the osteogenic effects and mechanical properties of these scaffolds, we evaluated the impact of hydroxyapatite (HAp) on the rheological characteristics of the 2.

Luminescent Er based single molecule magnets with fluorinated alkoxide or aryloxide ligands.

We report the synthesis, structures, and magnetic and luminescence properties of a series of new mono- and dinuclear Er complexes derived from sterically demanding aryloxide and fluorinated alkoxide ligands: [4-Bu-2,6-(PhCH)CHO]Er(THF) (1), [(CF)CO]Er(MeSiOH) (2), [(CF)CO]Er[(MeSi)NH] (3), [(CF)CO]Er(CHCH) (4), [(CF)CO]Er(-MeNCHCH) (5) and {[Ph(CF)CO]Er(μ-OC(CF)Ph)} (6). In compounds 1, 2, and 4, the Er ion is four-coordinated and adopts a distorted trigonal pyramidal geometry, while in 3, 5, and 6, the coordination geometry of Er is impacted by the presence of several relatively short Er⋯F distances, making them rather 6-coordinated. All compounds behave as field-induced Single Molecule Magnets (SMMs) and exhibit an Er characteristic near infrared (NIR) emission associated with the I → I transition with a remarkably long lifetime going up to 73 μs, which makes them multifunctional luminescent SMMs.

Reasoning on Pore Terminology in 3D Bioprinting.

Terminology is pivotal for facilitating clear communication and minimizing ambiguity, especially in specialized fields such as chemistry. In materials science, a subset of chemistry, the term "pore" is traditionally linked to the International Union of Pure and Applied Chemistry (IUPAC) nomenclature, which categorizes pores into "micro", "meso", and "macro" based on size. However, applying this terminology in closely-related areas, such as 3D bioprinting, often leads to confusion owing to the lack of consensus on specific definitions and classifications tailored to each field.

Ca(II) and Yb(II) complexes featuring M(C≡C) structural motif: enforced proximity or genuine η -bonding?

Bis(carbazolide) complexes M[3,6-tBu -1,8-(RC≡C) Carb] (THF) (R=SiMe , n=0, M=Ca, Yb; R=Ph, n=1, M=Ca, Yb; n=0, M=Yb) were synthesized through transamination reaction of M[N(SiMe ) ] (THF) with two molar equivalents of carbazoles. The complexes feature M(η -C≡C) structural motif composed of M(II) ions encapsulated by four acetylene fragments due to atypical for alkaline- and rare-earth metals η -interactions with triple C≡C bond. This interaction is evidenced experimentally by X-ray diffraction, Raman spectroscopy in the solid state and by NMR-spectroscopy in the solution.

Dual-Crosslinking of Gelatin-Based Hydrogels: Promising Compositions for a 3D Printed Organotypic Bone Model.

Gelatin-based hydrogels have emerged as a popular scaffold material for tissue engineering applications. The introduction of variable crosslinking methods has shown promise for fabricating stable cell-laden scaffolds. In this work, we examine promising composite biopolymer-based inks for extrusion-based 3D bioprinting, using a dual crosslinking approach.

A self-powered ingestible wireless biosensing system for real-time in situ monitoring of gastrointestinal tract metabolites.

Information related to the diverse and dynamic metabolite composition of the small intestine is crucial for the diagnosis and treatment of various diseases. However, our current understanding of the physiochemical dynamics of metabolic processes within the small intestine is limited due to the lack of in situ access to the intestinal environment. Here, we report a demonstration of a battery-free ingestible biosensing system for monitoring metabolites in the small intestine.

-Heterocyclic Carbene-Coordinated M(II) (M = Yb, Sm, Ca) Bisamides: Expanding the Limits of Intermolecular Alkene Hydrophosphination.

