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A series of heterobimetallic lantern complexes, [PtFe(SOCR) 4 (pyX)] where R = Me, X = H ( 1 ), X = NH 2 ( 2 ), X = SMe ( 3 ); R = Ph, X = H ( 4 ), X = NH 2 ( 5 ), X = SMe ( 6 ), have been prepared and characterized spectroscopically. Compounds 1 , 4 , and 5 are reported herein for the first time. The high-spin iron(II) sites of 1 - 6 have been investigated using 57 Fe Mössbauer spectroscopy. Although the isomer shift of these species is nearly identical, their quadrupole splitting exhibits a much larger variation. Moreover, the zero-field Mössbauer spectra of 3 - 5 show surprising changes over time which are likely indicative of small structural distortions. The field dependent Mössbauer study of 1 and 6 revealed a zero field splitting (ZFS) characterized by a relatively large and positive D value. The combined Density Functional Theory (DFT) and ab initio Complete Active Space Self-Consistent Field (CASSCF) investigation of 1 - 6 indicates that their ground state is best described using a linear combination of {|xz⟩, |yz⟩} states. Our theoretical analysis suggests that the ZFSs and magnitude of the quadrupole splitting of 1 - 6 are determined by the spin-orbit coupling of the three lowest orbital states which have a T 2g parentage.

The electronic structures and spectroscopic behavior of three high-spin Fe II complexes of fluorinated alkoxides were studied: square-planar {K(DME) 2 } 2 [Fe(pin F ) 2 ] ( S ) and quasi square-planar {K( C 222)} 2 [Fe(pin F ) 2 ] ( S' ) and trigonal-planar {K(18C6)}[Fe(OC 4 F 9 ) 3 ] ( T ) where pin F = perfluoropinacolate and OC 4 F 9 = tris -perfluoro- t -butoxide. The zero-field splitting (ZFS) and hyperfine structure parameters of the S = 2 ground states were determined using field-dependent 57 Fe Mössbauer and high-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopies. The spin Hamiltonian parameters were analyzed with crystal field theory and corroborated by density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) calculations. Whereas the ZFS tensor of S has a small rhombicity, E / D = 0.082, and a positive D = 15.17 cm -1 , T exhibits a negative D = -9.16 cm -1 and a large rhombicity, E / D = 0.246. Computational investigation of the structural factors suggests that the ground-state electronic configuration and geometry of T 's Fe site are determined by the interaction of [Fe(OC 4 F 9 ) 3 ] - with {K(18C6)} + . In contrast, two distinct countercations of S / S' have a negligible influence on their [Fe(pin F ) 2 ] 2- moieties. Instead, the distortions in S' are likely induced by the chelate ring conformation change from δλ, observed for S , to the δδ conformation, determined for S' .

There is considerable interest in MnOH x moieties, particularly in the stepwise changes in those O-H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOH x }, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pin F ) 2- including the first example of a crystallographically characterized mononuclear {Mn(iii)OH} with all O-donors, K 2 [Mn(OH)(pin F ) 2 ], 3. Complex 3 is prepared via deprotonation of K[Mn(OH 2 )(pin F ) 2 ], 1, the p K a of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large Δ E p , assigned to the Mn(iii/ii) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O-H bond in {Mn(ii)-OH 2 } is estimated to be 67-70 kcal mol -1 . Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K 2 [Mn(OAc)(pin F ) 2 ], 2, proposed to result from the oxidation of Et 2 O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et 2 O, but addition of O 2 at low temperature effects the formation of a new chromophore proposed to be a Mn(iv) species. The related complexes K(18C6)[Mn(iii)(pin F ) 2 ], 4, and (Me 4 N) 2 [Mn(ii)(pin F ) 2 ], 5, have also been prepared and their properties discussed in relation to complexes 1-3., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

