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In this work, the dithiolene complex iron(III) bis-maleonitriledithiolene [Fe(mnt) 2 ] is characterised and evaluated as a homogeneous CO 2 reduction catalyst. Electrochemically the Fe(mnt) 2 is reduced twice to the trianionic Fe(mnt) 2 3- state, which is correspondingly found to be active towards CO 2 . Interestingly, the first reduction event appears to comprise overlapping reversible couples, attributed to the presence of both a dimeric and monomeric form of the dithiolene complex. In acetonitrile Fe(mnt) 2 demonstrates a catalytic response to CO 2 yielding typical two-electron reduction products: H 2 , CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H 2 O as the proton source gave only H 2 and CO as products, whereas using 2,2,2-trifluoroethanol gave 38 % CHOOH faradaic efficiency with H 2 and CO as minor products., Competing Interests: The authors declare no conflict of interest., (© 2022 The Authors. ChemElectroChem published by Wiley-VCH GmbH.)

Four new, symmetrical, bis-bidentate ditopic Rdpt-type, Rat (R azine-triazole), ligands have been prepared, Lnpym-meta/para (n = 2 or 4), which contain bidentate n-pyrimidine/triazole binding pockets connected through an appropriate aromatic spacer, meta/para-phenyl, to enable assembly into dinuclear helicates or tetranuclear tetrahedral cages, respectively. The 3 : 2 self assembly reactions of each Lnpym-meta/para ligand with iron(ii) tetrafluoroborate gave the desired complexes, as shown by X-ray crystal structure determinations of the pair of helicates [FeII2(Lnpym-meta)3(BF4)4]·6CH3CN, with n = 2 (1·6CH3CN) or 4 (2·6CH3CN), and the pair of Td cages [FeII4(Lnpym-para)6(BF4)8]·xsolvent, with n = 2 (3·xsolvent) or 4 (4·xsolvent). Reversible FeII/III processes at Em = 0.95 ± 0.05 V vs. 0.01 M AgNO3/Ag in MeCN are a feature of 1-4, with little variation in the redox potential as a function of nuclearity, architecture or choice of n-pyrimidine isomer. In all four complexes the iron(ii) centres are low spin, despite having employed the weakest field diazines, the 2- and 4-pyrimidines, in these ditopic Rat ligands. Nevertheless this is an exciting proof of principle that Rdpt-type ligands (previously used to generate about 50 spin crossover-active complexes) can be extended into ditopic forms that are suitable for supramolecular assembly of helicates and cages.

Five metal complexes of the dithiolene ligand maleonitriledithiolate (mnt 2- ) with M=V, Fe, Co, Ni, Cu were studied as redox-active materials for nonaqueous redox flow batteries (RFBs). All five complexes exhibit at least two redox processes, making them applicable to symmetric RFBs as single-species electrolytes, that is, as both negolyte and posolyte. Charge-discharge cycling in a small-scale RFB gave modest performances for [(tea) 2 V mnt ], [(tea) 2 Co mnt ], and [(tea) 2 Cu mnt ] whereas [(tea)Fe mnt ] and [(tea) 2 Ni mnt ] (tea=tetraethylammonium) failed to hold any significant capacity, indicating poor stability. Independent negolyte- and posolyte-only battery cycling of a single redox couple, as well as UV/Vis spectroscopy, showed that for [(tea) 2 V mnt ] the negolyte is stable whereas the posolyte is unstable over multiple charge-discharge cycles; for [(tea) 2 Co mnt ], [(tea) 2 Ni mnt ], and [(tea) 2 Cu mnt ], the negolyte suffers rapid capacity fading although the posolyte is more robust. Identifying a means to stabilize V mnt 3-/2- as a negolyte, and Co mnt 2-/1- , Ni mnt 2-/1- , and Cu mnt 2-/1- as posolytes could lead to their use in asymmetric RFBs., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A family of five easily prepared tridentate monoanionic 2,5-dipyridyl-3-(R 1 )-4-(R 2 )-pyrrolide anions (dpp R1,R2 ) - , varying in the nature of the R 1 and R 2 substituents [R 1 , R 2 = CN, Ph; CO 2 Et, CO 2 Et; CO 2 Me, 4-Py; CO 2 Me, Me; Me, Me], has been used to generate the analogous family of neutral [Co II (dpp R1,R2 ) 2 ] complexes, two of which are structurally characterized at both 100 and 298 K. Both the oxidation and spin states of these complexes can be switched in response to appropriate external stimuli. All complexes, except [Co II (dpp Me,Me ) 2 ], exhibit gradual spin crossover (SCO) in the solid state, and SCO activity is observed for three complexes in CDCl 3 solution. The cobalt(II) centers in the low spin (LS) complexes are Jahn-Teller tetragonally compressed along the pyrrolide-Co-pyrrolide axis. The complexes in their high spin (HS) states are more distorted than in the LS states, as is also usually the case for SCO active iron(II) complexes. The reversible Co III/II redox potentials are predictably tuned by choice of substituents R 1 and R 2 , from -0.95 (Me,Me) to -0.45 (CN,Ph) V vs Fc + /Fc, with a linear correlation observed between E 1 / 2 (Co III/II ) and the Swain-Lupton parameters of the pyrrolide substituents.

