Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties.

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI•-)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2-){[MIIITPP]+}2·xC6H4Cl2 (M = Fe and x = 2 for 3, M = In and x = 1 for 4) were synthesized. The thioindigo (TI2-) dianion and metal (FeIII and InIII) atoms in TPPs maintain their initial charge states during the formation of 3 and 4, allowing the separation of paramagnetic FeIII or diamagnetic InIII ions by a diamagnetic TI2- bridge. Strong antiferromagnetic coupling is observed between FeIII (S = 5/2) centers in complex 3. Partial reduction of MnIII to MnII occurs upon the formation of 1 and 2, leading to assemblies containing three paramagnetic centers: MnII (S = 5/2), MnIII (S = 2), and TI•- radical anion (S = 1/2). Orthogonal arrangement of TPP and TI molecules in 1 provides strong ferromagnetic coupling. Weak antiferromagnetic coupling is realized in 2 due to the rotation of the TI bridge.

Single-Ion Magnetism of the [DyIII(hfac)4]- Anions in the Crystalline Semiconductor {TSeT1.5}●+[DyIII(hfac)4]- Containing Weakly Dimerized Stacks of Tetraselenatetracene.

The oxidation of tetraselenatetracene (TSeT) by tetracyanoquinodimethane in the presence of dysprosium(III) tris(hexafluoroacetylacetonate), DyIII(hfac)3, produces black crystals of {TSeT1.5}●+[DyIII(hfac)4]- (1) salt, which combines conducting and magnetic sublattices. It contains one-dimensional stacks composed of partially oxidized TSeT molecules (formal averaged charge is +2/3). Dimers and monomers can be outlined within these stacks with charge and spin density redistribution. The spin triplet state of the dimers is populated above 128 K with an estimated singlet-triplet energy gap of 542 K, whereas spins localized on the monomers show paramagnetic behavior. A semiconducting behavior is observed for 1 with the activation energy of 91 meV (measured by the four-probe technique for an oriented single crystal). The DyIII ions coordinate four hfac- anions in [DyIII(hfac)4]-, providing D2d symmetry. Slow magnetic relaxation is observed for DyIII under an applied static magnetic field of 1000 Oe, and 1 is a single-ion magnet (SIM) with spin reversal barrier Ueff = 40.2 K and magnetic hysteresis at 2 K. Contributions from DyIII and TSeT●+ paramagnetic species are seen in EPR. The DyIII ion rarely manifests EPR signals, but such signal is observed in 1. It appears due to narrowing below 30 K and has g4 = 6.1871 and g5 = 2.1778 at 5.4 K.

Paramagnetic {[Fe(CO)2]2-µ2-η2:η2-η2:η2-(C60)2}2- Dimer Bridged by Iron Atoms and C-C Bonds: Effect of Starting Iron Carbonyls on Structures and Properties of Negatively Charged Iron-Bridged Fullerene Dimers.

The reaction between an excess of Fe(CO)5 with {Cryptand(K+)}(C60•-) produced the salt {Cryptand(K+)}2{[Fe(CO)2]2-µ2-η2:η2-η2:η2-(C60)2}2-·4C6H4Cl2 (1) containing negatively charged iron-bridged fullerene dimers. In these dimers, the C60 cages are linked via two Fe(CO)2 fragments, forming short Fe-C(C60) bonds with a length of 2.070(3) Å and via two intercage C-C bonds with a length of 1.566(3) Å. Interfullerene center-to-center distance is short, being 9.02 Å. Thus, the coordination-induced dimerization of fullerenes is observed in 1. The dimer is negatively charged, with additional negative electron density mainly localized on iron atoms and, to a lesser extent, on the C60 cages, as revealed by optical and electron paramagnetic resonance spectra. These dimers have a diamagnetic singlet ground state with a small singlet-triplet gap of 25 K; consequently, they transfer to a paramagnetic state with two S = 1/2 spins per dimer above 50 K. Previously, different dimers with isomeric structures were obtained starting from {Cryptand(K+)}(C60•-) and Fe3(CO)12. However, these dimers exhibit diamagnetic properties, owing to the formation of a Fe-Fe bond. In contrast, in dimer 1, the Fe atoms are positioned too far apart to form such a bond, preserving the spin on Fe. We assume that both dimers are formed through the same [Fe(CO)3](C60•-) intermediate, but the subsequent interaction of this intermediate with Fe3(CO)12 or its dimerization yields different dimers. Therefore, the starting carbonyls can control the structures and properties of the resulting dimers.

Synthesis, X-ray Structures, and Optical and Magnetic Properties of Cu(II) Octafluoro-octakisperfluoro(isopropyl)phthalocyanine: The Effects of Electron Addition and Fluorine Accretion.