High quality epitaxial thin films of the quasi-one dimensional conductor K 0.3 MoO 3 have been successfully grown on SrTiO 3 (100), SrTiO 3 (110), and SrTiO 3 (510) substrates via pulsed laser deposition. Scanning electron microscopy revealed quasi-one dimensional rod-shaped structures parallel to the substrate surface, and the crystal structure was verified by using X-ray diffraction. The temperature dependence of the resistivity for the K 0.3 MoO 3 thin films demonstrates a metal-to-semiconductor transition at about 180 K. Highly anisotropic resistivity was also observed for films grown on SrTiO 3 (510)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The achievement of atomic control over the organic-inorganic interface is key to engineering electronic and spintronic properties of molecular devices. We leverage insights from inorganic chemistry to create hard-soft acid-base (HSAB) theory-derived design principles for incorporation of single molecules onto metal electrodes. A single molecule circuit is assembled via a bond between an organic backbone and an under-coordinated metal atom of the electrode surface, typically Au. Here, we study molecular composition factors affecting the junction assembly of coordination complexes containing transition metals atoms on Au electrodes. We employ hetero- and homobimetallic lantern complexes and systematically change the coordination environment to vary the character of the intramolecular bonds relative to the electrode-molecule interaction. We observe that trends in the robustness and chemical selectivity of single molecule junctions formed with a range of linkers correlate with HSAB principles, which have traditionally been used to guide atomic arrangements in the synthesis of coordination complexes. We find that this similarity between the intermolecular electrode-molecule bonding in a molecular circuit and the intramolecular bonds within a coordination complex has implications for the design of metal-containing complexes compatible with electrical measurements on metal electrodes. Our results here show that HSAB principles determine which intramolecular interactions can be compromised by inter molecule-electrode coordination; in particular on Au electrodes, soft-soft metal-ligand bonding is vulnerable to competition from soft-soft Au-linker bonding in the junction. Neutral donor-acceptor intramolecular bonds can be tuned by the Lewis acidity of the transition metal ion, suggesting future synthetic routes toward incorporation of transition metal atoms into molecular junctions for increased functionality of single molecule devices.

A new template condensation reaction has been discovered in a mixture of Pt(II), thiobenzamide, and base. Four complexes of the general form [Pt(ctaPh R ) 2 ], R = CH 3 ( 1a ), H ( 1b ), F (1c ), Cl ( 1d ), cta = c ondensed t hio a mide, have been prepared under similar conditions and thoroughly characterized by 1 H NMR and UV-vis-NIR spectroscopy, (spectro)electrochemistry, elemental analysis, and single-crystal X-ray diffraction. The ligand is redox active and can be reduced from the initial monoanion to a dianionic and then trianionic state. Chemical reduction of 1a with [Cp 2 Co] yielded [Cp 2 Co] 2 [Pt(ctaPh CH3 ) 2 ], [Cp 2 Co] 2 [1a] , which has been similarly characterized with the addition of EPR spectroscopy and SQUID magnetization. The singly reduced form containing [1a] 1- , (nBu 4 N)[Pt(ctaPh CH3 ) 2 ], has been generated in situ and characterized by UV-vis and EPR spectroscopies. DFT studies of 1b , [1b] 1- , and [1b] 2- confirm the location of additional electrons in exclusively ligand-based orbitals. A detailed analysis of this redox-active ligand, with emphasis on the characteristics that favor noninnocent behavior in six-membered chelate rings, is included.