Iron(ii) spin crossover (SCO) materials have been widely studied as molecular switches with a wide variety of potential applications, including as displays, sensors, actuators or memory components. Most SCO materials have been either monometallic or polymeric, and it is only relatively recently that chemists have really started to focus on linking multiple metal centres together within the one, discrete, molecule in an effort to enhance the SCO properties, such as abrupt, hysteretic, and multistep switching, as well as the potential for quantum cellular automata, whilst still being readily amenable to characterisation. Here we present a review of the ligand designs of the last two decades that have led to self assembly of discrete di- to poly-nuclear iron(ii) complexes of helicate, cage, cube, and other supramolecular architectures with rich SCO activity, and to an increased focus on host-guest interactions. Analysis of selected octahedral distortion parameters (Σ, CShM) reveals interesting differences between these structural types, for example that the iron(ii) centres in grids are generally significantly more distorted than those in squares or cages, yet are still SCO-active. Of the 127 complexes reviewed (79 published 2012-Feb. 2018), 54% are dinuclear, 10% trinuclear, 31% tetranuclear, and the remaining 5% are penta, hexa and octanuclear. Of the 93 designer ligands utilised in these polynuclear architectures: 60 feature azoles; 55 provide all donors to the Fe(ii) centres (no co-ligands coordinated) and form exclusively 5-membered chelate rings via either bidentate azole-imine/pyridine or tridentate heterocycle-imine/amine/thioether/pyridine-heterocycle binding pockets.

Seventeen cobalt complexes-eleven dinuclear cobalt(II) complexes and three tetranuclear cobalt complexes (two mixed valent) of ditopic ligands, with varying N-donor aromatic bridging moieties and pendant pyridine side arms, as well as three mononuclear cobalt(II) complexes of Schiff base macrocyclic ligands-have been screened for photocatalytic hydrogen evolution reaction (HER) activity. All 17 complexes are active catalysts for the HER, in both DMF and aqueous solution, in tandem with the [Ru(bpy) 3 ] 2+ (bpy=2,2'-bipyridine) photosensitiser. All are benchmarked to the literature standard [Co III (dmgH) 2 (py)Cl] (dmg=dimethylglyoxime, py=pyridine) under identical conditions. Two families of dinuclear cobalt(II) complexes of bis-tetradentate ligands that provide a triazole bridging moiety and mononuclear cobalt(II) complexes of tetradentate Schiff base macrocycles were found to be the most active catalysts, outperforming [Co III (dmgH) 2 (py)Cl] by two- to three-fold. Within these two families, the use of shorter alkyl linkers between the N donors, and hence, smaller chelate ring sizes, was found to significantly enhance catalytic performance, whereas the variation of peripheral functional groups was found to have little effect. This last point will be convenient for subsequent surface immobilisation studies., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Monitoring the spin states of species in solution is a crucial aspect of understanding magnetic properties as well as spin-labile sensing, supramolecular, catalytic and biochemical processes. Herein, we describe the first quantitative variable-pressure and variable-temperature method of determining spin states in solution, demonstrate that it is accurate, and identify a simultaneous T and P sensor system.

