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The research on electron transfer coupled spin transition regulating the valence state and spin state transition of metal ions is promising and challenging. Herein, we report a cyano-bridged {Fe III2 Fe II2 } molecular square complex, {[Fe(Tp)(CN)3]2 [Fe(bnbpen)]2}(ClO4)2·8CH3OH (1·8CH3OH, bnbpen = N,N′-bis-(2-naphthylmethyl)-N,N′-bis(2-picolayl)-ethylenediamine), and its free of solvents form (1). Combined single-crystal X-ray diffraction, temperature-dependent infrared (IR) spectra, magnetic measurements, and Mössbauer spectra reveal that 1·8CH3OH and 1 exhibit reversible one-step and two-step electron transfer coupled spin transition (ETCST) with temperature change, between the low-temperature state {FeII,LS(μ-CN)FeIII,LS}2 (LS = low spin, HS = high spin) and the high-temperature state {FeIII,LS(μ-CN)FeII,HS}2, respectively. [ABSTRACT FROM AUTHOR]

A key challenge in the design of magnetic molecules with intramolecular charge transfer behavior is to obtain reversible magnetic bistability triggered by external stimuli. Here, we show that two dinuclear metal complexes, [(bbp)Fe(CN)3Mn(Py5Me2)]·2.5CH3OH (4) and [(bbp)Fe(CN)3Ni(Py5Me2)]·2.5CH3OH (5) (Py5Me2 = 2,6-bis(1,1-di(pyridine-2-yl)ethyl)pyridine, H2bbp = 2,6-bis(benzimidazole-2-yl)pyridine), were self-assembly synthesized by (Bu4N)2[(bbp)FeIII(CN)3] and [Mn(Py5Me2)(OH2)](ClO4)2 or [Ni(Py5Me2)(OH2)](ClO4)2, respectively. Complexes 4 and 5 exhibited intramolecular metal-to-metal charge transfer with the addition of acids or bases in solution by UV–visible spectrophotometric measurements and electrochemistry studies, and concomitant switching of the {FeIII(μ-CN)MnII/NiII} state to the {FeII(μ-CN)MnIII/NiIII} state. [ABSTRACT FROM AUTHOR]

Cyano-bridged mixed-valence {Fe6} hexanuclear complexes {[Tp4-MeFeII(CN)3]2[FeIII(Tpa)]2[FeIII(OR)(Tpa)]2}·6ClO4·S (Tp4-Me = tri(4-methyl-pyrazol-1-yl)borate, Tpa = tris(2-pyridylmethyl)amine; R = –CH3, S = 8MeOH 1, R = –C2H5, S = 6EtOH 2) have been obtained by building the units of [Tp4-MeFe(CN)3]− and [Fe(Tpa)]2+ in methanol and ethanol, respectively. Complex 1 exhibited single-crystal-to-single-crystal (SCSC) transformation to give {[Tp4-MeFeII(CN)3]2[FeIII(Tpa)]2[FeIII(OH)(Tpa)]2}·6ClO4·8H2O (3) in water. Detailed analysis of the coordination environment of the FeIII centers on the square lattice and magnetic susceptibility measurements of all the complexes confirmed their Fe3+ spin-crossover (SCO) properties (T1/2 = 178 K, 1; 185 K, 2; 208 K, 3). [ABSTRACT FROM AUTHOR]

Understanding the functionality of the modification layer in regulating the charge transfer process at the semiconductor/electrolyte interface is of great significance to the rational design of photoelectrocatalytic water oxidation systems. Herein, by systematically investigating and comparing the charge transfer kinetics behaviors over ferrihydrite (Fh)- and cobalt phosphate (CoPi)-modified hematite (Fe2O3) photoanodes, we unveiled the essential relation between photocurrent enhancement and the charge transfer process. With the hole-storage material Fh as a reference, it was found that CoPi demonstrates high hole-storage capacity at a low bias region (<1.0 V vs. RHE) due to the effective release of Fermi level pinning. Afterwards, the stored holes would be timely injected into the electrolyte for water oxidation, caused by the enhanced charge separation in the presence of CoPi. In contrast, the decoration of Fh can only slightly passivate the surface states and promote hole injection in the high potential region. Subsequently, superior hole-storage capacity in the low-potential region is recognized as a crucial factor for photocurrent enhancement. These combined results provide new insights into the understanding of interfacial charge transfer kinetics. [ABSTRACT FROM AUTHOR]

Six Dy(III) single-ion magnets (SIMs) [Dy(n-OMe-bbpen)X] were synthesized by a solvothermal reaction with three positional isomers (ortho, meta, and para) of ligands n-OMe-H2bbpen and dysprosium halides DyX3, (n-OMe-H2bbpen = N,N′-bis(2-hydroxy-n-methoxybenzyl)-N,N′-bis(2-methylpyridyl)ethylenediamine; n = 3, X = Cl, 1; n = 3, X = Br, 2; n = 4, X = Cl, 3; n = 4, X = Br, 4; n = 5, X = Cl, 5; n = 5, X = Br, 6). Dynamic magnetic measurements revealed that the six complexes possess notably different effective barriers of magnetic reversal: 872.0 K (1), 1210.1 K (2), 137.9 K (3), 602.6 K (4), 907.0 K (5) and 1216.7 K (6). 6 showed the best performance as SIMs among the six Dy(III) complexes. Moreover, the magnetic hysteresis loops of 6 remained open at 21 K. The crystal structures indicate the switching of local symmetry around Dy(III) ion, aroused by the variation in intermolecular interactions and steric effects. This switch is primarily correlated with the distinction of magnetic properties. In addition, ab initio calculations confirmed that the different electrostatic potential around Dy(III) ion stemming from the electronic effect of the OMe-substituted group is another factor leading to the distinction in magnetic properties. This work warns us that when designing ligands for Dy-SIMs, the effect of positional isomerism on magnetic performance must be considered, which is one of the factors that can easily be overlooked. [ABSTRACT FROM AUTHOR]