A new air-stable catalyst for the oxidative dehydrogenation of benzylic alcohols under ambient conditions has been developed. The synthesis and characterization of this compound and the related monomeric and dimeric V(IV)- and V(V)-pin F (pin F = perfluoropinacolate) complexes are reported herein. Monomeric V(IV) complex (Me 4 N) 2 [V(O)(pin F ) 2 ] ( 1 ) and dimeric (μ-O) 2 -bridged V(V) complex (Me 4 N) 2 [V 2 (O) 2 (μ-O) 2 (pin F ) 2 ] ( 3a ) are prepared in water under ambient conditions. Monomeric V(V) complex (Me 4 N)[V(O)(pin F ) 2 ] ( 2 ) may be generated via chemical oxidation of 1 under an inert atmosphere, but dimerizes to 3a upon exposure to air. Complexes 1 and 2 display a perfectly reversible V IV/V couple at 20 mV (vs Ag/AgNO 3 ), whereas a quasi-reversible V IV/V couple at -865 mV is found for 3a . Stoichiometric reactions of 3a with both fluorenol and TEMPOH result in the formation of (Me 4 N) 2 [V 2 (O) 2 (μ-OH) 2 (pin F ) 2 ] ( 4a ), which contains two V(IV) centers that display antiferromagnetic coupling. In order to structurally characterize the dinuclear anion of 4a , {K(18C6)} + countercations were employed, which formed stabilizing K···O interactions between the counterion and each terminal oxo moiety and H-bonding between the oxygen atoms of the crown ether and μ-OH bridges of the dimer, resulting in {K(18C6)} 2 [V 2 (O) 2 (μ-OH) 2 (pin F ) 2 ] ( 4b ). The formal storage of H 2 in 4a is reversible and proton-coupled electron transfer (PCET) from crystals of 4a regenerates 3a upon exposure to air over the course of several days. Furthermore, the reaction of 3a (2%) under ambient conditions with excess fluorenol, cinnamyl alcohol, or benzyl alcohol resulted in the selective formation of fluorenone (82% conversion), cinnamaldehyde (40%), or benzaldehyde (7%), respectively, reproducing oxidative alcohol dehydrogenation (OAD) chemistry known for VO x surfaces and demonstrating, in air, the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones.

The synthesis and characterization of a series of Sn(ii) and Sn(iv) complexes supported by the highly electron-withdrawing dianionic perfluoropinacolate (pin F ) ligand are reported herein. Three analogs of [Sn IV (pin F ) 3 ] 2- with NEt 3 H + (1), K + (2), and {K(18C6)} + (3) counter cations and two analogs of [Sn II (pin F ) 2 ] 2- with K + (4) and {K(15C5) 2 } + (5) counter cations were prepared and characterized by standard analytical methods, single-crystal X-ray diffraction, and 119 Sn Mössbauer and NMR spectroscopies. The six-coordinate Sn IV (pin F ) complexes display 119 Sn NMR resonances and 119 Sn Mössbauer spectra similar to SnO 2 (cassiterite). In contrast, the four-coordinate Sn II (pin F ) complexes, featuring a stereochemically-active lone pair, possess low 119 Sn NMR chemical shifts and relatively high quadrupolar splitting. Furthermore, the Sn(ii) complexes are unreactive towards both Lewis bases (pyridine, NEt 3 ) and acids (BX 3 , Et 3 NH + ). Calculations confirm that the Sn(ii) lone pair is localized within the 5s orbital and reveal that the Sn 5p x LUMO is energetically inaccessible, which effectively abates reactivity.

The new PtVO(SOCR)4 lantern complexes, 1 (R = CH3) and 2 (R = Ph) behave as neutral O-donor ligands to Ln(OR)3 with Ln = Ce, Nd. Four heterotrimetallic complexes with linear {LnOVPt} units were prepared: [Ln(ODtbp)3{PtVO(SOCR)4}] (Ln = Ce, 3Ce (R = CH3), 4Ce (R = Ph); Nd, 3Nd (R = CH3), 4Nd (R = Ph); ODtbp = 2,6-ditertbutylphenolate). Magnetic characterization confirms slow magnetic relaxation behaviour and suggests antiferromagnetic coupling across {Ln-O[double bond, length as m-dash]V} in all four complexes, with variations tunable as a function of Ln and R.