A series of NHC-stabilized amido compounds (NHC)M[N(SiMe)] (M = Yb(II), Sm(II), Ca(II); = 1, 2) showed remarkable catalytic efficiency in addition of PhPH and PH to alkenes under mild conditions and low catalyst loading. The effect of σ-donor capacity of NHCs on catalytic activity in hydrophosphination of styrene with PhPH and PH was revealed. For the series of three-coordinate complexes , a tendency to increase the catalytic activity with growth of σ-donating strength of the carbene ligand was clearly demonstrated.

π-Carbazolyl supported bis(alkyl) complexes of Sc, Y and La for α-olefin polymerization and hydrogenation.

A series of new half-sandwich bis(alkyl) rare-earth metal complexes coordinated by a sterically demanding 1,3,6,8-tetra--butyl-carbazol-9-yl ligand [BuCarb]La(CHCH)(THF) (1-La), [BuCarb]Ln(-NMeCHCH) (Ln = Sc (2-Sc), Y (2-Y), La (2-La), [BuCarb]Ln(CHSiMe)(THF) (Ln = Sc (3-Sc), Y (3-Y)), were synthesized. 1-La, 2-La, and 2-Y were prepared by an alkane elimination protocol, while 2-Sc, 3-Sc, and 3-Y became accessible only when salt metathesis reactions of BuCarbK with RLn(THF)[BPh] were employed. X-ray analysis revealed that in all complexes the carbazolyl ligand exhibits π-coordination with metal ions.

Sc and Y bis(alkyl) complexes supported by bidentate and tridentate amidinate ligands. Synthesis, structure and catalytic activity in polymerization of isoprene and 1-heptene.

A series of bis(alkyl) complexes {(Bu)C[N(2,6-MeCH)]}Ln(CHSiMe)(THF) (Ln = Y, = 1 (1); Ln = Sc, = 1 (2)), {2-[PhP(O)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (3), {2-[PhP(NPh)]CHNC(Bu)N(2,6-MeCH)}Sc(CHSiMe) (4) coordinated by bidentate (N,N) and tridentate (N,N,O; N,N,N) amidinate ligands are synthesized using an alkane elimination approach. Yttrium complex 1 demonstrated a half-life of ∼2.5 days at room temperature in benzene-D6 (CD) solution, whereas scandium complexes proved to be much more stable (25 d (2), 30 d (3) and 42 d (4)).

2-Imino-2,3-dihydrobenzoxazole-a useful platform for designing rare- and alkaline earth complexes with variable di- and trianionic O,N,N, ligands.

The reactions of 2-imino-2,3-dihydrobenzoxazole LH with M[N(SiMe)](THF) (M = Yb and Ca) and Y(CHSiMe)(THF) proceed with the opening of the dihydrobenzoxazole ring and the elimination of HN(SiMe) or SiMe. Besides, in the case of Yb[N(SiMe)](THF), an electron transfer from Yb(II) to L takes place and Yb(III) complex 1 is coordinated by a dianionic phenolate ligand containing a pendant radical-anionic diazabutadiene fragment form. When LH is reacted with Ca[N(SiMe)](THF), C-H bond activation of a methyl fragment by imino nitrogen occurs and affords a dimeric calcium complex 2.

Using N-Heterocyclic Carbenes as Weak Equatorial Ligands to Design Single-Molecule Magnets: Zero-Field Slow Relaxation in Two Octahedral Dysprosium(III) Complexes.

We report the synthesis, structures, and magnetic investigations of two new octahedral dysprosium complexes, based on the original N-heterocyclic carbene (NHC) tridentate bis(phenoxide) ligand, of the respective formulas -[DyL(THF)Cl] () and -[DyL(THF)][BPh] (), where L = 1,3-bis(3,5-di--butyl-2-oxidophenyl)-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium chloride and THF = tetrahydrofuran. The short Dy-O distances in the axial direction in association with the weak donor ability of the NHC moiety provide a suitable environment for slow relaxation of magnetization, overcoming the previous single-molecule magnets based on NHC ligands.

Amine-boranes reactions promoted by lanthanide(II) ions.