Self-assembly of 1:1:2 M II (BF 4 ) 2 (M=Zn or Fe), pyrazine-2,5-dicarbaldehyde (1) and 2-(2-aminoethyl)pyridine gave trimetallic triangle architectures rather than the anticipated tetrametallic [2×2] squares. Options for the nontrivial synthesis of 1 are considered, and synthetic details provided for both preferred routes. Rare cyclohelicate triangle architectures are observed for the pair of structurally characterized yellow-brown [Zn 3 L 3 ](BF 4 ) 6 and dark green [Fe 3 L 3 ](BF 4 ) 6 complexes of the neutral bis-terdentate Schiff base L. In order to form these pyrazine-edged triangles, the octahedral metal ions-with all 6 N-donors provided by the terdentate binding pockets of two L-are located 0.4-0.5 Å out of the plane of the bridging pyrazines, towards the center of the triangle. Density functional theory calculations confirm that simple particle counting entropic arguments, which predict triangles over squares, are correct here, with the triangles shown to be energetically favored over the corresponding squares. However, importantly, DFT analysis of these and related triangle versus square systems also show that vibrational contributions to entropy dominate and may significantly influence the preferred architecture, such that simple particle counting cannot in general be reliably employed to predict the observed architecture., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Access to a new family of thioether-linked PSRT ligands, 4-substituted-3,5-bis{[(2-pyridylmethyl)sulfanyl]methyl}-4H-1,2,4-triazoles (analogues of the previously studied amino-linked PMRT ligands), has been established. Four such ligands have been prepared, PSPhT, PS(i)BuT, PS(t-Bu)PhT, and PS(Me)PhT, with R = Ph, (i)Bu, (t-Bu)Ph, and (Me)Ph, respectively. Three dinuclear colorless to pale green iron(II) complexes, [Fe(II)2(PSRT)2](BF4)4·solvent, featuring N4S2 donor sets, were prepared. Single-crystal structure determinations on [Fe(II)2(PSPhT)2](BF4)4·2MeCN·H2O, [Fe(II)2(PSPhT)2](BF4)4·2(1)/2MeCN·(1)/2H2O·THF, [Fe(II)2(PS(Me)PhT)2](BF4)4·2MeCN, and [Fe(II)2(PS(i)BuT)2](BF4)4·4MeCN reveal that all four are stabilized in the [HS-HS] state to 100 K and that both possible binding modes of the bis-terdentate ligands, cis- and trans-axial, are observed. Variable-temperature magnetic susceptibility studies of air-dried crystals (solvatomorphs of the single crystal samples) reveal the first examples of spin crossover (SCO) for a dinuclear iron(II) complex with N4S2 coordination. Specifically, [Fe(II)2(PSPhT)2](BF4)4·2(1)/2H2O undergoes a multistep but complete SCO from [HS-HS] to [LS-LS], whereas [Fe(II)2(PS(Me)PhT)2](BF4)4·1(1)/2MeCN·2H2O exhibits a half-SCO from [HS-HS] to [HS-LS]. In contrast, [Fe(II)2(PS(i)BuT)2](BF4)4·MeCN·H2O remains [HS-HS] down to 50 K. The reflectance spectrum of pale green [Fe(II)2(PSPhT)2](BF4)4·(1)/2CHCl3·2(1)/2H2O (solvatomorph A) reveals a trace of LS character (572 nm band (1)A1g → (1)T1g). Evans' (1)H NMR method and UV-vis spectroscopy studies revealed that on cooling dark green acetonitrile solutions of these complexes from 313 to 233 K, all three undergo SCO centered at or near room temperature. The tendency of the complexes to go LS in solution reflects the electronic impact of R on the σ-donor strength of the PSRT ligand, whereas the opposite trend in stabilization of the LS state is seen in the solid state, where crystal packing effects, of the R group and solvent content, dominate the SCO behavior.

A family of three new mononuclear complexes of the general form [Fe(L(pz))2(NCE)2] has been prepared (L(pz) = 4-p-tolyl-3-(2-pyrazinyl)-5-(2-pyridyl)-1,2,4-triazole; E = S, Se, BH3). All three exhibit spin crossover, in two cases with hysteresis, with T1/2 being predictably tuned by varying the coordinated anion.

Two processing methods were examined for the recovery of Salmonella from naturally contaminated alfalfa seed. Seed samples, from each of three investigations, were processed by sprouting and shredding before preenrichment and culture. In lot A, Salmonella serotype Newport was isolated from 3 of 30 sample units with the sprouting method and 2 of 30 with the shredding method. In lot B, three serotypes in various combinations were isolated from 10 of 30 sample units with the sprouting method and 9 of 30 with the shredding method. In lot C, Salmonella group C1 was isolated from 27 of 30 sample units with the sprouting method and 24 of 30 with the shredding method. Additionally, serotype Newport was found in one lot C sample unit. Using shredded seed data, a most probable number (MPN) for Salmonella contamination per lot was calculated. Serotype Newport was estimated at 0.07 MPN/100 g in lot A; the concentration for three serotypes was estimated to be 0.36 MPN/100 g in lot B; Salmonella group C1 was estimated at 1.8 MPN/100 g in lot C. Our success in isolating Salmonella from alfalfa seeds was likely attributed to the volume of material tested and the quick acquisition of the seeds after the outbreak was identified. Shredding the seeds was easier and yielded definitive results more quickly than sprouting.