Four groups of rare-earth complexes, comprising 11 new compounds, with fluorinated O-donor ligands ([K(THF) 6 ][Ln(OC 4 F 9 ) 4 (THF) 2 ] ( 1-Ln ; Ln = Ce, Nd), [K](THF) x [Ln(OC 4 F 9 ) 4 (THF) y ] ( 2-Ln ; Ln = Eu, Gd, Dy), [K(THF) 2 ][Ln(pin F ) 2 (THF) 3 ] ( 3-Ln ; Ln = Ce, Nd), and [K(THF) 2 ][Ln(pin F ) 2 (THF) 2 ] ( 4-Ln ; Ln = Eu, Gd, Dy, Y) have been synthesized and characterized. Single-crystal X-ray diffraction data were collected for all compounds except 2-Ln . Species 1-Ln , 3-Ln , and 4-Ln are uncommon examples of six-coordinate (Eu, Gd, Dy, and Y) and seven-coordinate (Ce and Nd) Ln III centers in all-O-donor environments. Species 1-Ln , 2-Ln , 3-Ln , and 4-Ln are all luminescent (except where Ln = Gd and Y), with the solid-state emission of 1-Ce being exceptionally blue-shifted for a Ce complex. The emission spectra of the six Nd, Eu, and Dy complexes do not show large differences based on the ligand and are generally consistent with the well-known free-ion spectra. Time-dependent density functional theory results show that 1-Ce and 3-Ce undergo allowed 5f → 4d excitations, consistent with luminescence lifetime measurements in the nanosecond range. Eu-containing 2-Eu and 4-Eu , however, were found to have luminescence lifetimes in the millisecond range, indicating phosphorescence rather than fluorescence. The performance of a pair of multireference models for prediction of the Ln = Nd, Eu, and Dy absorption spectra was assessed. It was found that spectroscopy-oriented configuration interaction as applied to a simplified model in which the free-ion lanthanide was embedded in ligand-centered Löwdin point charges performed as well (Nd) or better (Eu and Dy) than canonical NEVPT2 calculations, when the ligand orbitals were included in the treatment.

A Cu(i) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4F9)2], was previously shown to form a trinuclear copper-dioxygen species with a {Cu3(μ3-O)2} core, TOC4F9, upon reactivity with O2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of TOC4F9 formation using stopped-flow spectroscopy. The TOC4F9 complex performs catalytic oxidase conversion of hydroquinone (H2Q) to benzoquinone (Q). TOC4F9 also demonstrated hydroxylation of 2,4-di-tert-butylphenolate (DBP) to catecholate, making TOC4F9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for TOC4F9, to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of TOC4F9 are compared to those of its bidentate counterpart, TpinF, formed from K[Cu(pinF)(PR3)]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.

Investigation of Cu-O2 oxidation reactivity is important in biological and anthropogenic chemistry. Zeolites are one of the most promising Cu/O based oxidation catalysts for development of industrial-scale CH4 to CH3OH conversion. Their oxidation mechanisms are not well understood, however, highlighting the importance of the investigation of molecular Cu(i)-O2 reactivity with O-donor complexes. Herein, we give an overview of the synthesis, structural properties, and O2 reactivity of three different series of O-donor fluorinated Cu(i) alkoxides: K[Cu(OR)2], [(Ph3P)Cu(μ-OR)2Cu(PPh3)], and K[(R3P)Cu(pinF)], in which OR = fluorinated monodentate alkoxide ligands and pinF = perfluoropinacolate. This breadth allowed for the exploration of the influence of the denticity of the ligand, coordination number, the presence of phosphine, and KF/O interactions on their O2 reactivity. KF/O interactions were required to activate O2 in the monodentate-ligand-only family, whereas these connections did not affect O2 activation in the bidentate complexes, potentially due to the presence of phosphine. Both families formed trisanionic, trinuclear cores of the form {Cu3(μ3-O)2}3-. Intramolecular and intermolecular substrate oxidation were also explored and found to be influenced by the fluorinated ligand. Namely, {Cu3(μ3-O)2}3- from K[Cu(OR)2] could perform both monooxygenase reactivity and oxidase catalysis, whereas those from K[(R3P)Cu(pinF)] could only perform oxidase catalysis.