The catalytic activity in amine-borane dehydrogenation is shown for the first time for Ln(II) species using complexes [{(Bu-CH)CH}M·L] (M = Yb, Sm, L = (DME), TMEDA). The protonation of M(II)-C bonds with HNRRBH affords amidoborane complexes [M(NRRBH)L], which under excess HNMeBH transform to [NMeBHNMeBH] derivatives, both serving as the dehydrocoupling intermediates.

High magnetization reversal barriers in luminescent dysprosium octahedral and pentagonal bipyramidal single-molecule magnets based on fluorinated alkoxide ligands.

We report the synthesis and structures of three luminescent dysprosium(iii) complexes based on fluorinated alkoxide ligands of formulas [Dy(L1)2(THF)4][BPh4]·0.5THF (1), [Dy(L2)2(THF)5][BPh4]·2.5THF (2) and [Dy(L3)2(THF)5][BPh4]·2THF (3) (L1 = (CF3)3CO-, L2 = C6F5C6F4O-, L3 = C6F5C(CH3)O-).

Ln(II) amido complexes coordinated by ring-expanded N-heterocyclic carbenes - promising catalysts for olefin hydrophosphination.

First Ln(ii) ring-expanded NHC complexes (er-NHC)Ln[N(SiMe3)2]2 (Ln = Sm, Yb) are synthesized and proved to be highly efficient pre-catalysts for the intermolecular hydrophosphination of such indolent substrates as 1-alkenes, cyclohexene and norbornene.

Carbon-coated magnetic nanoparticles as a removable protection layer extending the operation lifetime of bilirubin oxidase-based bioelectrode.

One of the factors hindering the development of enzymatic biosensors and biofuel cells in real-life applications is the time-dependant degradation of the biocatalysts on electrode surfaces. In this work, we present a new practical approach for extending the operation lifetimes of bioelectrocatalytic assemblies based on bilirubin oxidase (BOD). As evident by both spectroscopic and electrochemical measurements, an adsorption of carbon-coated magnetic nanoparticles (ccMNPs) onto a BOD/carbon nanotubes-deposited surface yields a stable bioelectrocathode system for mediatorless oxygen reduction.

Single-molecule magnet behavior in heterolopetic Dy-chloro-diazabutadiene complexes: influence of the nuclearity and ligand redox state.

We report the synthesis, structure and magnetic properties investigations of a series of new dysprosium heteroleptic mono- and dinuclear complexes based on the association of chloride and different diazabutadiene (DAD2R = [2,6-iPr2C6H3N-CR[double bond, length as m-dash]CR-NC6H3iPr2-2,6]; R = H, Me) ligands showing different redox states. While using dianionic DAD2R ligands affords the formation of dichloro-bridged dinuclear complexes [Dy2(DAD2R)(μ-Cl)2(THF)2] (R = H (1), Me (2)), two different mononuclear complexes of general formula [DyCl2(DAD2R)(THF)2] (R = H (3), Me (4)) could be obtained with either a radical monoanionic and a monoanionic DAD2R state, respectively. Remarkably, all the complexes exhibit a slow relaxation of their magnetization where the relaxation dynamics depends on both the nuclearity of the system and the DAD2R redox state.

Synthesis, Structure, Magnetic and Photoluminescent Properties of Dysprosium(III) Schiff Base Single-Molecule Magnets: Investigation of the Relaxation of the Magnetization.

We report here the synthesis, structure, magnetic and photoluminescent properties of three new bifunctional Schiff-base complexes [Dy(L ) (py) ][B(Ph) ]⋅py (1), [Dy(L ) Cl(DME)] ⋅ 0.5DME (2) and [Dy(L ) Cl] ⋅ 2.5(C H ) (3) (HL =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxy-5-methylphenyl)imino]methyl]; HL =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxyphenyl)imino]methyl]).

Single-molecule magnet behavior in luminescent carbazolyl Dy(iii) octahedral complexes with a quasi linear N-Dy-N angle.

