New talent: Americas, 2020
Welcome to the New Talent: Americas themed issue of Dalton Transactions, guest edited by Ana Maria Da Costa Ferreira, Neal Mankad and Georgii Nikonov.
Evaluating aqueous flow battery electrolytes: a coordinated approach
Here, we outline some basic pitfalls in the electrochemical investigation of aqueous metal complexes, advocate for the use of bulk electrolysis in redox flow cells for electrolyte analysis, and demonstrate methods of operation and performance of a lab scale redox flow battery.
In need of a second-hand? The second coordination sphere of ruthenium complexes enables water oxidation with improved catalytic activity
A ligand dangling arm, acting as an intramolecular proton acceptor, drastically increasing the catalytic activity of Ru-complexes for water oxidation.
What is holding back the development of antiviral metallodrugs? A literature overview and implications for SARS-CoV-2 therapeutics and future viral outbreaks
Despite a significative classical literature, metallodrugs have struggled to reach clinical practice. In light of the COVID-19 outbreak, this review aims at further encouraging and promoting the development of metallodrugs as viable antiviral agents.
A bioinorganic chemistry perspective on the roles of metals as drugs and targets against Mycobacterium tuberculosis – a journey of opportunities
Bioinorganic approaches in developing metallodrugs for tuberculosis are discussed, along with our understanding of key metalloproteins with drug target opportunities.
The chemical and physical properties of tetravalent lanthanides: Pr, Nd, Tb, and Dy
The thermochemistry, descriptive chemistry, spectroscopy, and physical properties of the tetravalent lanthanides (Pr, Nd, Tb and Dy) in extended phases, gas phase, solution, and as isolable molecular complexes are presented.
Synthesis of atomically precise single-crystalline Ru2-based coordination polymers
Metallopolymerization of kinetically inert Ru2 metallomonomers via construction of Ag–N bonds provides access to atomically precise single-crystalline Ru2-based coordination polymers with varied network topology and primary coordination sphere.
Squeezing Bi: PNP and P2N3 pincer complexes of bismuth
Stable neutral and highly-reactive cationic Bi complexes featuring NNN and PNP pincer ligands are debuted.
Systematically altering the lipophilicity of rhenium(I) tricarbonyl anticancer agents to tune the rate at which they induce cell death
Increasing the lipophilicity of rhenium-based anticancer agents increases the rate at which they induce their biological effects.
Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure
Strong C–O bonds in pyrone and coumarin esters can undergo oxidative addition to Pd(0), with the reaction conditions and substrate structure controlling the outcome.
Alkali-metal- and halide-free dinuclear mixed-valent samarium and europium complexes
The synthesis of alkali metal- and halide-free mixed valent dilanthanide complexes supported by a calixpyrrole ligand is described. Bond activation using both a base and one-electron reductant is showcased.
Bis(pentafluorophenyl)phenothiazylborane – an intramolecular frustrated Lewis pair catalyst for stannane dehydrocoupling
A Lewis acidic aminoborane (1) was shown to catalytically dehydrocouple stannanes through an unexpected heterolytic frustrated Lewis pair mechanism rather than a homolytic process.
P-Alkynyl functionalized benzazaphospholes as transmetalating agents
Exposure of 10π-electron benzazaphosphole 1 to HCl, followed by nucleophilic substitution with the Grignard reagent BrMgCCPh afforded alkynyl functionalized 3 featuring an exocyclic –CC–Ph group with an elongated P–C bond (1.7932(19) Å).
Electrochemical, mechanistic, and DFT studies of amine derived diphosphines containing Ru(II)–cymene complexes with potent in vitro cytotoxic activity against HeLa and triple-negative breast cancer cells MDA-MB-231
Electrochemical/chemical, cytotoxic and DNA interaction studies of P–NR–P containing ruthenium–cymene complexes [RuCl(η6-p-cymene)(P–NR–P)]X.