Oxidation of distorted square-planar perfluoropinacolate Co compound [CoII(pinF)2]2-, 1, to [CoIII(pinF)2]1-, 2, is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm-1; |E| = 18.0 cm-1, (E/D = 0.27), g⊥ = 2.10, g‖ = 2.25 and χTIP = 1950 × 10-6 cm3 mol-1. This Co(iii) species, 2, reacts with ROS to oxidise two (pinF)2- ligands to form tetrahedral [CoII(Hpfa)4]2-, 3.

As the scale of microelectronic circuit devices approaches the atomic limit, the study of molecular-based wires and magnets has become more prevalent. Compounds with quasi-1D geometries have been investigated for their electronic conductivity and magnetic properties with potential use as nanoscale circuit components and information storage devices. To increase the number of compositionally tailored molecular systems available to study, we have taken a building-block, bottom-up approach to the development of improved electronic structure and magnetic properties of quasi-1D arrays. Over the past decade, a large family of asymmetric complexes that can assemble into extended arrays has resulted. Lantern (or paddle-wheel) complexes with conventional {O, O} donor carboxylates are legion, but by the use of monothiocarboxylate ligands and hard-soft Lewis acid-base principles, dozens of new lantern complexes of the form [PtM(SOCR) 4 (L)] (M = Mg, Ca, Cr, Mn, Fe, Co, Ni, Zn; R = Ph (tba = thiobenzoate), CH 3 (SAc = thioacetate); L = neutral or anionic ligand) have been prepared. Depending on M and L, new intermolecular arrangements have resulted, and the magnetic properties have proven particularly interesting. In the solid state, the [PtM(SOCR) 4 (L)] building blocks are sometimes isolated, sometimes form dimers, and can be induced to form infinite chains. The versatility of the lantern motif was demonstrated with a range of axial ligands to form both terminal and bridged complexes with various 3d metals and two different substituted thiocarboxylate backbone ligands. Within the dozens of crystallographically characterized compounds that make up this family of lanterns, several different structural motifs of solid-state dimerization were observed and divided into four distinct categories on the basis of their Pt···Pt and Pt···S distances and relative monomer orientations. Among all of these compounds, three novel magnetic phenomena were observed. Initially, long-range antiferromagnetic coupling between two metals more than 8 Å apart was observed in solid-state dimers formed via metallophilic Pt···Pt interactions and could induced by choice of the terminal L group. An infinite chain was prepared in [PtCr(tba) 4 (NCS)] ∞ that displays ferromagnetic coupling between Cr centers with J/ k B = 1.7(4) K. Homobimetallic quasi-1D chains of the form [Ni 2 (SOCR) 4 (L)] ∞ (R = Ph, CH 3 ; L = DABCO, pyz) were also prepared with S = 1 {Ni 2 } building blocks in which the Ni centers have two different spin states with weak antiferromagnetic coupling along the chain, such that -0.18 > J/ k B > -0.24 K. In the [Ni 2 (tba) 4 (quin)] derivative, a solid-state dimer forms with a bridging square conformation by interlantern Ni 2 S 2 interactions and displays unusual S = 1 configurations on both Ni centers and weak antiferromagnetic coupling between them.