We report the synthesis, photoluminescence and magnetic properties of two octahedral dysprosium complexes [DyR2(py)4][BPh4]·2py (1) and [DyR2(THF)4][BPh4] (2) (R = carbazolyl, py = pyridine, THF = tetrahydrofuran) exhibiting a quasi linear N-Dy-N angle in the axial direction, suitable for providing a coordination environment allowing the zero-field slow relaxation of magnetization.

Synthesis, structure and magnetic properties of a series of Ln(iii) complexes with radical-anionic iminopyridine ligands: effect of lanthanide ions on the slow relaxation of the magnetization.

We report the investigation of synthesis, structure and magnetic properties of a series of homoleptic Ln(iii) complexes coordinated by radical-anionic iminopyridine ligands of general formula [Ln(IPy)]·solv (IPy = iminopyridine; Ln = Tb, Dy, Er, Y, Gd). The dysprosium analogue exhibits a zero-field Single-Molecule Magnet (SMM) behavior.

Power Generation by Selective Self-Assembly of Biocatalysts.

Through a careful chemical and bioelectronic design we have created a system that uses self-assembly of enzyme-nanoparticle hybrids to yield bioelectrocatalytic functionality and to enable the harnessing of electrical power from biomass. Here we show that mixed populations of hybrids acting as catalyst carriers for clean energy production can be efficiently stored, self-assembled on functionalized stationary surfaces, and magnetically re-collected to make the binding sites on the surfaces available again. The methodology is based on selective interactions occurring between chemically modified surfaces and ligand-functionalized hybrids.

Alternative (κ-N:η-arene vs.κ-N,N) coordination of a sterically demanding amidinate ligand: are size and electronic structure of the Ln ion decisive factors?

The amine elimination reaction of equimolar amounts of ansa-bis(amidine) CH-1,2-{NC(tBu)NH(2,6-iPrCH)} (LH) and [(MeSi)N]Yb(THF) affords a bis(amidinate) Yb complex [CH-1,2-{NC(tBu)N(2,6-iPrCH)}]Yb(THF) (1) in 68% yield. Complex 1 features a rather rare η-amido:η-arene coordination of both amidinate fragments to the Yb ion, resulting in the formation of a bent bis(arene) structure. Oxidation of 1 by I regardless of the molar ratio of reagents (2 : 1 or 1 : 1) leads to the formation of the Yb species [{(2,6-iPrCH)[double bond, length as m-dash]NC(tBu)NH}-CH-1,2-{NC(tBu)N(2,6-iPrCH)}]YbI(THF) (2) in which only one amidinate fragment is coordinated to the ytterbium ion in κ-N,N'-chelating coordination mode, while the second NCN fragment is protonated in the course of the reaction and is not bound to the metal ion.

Correction: Amido Ca(ii) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes.

Correction for 'Amido Ca(ii) complexes supported by Schiff base ligands for catalytic cross-dehydrogenative coupling of amines with silanes' by Natalia V. Forosenko et al., Dalton Trans.

Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C-C Multiple Bonds.

A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [( p- tBu-CH)CH]M(L ) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by the salt-metathesis reaction of MI(THF) ( n = 0-2) and [( p- tBu-CH)CH]Na. In complex 1, the benzhydryl ligands are bound to the metal center in η-coordination mode. Unlike complex 1, in isomorphous complexes 3 and 4, due to the coordination unsaturation of the metal center, the both benzhydryl ligands coordinate to the metal in η-fashion.

Single-molecule magnet behaviour in a Dy(iii) pentagonal bipyramidal complex with a quasi-linear Cl-Dy-Cl sequence.

We report the synthesis and magnetic investigation of a dysprosium pentagonal bipyramidal complex [Dy(THF)5Cl2][BPh4] (1) exhibiting a linear Cl-Dy-Cl sequence suitable for providing a coordination environment allowing a zero-field slow relaxation of the magnetization. Besides, the complex also shows dual luminescence originating from [BPh4]- and Dy3+.