Electrocatalytic water oxidation reaction promoted by cobalt-Prussian blue and its thermal decomposition product under mild conditions
Water oxidation studies with Co-Prussian blue and Co3O4. Figure adapted from ‘Under the Wave off Kanagawa’ (Kanagawa oki nami ura), also known as ‘The Great Wave’, from the series ‘Thirty-six Views of Mount Fuji’ (‘Fugaku sanjūrokkei’) by K. Hokusai.
Inorganic clusters as metalloligands: ligand effects on the synthesis and properties of ternary nanopropeller clusters
Subtle stereoelectronic changes of the surface capping ligands have long-ranging consequences in the synthesis and chemistry of ternary transition metal selenide clusters.
Silver(I) complexes of 3-methoxy-4-hydroxybenzaldehyde thiosemicarbazones and triphenylphosphine: structural, cytotoxicity, and apoptotic studies
Cytotoxic silver(I) complex triggers mitochondrial dysfunction and induces apoptosis in the MDA-MB-231 cells.
Origin of the 29Si NMR chemical shift in R3Si–X and relationship to the formation of silylium (R3Si+) ions
The origin in deshielding of 29Si NMR chemical shifts in R3Si–X, where X = H, OMe, Cl, OTf, [CH6B11X6], toluene, and OX (OX = surface oxygen), as well as iPr3Si+ and Mes3Si+ were studied using DFT methods.
Anticancer and antitrypanosomal activities of trinuclear ruthenium compounds with orthometalated phenazine ligands
Four metalo-intercalators ([Ru3(μ3-O)(μ2-OAc)5(L)(py)2]PF6, L = phenazines) present high DNA intercalation constants and high HSA affinity. They are active against melanoma cancer and T. Cruzi parasite.
Mononuclear lanthanide(III)-oxamate complexes as new photoluminescent field-induced single-molecule magnets: solid-state photophysical and magnetic properties
Lanthanide(III)-oxamate complexes can switch into Light Conversion Molecular Devices (LCMDs) or field-induced Single-Molecule Magnets (SMMs) depending on the external stimulus.
Responsive fluorinated nanoemulsions for 19F magnetic resonance detection of cellular hypoxia
A highly fluorinated Cu2+ complex for 19F MR sensing of cellular hypoxia as nanoemulsion formulations.
Investigation of cobalt(III)–phenylalanine complexes for hypoxia-activated drug delivery
L-Phenylalanine (L-Phe) was used as a ligand model for the anticancer drug melphalan. CoIII–Phe complexes were successfully designed for hypoxia-selective release of L-Phe from CoIII–Phe upon Co3+/Co2+ reduction by ascorbic acid.
Robust Mn(III) N-pyridylporphyrin-based biomimetic catalysts for hydrocarbon oxidations: heterogenization on non-functionalized silica gel versus chloropropyl-functionalized silica gel
Simple neutral and cationic Mn porphyrins were immobilized on ordinary chromatographic silica or chloropropyl-functionalized silica supports to yield efficient and reusable biomimetic catalysts for C–H activation and oxyfunctionalization of alkanes.
A novel green approach based on ZnO nanoparticles and polysaccharides for photocatalytic performance
Novel green photocatalysts based on ZnO in the presence of arabic gum (AGZ) or karaya gum (KGZ) were synthesized by a sol–gel method for photocatalytic performance.
EXAFS investigations of temperature-dependent structure in cobalt-59 molecular NMR thermometers
EXAFS spectroscopy was used to study the temperature-dependent molecular structures of a series of cobalt-59 NMR thermometers.
Transmembrane Cu(I) P-type ATPase pumps are electrogenic uniporters
Real-time transport analyses define transmembrane Cu(I)-pumps as electrogenic uniporters.
Abnormal co-doping effect on the red persistent luminescence SrS:Eu2+,RE3+ materials
Rapidly prepared SrS:Eu2+,RE3+ exhibits long red persistent luminescence independent of the rare earth co-dopant due to a high Schottky defect concentration.