Total control over the electronic spin relaxation in molecular nanomagnets is the ultimate goal in the design of new molecules with evermore realizable applications in spin-based devices. For single-ion lanthanide systems, with strong spin-orbit coupling, the potential applications are linked to the energetic structure of the crystal field levels and quantum tunneling within the ground state. Structural engineering of the timescale of these tunneling events via appropriate design of crystal fields represents a fundamental challenge for the synthetic chemist, since tunnel splittings are expected to be suppressed by crystal field environments with sufficiently high-order symmetry. Here, we report the long missing study of the effect of a non-linear (C 4 ) to pseudo-linear (D 4d ) change in crystal field symmetry in an otherwise chemically unaltered dysprosium complex. From a purely experimental study of crystal field levels and electronic spin dynamics at milliKelvin temperatures, we demonstrate the ensuing threefold reduction of the tunnel splitting.

Superparamagnetic nanoparticles with a high initial magnetic susceptibility χ o are of great interest in a wide variety of chemical, biomedical, electronic, and subsurface energy applications. In order to achieve the theoretically predicted increase in χ o with the cube of the magnetic diameter, new synthetic techniques are needed to control the crystal structure, particularly for magnetite nanoparticles larger than 10 nm. Aqueous magnetite dispersions (Fe 3 O 4 ) with a χ o of 3.3 (dimensionless SI units) at 1.9 vol %, over 3- to 5-fold greater than those reported previously, were produced in a one-pot synthesis at 210 °C and ambient pressure via thermal decomposition of Fe(II) acetate in triethylene glycol (TEG). The rapid nucleation and focused growth with an unusually high precursor-to-solvent molar ratio of 1:12 led to primary particles with a volume average diameter of 16 nm and low polydispersity according to TEM. The morphology was a mixture of stoichiometric and substoichiometric magnetite according to X-ray diffraction (XRD) and Mössbauer spectroscopy. The increase in χ o with the cube of magnetic diameter as well as a saturation magnetization approaching the theoretical limit may be attributed to the highly crystalline structure and very small nonmagnetic layer (∼1 nm) with disordered spin orientation on the surface.

Cu I complexes of the form K[(R 3 P)Cu(pin F )], in which (pin F ) 2- is the bidentate, oxygen-donating ligand perfluoropinacolate, were synthesized and characterized. Low-temperature oxygenation of the K[(R 3 P)Cu(pin F )(PR 3 )] species resulted in a trisanionic bis(μ 3 -oxo) trinuclear copper(II,II,III) core characterized by UV/Vis spectroscopy (λ max [nm] = 330, 535, 630), cryospray-ionization mass spectrometry, and X-band electron paramagnetic resonance spectroscopy (derivative resonance at 3300 G, Δm s =2 at 1500 G). The kinetic behavior of the trimeric {Cu 3 O 2 } species was quantified by stopped-flow spectroscopy and the associated electronic structures were investigated by DFT calculations. An asymmetric {Cu 3 O 2 } species, As T pinF , which bears a structure similar to multicopper oxidases, forms prior to full formation of the symmetric trinuclear core, Sy T pinF . The trimer catalytically oxidizes para-hydroquinone to benzoquinone (a form of oxidase chemistry)., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Four new quasi-1D Ni 2 -lantern chain complexes of the form [Ni 2 (SOCR) 4 (L)] ∞ (R = Ph, L = DABCO (1); R = Ph, L = pyz (2); R = CH 3 , L = DABCO (3); R = CH 3 , L = pyz (4)) were prepared from the reaction of [Ni 2 (SOCR) 4 (EtOH)], R = CH 3 or Ph, with the N,N'-donor bridging ligands pyrazine (pyz) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Reaction of [Ni 2 (tba) 4 (EtOH)], (tba = thiobenzoate) with the mono-N donor ligand quinuclidine (quin) gave the discrete Ni 2 -lantern complex [Ni 2 (tba) 4 (quin)] (5), whereas reaction with pyridine led to fragmentation of the lantern and formation of the known [Ni(tba) 2 (py) 2 ] (6). Single-crystal X-ray diffraction reveals 2-4 to be 1D chain complexes comprising DABCO or pyz ligands which bridge the Ni 2 -lantern units. Complex 5 forms dimers through two equivalent NiS interactions. The Ni-Ni distances within the Ni 2 -lanterns are 2.5316(18)-2.595(2) Å for the 1D chain complexes 2-4, and 2.5746(4) Å in the dimeric complex 5, respectively. Comparing the solid state magnetism of 5 to precursor [Ni 2 (tba) 4 (EtOH)] demonstrates a change in coupling upon change of capping ligand. Meanwhile, chains 1-4 exhibit magnetic properties consistent with an S = 1 system, due to a mixed valent system where the two Ni centers differ in spin state, while 5 possesses two S = 1 Ni(ii) centers. DFT calculations confirm low-spin S = 0 {NiS 4 } and high-spin S = 1 {NiO 4 } centers in each lantern. Fits to the magnetic susceptibility data of the chains suggest a weak antiferromagnetic mean field interaction is present that is largely 1-D in nature, though neither pyrazine nor DABCO promote significant magnetic interaction between neighboring Ni 2 -lanterns.