Two mononuclear Dy3+ compounds [Dy(bmbpen-F)X] (X = Cl, 1; Br, 2) with a pentagonal bipyramidal (PBP) geometry were obtained from N,N′-bis-(5-methyl-2-hydroxybenzyl)-N,N′-bis(5-fluoro-2-methylpyridyl)ethylenediamine (H2bmbpen-F) and dysprosium halides. The magnetic anisotropy and single-molecule magnet (SMM) behavior of these PBP compounds were regulated by introducing both electron-withdrawing F atoms into the equatorial pyridine rings and electron-donating –CH3 groups into the axial phenolic hydroxyl rings. The results of magnetic characterization show that 1 and 2 exhibit single molecule magnet behavior with magnetization reversal barriers of 990(13) and 1189(16) K under a zero dc external field and magnetic hysteresis loops up to 26 K and 36 K, respectively. The results of ab initio calculations are consistent with the experimental observations, confirming that the simultaneous introduction of electron-withdrawing groups into the equatorial positions and electron-donating groups into the axial positions can lead to PBP Dy-SMMs with improved properties. [ABSTRACT FROM AUTHOR]

The reactions of tricyanometallate precursors, (Ph3PMe)[(Tp4-Me)Fe(CN)3·0.5CH3CN] (1) (Tp4-Me = tri(4-methyl-pyrazol-1-yl)borate) and (NBu4)[(MeTp)Fe(CN)3] (MeTp = methyltris(pyrazolyl)borate) with the presence of the tetradentate tpa ligand (tpa = tris(2-pyridylmethyl)amine) and Fe(ClO4)2·6H2O afford two new cyano-bridged mixed-valence {FeIII2FeII2} molecular squares: [(Tp4-Me)FeIII(CN)3]2[FeII(tpa)]2·2ClO4·H2O (2·H2O) and [(MeTp)FeIII(CN)3]2[FeII(tpa)]2·2ClO4·CH3OH (3·CH3OH). Solvent-exchange compounds of 3·CH3OH, [(MeTp)FeIII(CN)3]2[FeII(tpa)]2·2ClO4·2H2O (3·2H2O), and their solvent-free form (2 and 3) are also obtained, respectively. The spin crossover (SCO) properties of all compounds are confirmed by detailed structural analyses of the coordination environments of the FeII centres and magnetic susceptibility measurements. All compounds exhibit SCO behaviour near room temperature (T1/2 = 320 K for 2·H2O; 302 K for 2; 292 K for 3·CH3OH; 306 K for 3·2H2O and 290 K for 3) and reversible single-crystal to single-crystal (SC–SC) transformations induced by guest desorption and resorption or solvent exchange. The transition temperature close to room temperature can be tuned by the dehydration and re-hydration processes. The structure–property analysis discloses that the distorted {Fe4(μ-CN)4} core and deviations of bent 〈Fe−N≡C angles play a key role in tuning the transition temperature of these similar mixed-valence {FeIII2FeII2} complexes. [ABSTRACT FROM AUTHOR]

Solvothermal reactions of 2,5-thiophenedicarboxylate (H2tdc) and N-auxiliary ligands in the presence of cobalt(ii), zinc(ii) and cadmium(ii) salts have given rise to seven new metal–organic frameworks, namely, [Co2(tdc)2(bpp)2(H2O)·(H2O)]n (bpp = 1,3-bis(4-pyridyl)propane) (1), [Cd(tdc)(bpp)(H2O)·(H2O)2]n (2), [Zn2(tdc)2(bbi)2·(H2O)2]n (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (3), [Co4(tdc)3(bimb)4(H2O)5·(tdc)·(DMF)·(H2O)2]n (bimb = 4,4′-bis(1-imidazolyl)biphenyl) (4), [Zn4(O)(tdc)3(bimb)4·(H2O)5.25·(CH3OH)]n (5), [Cd4(tdc)4(bimb)6·(H2O)2·(CH3OH)2·(DMF)4] (6) and [Co2(tdc)2(tib)2·(H2tdc)·(DMF)2] (tib = 1,3,5-tris(1-imidazolyl)benzene) (7), which exhibit structural diversity. Compounds 1–3 display 3D 2-fold interpenetrating 8-connected tsi net, 2D 4-connected sql net, and 3D 5-fold interpenetrating 4-connected dia net, respectively; while compound 4 features an extremely rare 3D 7-connected hxg-d cationic net and compound 5 adopts a 3D trinodal (4,4,6)-connected net with a new topology structure. For compounds 6 and 7, the topology in the structures were determined as 3D 3-fold interpenetrating 5-connected bnn net and 3D 2-fold interpenetrating binodal (3,5)-connected net, respectively. In the solid state, complexes 1, 4 and 5 exhibit nonlinear optical properties, and complex 5 has also been evaluated as a promising visible-light-driven photocatalyst for degradation of organic pollutants. The magnetic investigation of complexes 1 and 4 shows that there exists spin-canted antiferromagnetism for 1, whereas strong antiferromagnetic interaction and/or the depopulation of the higher energy Kramers doublets of the Co(ii) centers are dominant in 4. [ABSTRACT FROM AUTHOR]