Spectroscopic characterization of a new Re(I) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications
A novel Re(I) complex with a thiosemicarbazone derivative is described and fully characterized. Its was further explored as CO2 reduction electrocatalyst, being the first complex with a thiosemicarbazone derivative applied to this goal.
Heterometallic trinuclear oxo-centered clusters as single-source precursors for synthesis of stoichiometric monodisperse transition metal ferrite nanocrystals
Solvothermal reactions of MIIFe2III(μ3-O)(μ2-O2CR)6(H2O)3 (R = CF3, M = Fe, Co, Ni, Cu, Zn) clusters produce monodisperse, phase-pure MFe2O4 nanocrystals.
Novel syntheses of carbazole-3,6-dicarboxylate ligands and their utilization for porous coordination cages
A benzyl-protecting strategy affords access to large quantities of carbazole-based ligands or molecular adsorbents with tunable inter-cage interactions.
Synthesis, characterization, and electrochemical properties of a first-row metal phthalocyanine series
A first-row metal phthalocyanine series is synthesized and the effects of axial metal-ligand substitution is investigated electrochemically and in the context of charge carriers for redox-flow batteries.
Determining the coordination environment and electronic structure of polymer-encapsulated cobalt phthalocyanine under electrocatalytic CO2 reduction conditions using in situ X-Ray absorption spectroscopy
In situ X-ray absorbance spectroscopy measurements show that encapsulating cobalt phthalocyanine within coordinating polymers leads to axial ligation of Co and results in enhanced rates for electrocatalytic CO2 reduction.
Sulfur transfer reactions of a zinc tetrasulfanido complex
The sulfur transfer reactions of a zinc tetrasulfanido complex are explored and contrasted with those of metal polysulfidos.
The leaving group in Au(I)–phosphine compounds dictates cytotoxic pathways in CEM leukemia cells and reactivity towards a Cys2His2 model zinc finger
The leaving group L in [(R3P)AuL]n+ regulates the cytotoxic mechanism against CEM leukemia cells and the reactivity towards Sp1 ZnF3.
X1INH, an improved next-generation affinity-optimized hydrazonic ligand, attenuates abnormal copper(I)/copper(II)-α-Syn interactions and affects protein aggregation in a cellular model of synucleinopathy
By tuning the copper(I)/copper(II) affinity of a novel N-acylhydrazone, a more soluble, hydrolysis resistant and less toxic improved Metal–Protein Attenuating Compound for the bioinorganic management of metal-enhanced aggregopathies was obtained.
Platinum complexes of a boron-rich diphosphine ligand
Herein, we describe the preparation, characterization, and reactivity of two PtII bis-hydrocarbyl complexes containing the 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P2BCy4) ligand.
Photophysical, photodynamical, redox properties and BSA interactions of novel isomeric tetracationic peripheral palladium(II)-bipyridyl porphyrins
Exploring photophysical/ROS species of Pd(II)-porphyrins.
Spin-frustration with two quasi-degenerated spin states of a copper(II) heptanuclear complex obtained from an amino acid ligand
A Cu(II) heptanuclear complex, Cu7atac, synthesized from an amino acid ligand showed to be an antiferromagnetic spin-frustrated bis-triangular system. Cu7atac might be a promising qubit candidate for quantum information storage.
Self-assembled gold nanoparticles and amphiphile peptides: a colorimetric probe for copper(II) ion detection
We show that arginine/phenylalanine based peptides can be used to control the aggregation of gold nanoparticles in different ways. The arrangement provides a colorimetric approach to detect Cu2+ ions in water.
Rapid mechanochemical synthesis of metal–organic frameworks using exogenous organic base
We describe the mechanochemical, solvent-free synthesis of metal–organic frameworks using liquid organic base for the first time.
Photoinduced electron transfer dynamics of AuNPs and Au@PdNPs supported on graphene oxide probed by dark-field hyperspectral microscopy
The time scale for interfacial photoinduced electron transfer (PeT) in plasmonic nanoparticles is not well established and the details are still under debate.