Exploitation of HSAB preferences allows for high-yield, one-pot syntheses of lanthanide complexes chelated by two Pd or Pt metalloligands, [M II (SAc) 4 ] 2- (SAc - = thioacetate, M = Pd, Pt). The resulting complexes with 8 oxygen donors surrounding the lanthanides can be isolated in crystallographically tetragonal environments as either [NEt 4 ] + (space group: P 4/ mcc ) or [PPh 4 ] + (space group: P 4/ n ) salts. In the case of M = Pt, the complete series of lanthanide complexes has been structurally characterized as the [NEt 4 ] + salts (except for Ln = Pm), while the [PPh 4 ] + salts have been structurally characterized for Ln = Gd-Er, Y. For M = Pd, selected lanthanide complexes have been structurally characterized as both salts. The only significant structural difference between salts of the two counter ions is the resulting twist angle connecting tetragonal prismatic and tetragonal anti-prismatic configurations, with the [PPh 4 ] + salts approaching ideal D 4d symmetry very closely ( φ = 44.52-44.61°) while the [NEt 4 ] + salts exhibit intermediate twist angles in the interval φ = 17.28-27.41°, the twist increasing as the complete 4f series is traversed. Static magnetic properties for the latter half of the lanthanide series are found to agree well in the high temperature limit with the expected Curie behavior. Perpendicular and parallel mode EPR spectroscopy on randomly oriented powder samples and single crystals of the Gd complexes with respectively Pd- and Pt-based metalloligands demonstrate the nature of the platinum metal to strongly affect the spectra. Consistent parametrization of all of the EPR spectra reveals the main difference to stem from a large difference in the magnitude of the leading axial term, B 02, this being almost four times larger for the Pt-based complexes as compared to the Pd analogues, indicating a direct Pt(5d z 2 )-Ln interaction and an arguable coordination number of 10 rather than 8. The parametrization of the EPR spectra also confirms that off-diagonal operators are associated with non-zero parameters for the [NEt 4 ] + salts, while only contributing minimally for the [PPh 4 ] + salts in which lanthanide coordination approximates D 4d point group symmetry closely.

Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR) 4 (L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal-metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc) 4 (OH 2 )] (1), [PtMg(tba) 4 (OH 2 )] (2), [PtCa(tba) 4 (OH 2 )] (3), [PtZn(tba) 4 (OH 2 )] (4), and a mononuclear control (Ph 4 P) 2 [Pt(SAc) 4 ] (5) have been synthesized. Crystallographic data show close Pt-M contacts enforced by the lantern structure in each dinuclear case. 195 Pt-NMR spectroscopy of 1-4, (Ph 4 P) 2 [Pt(SAc) 4 ] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH 3 (thioacetate, SAc), C 6 H 5 (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc) 4 (OH 2 )], and computational studies demonstrate significant dative character. In all of 1-4, the short Pt-M distances suggest that metal-only Lewis donor (Pt)-Lewis acceptor (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic.

A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.