A hemilabile manganese(I)–phenol complex and its coordination induced O–H bond weakening
Synthesis and characterization of [(HPO)(PO)Mn(CO)2 (H1), a phenol bound first-row transition metal complex, is reported. Thermochemical analysis of H1 indicated the presence of coordination induced O–H bond weakening.
Water dispersible ligand-free rare earth fluoride nanoparticles: water transfer versus NaREF4-to-REF3 phase transformation
Crystalline phase and rare-earth (RE) ion choice were identified as key parameters for NaREF4-to-REF3 phase transformation versus water transfer during ligand removal from small NaREF4 nanoparticles at low pH.
Identification of key functionalization species in the Cp*Ir(III)-catalyzed-ortho halogenation of benzamides
Cp*Ir(III) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source.
Site-selective halogenation of mixed-valent vanadium oxide clusters
Here, we expand on the synthesis and characterization of chloride-functionalized polyoxovanadate-alkoxide (POV-alkoxide) clusters, to include the halogenation of mixed-valent vanadium oxide assemblies.
Ru(II)-Naphthoquinone complexes with high selectivity for triple-negative breast cancer
Ru(II)/lapachol complex shows significant selectivity for triple negative breast cancer (TNBC) compared to the non-tumor human breast epithelial cell line.
Zn-Templated synthesis of substituted (2,6-diimine)pyridine proligands and evaluation of their iron complexes as anolytes for flow battery applications
Zn2+ templating enables synthesis of redox ‘non-innocent’ diimine pyridine ligands with strong electron-withdrawing groups, allowing construction of iron complexes with multiple ligand-based reductions for application in redox flow batteries.
A molecular boron cluster-based chromophore with dual emission
Bromination of the luminescent borane, anti-B18H22, via electrophilic substitution using AlCl3 and Br2, yields the monosubstituted derivative 4-Br-anti-B18H21 as an air-stable crystalline solid.
Understanding the photophysical properties of rhenium(I) compounds coordinated to 4,7-diamine-1,10-phenanthroline: synthetic, luminescence and biological studies
The photophysical properties of fac-[Re(L)(Am2phen)(CO)3]0/+ provided new insights into excited-state deactivation through an unusual inversion between two MLCT excited states.
Evaluation of cobalt complexes with tripod ligands for zinc finger targeting
We report the ability of CoII and CoIII complexes of tri(2-pyridylmethyl)amine and N,N-di(2-pyridylmethyl)glycinate to disrupt zinc fingers.
Tunable carbocation-based redox active ambiphilic ligands: synthesis, coordination and characterization
Synthesis of carbenium-based ligands that are ambiphilic, redox active, and easily tunable along with their coordination to Co(II) and Ni(II).
Reductive halocyclosilazane polymerization
The synthesis and polymerization of a chloroformed-functionalized six-membered cyclosilazane (Si5N) is reported.
Altering the optoelectronic properties of boron difluoride formazanate dyes via conjugation with platinum(II)-acetylides
The absorption, emission, and electrochemical properties of conjugates of boron difluoride formazanate dyes and Pt(II)-acetylides are systematically studied.
Azo-triazolide bis-cyclometalated Ir(III) complexes via cyclization of 3-cyanodiarylformazanate ligands
Sterically encumbered iridium-bound formazanate ligands undergo redox-neutral cyclization to form azo-triazolides, a new class of redox-active chelating ligand.
About this collection
This themed issue aims to reflect the strength and vitality of inorganic chemistry in the Americas and is guest-edited by Professors Georgii Nikonov (Brock University, Canada), Neal Mankad (University of Illinois at Chicago, USA), and Ana Maria da Costa Ferreira (University of São Paulo, Brazil). Emerging new talent from across the Americas is showcased from a broad spectrum of inorganic chemistry and highlights new perspectives on the subject.