The stepwise reduction of copper(II) 1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23,24-octakisperfluoro(isopropyl) phthalocyanine (CuIIF64Pc) in o-dichlorobenzene (C6H4Cl2) by potassium graphite in the presence of cryptand(K+), abbreviated L+, results in the formation of (L+)[CuII(F64Pc•3-)]-·2C6H4Cl2 (1), (L+)2[CuII(F64Pc4-)]2-·C6H4Cl2 (2), and (L+)2[CuII(F64Pc4-)]2- (3) complexes. Single-crystal X-ray structures revealed their composition and a monotonic increase with increased phthalocyanine (Pc) negative charges of the magnitude of alternative shortening and elongation of the prior equivalent Nmeso-C bonds. The complexes are separated by bulky i-C3F7 substituents, large cryptand counterions, and solvent molecules. Weak, new bands are generated in the visible and near-infrared (NIR) domains upon reductions. The one-electron reduced complex, [CuII(F64Pc•3-)]-, is a diradical, exhibiting broad electron paramagnetic resonance (EPR) signals, with intermediate parameters between those typical to CuII and F64Pc•3-. The two-electron reduced complexes, [CuII(F64Pc4-)]2-, contain a diamagnetic F64Pc4- macrocycle and a single spin, S = 1/2, on CuII. The bulky perfluoroisopropyl groups are suppressing intermolecular π-π interactions between Pcs in the [CuII(F64Pcn-)](n-2)- (n = 3, 4) anions, 1-3, similar to the case of the nonreduced complex. However, π-π interactions between 1 and o-dichlorobenzene are observed. The d9 and Pc electrons in 1 are antiferromagnetically coupled, J = -0.56 cm-1, as revealed by superconducting quantum interference device (SQUID) magnetometry, but the coupling is at least 1 order of magnitude smaller compared with the coupling observed for CuII(F8Pc•3-) and CuII(F16Pc•3-), a testimony to the F accretion effect of rendering the Pc macrocycle progressively more electron-deficient. The data for CuII(F64Pc) provide structural, spectroscopic, and magnetochemical insights, which establish a trend of the effects of fluorine and charge variations of fluorinated Pcs within the macrocycle series CuII(FxPc), x = 8, 16, 64. Diamagnetic Pcs might be useful for photodynamic therapy (PDT) and related biomedical applications, while the solvent-processable biradicalic nature of the monoanion salts may constitute the basis for designing robust, air-stable electronic, and magnetically condensed materials.

Weak Antiferromagnetic Exchange and Ferromagnetic Alignment of FeII (S=2) Spins in Differently Charged {HAT ⋠(FeII Cl2 )3 }n (n=2- and 3-) Assemblies of Hexaazatriphenylenes (HAT).

Hexaazatrianthracene (HATA) and hexaazatriphenylenehexacarbonitrile {HAT(CN)6 } are reduced by metallic iron in the presence of crystal violet (CV+ )(Cl- ). Anionic ligands are produced, which simultaneously coordinate three FeII Cl2 to form (CV+ )2 {HATA ⋅ (FeII Cl2 )3 }2- ⋅ 3 C6 H4 Cl2 (1) and (CV+ )3 {HAT(CN)6. (FeII Cl2 )3 }3- ⋅ 0.5CVCl ⋅ 2.5 C6 H4 Cl2 (2). High-spin (S=2) FeII atoms in both structures are arranged in equilateral triangles at a distance of 7 Å. An antiferromagnetic exchange is observed between FeII in {HATA ⋅ (FeII Cl2 )3 }2- (1) with a Weiss temperature (Θ) of -80 K, the PHI estimated exchange interaction (J) is -4.7 cm-1 . The {HAT(CN)6 ⋅ (FeII Cl2 )3 }3- assembly is obtained in 2. The formation of HAT(CN)6 .3- is supported by the appearance of an intense EPR signal with g=2.0037. The magnetic behavior of 2 is described by a strong antiferromagnetic coupling between the FeII and HAT(CN)6 .3- spins with J1 =-164 cm-1 (-2 J formalism) and by a weaker antiferromagnetic coupling between the FeII spins with J2 =-15.4 cm-1 . The stronger coupling results in the spins of the three FeII Cl2 units to be aligned parallel to each other in the assembly. As a result, an increase of the χM T values is observed with the decrease of temperature from 9.82 at 300 K up to 15.06 emu ⋅ K/mol at 6 K, and the Weiss temperature is also positive being at +23 K. Thus, a change in the charge and spin state of the HAT-type ligand to ⋅3- results in ferromagnetic alignment of the FeII spins, yielding a high-spin (S=11/2) system. DFT calculations showed that, due to the high symmetry and nearly degenerated LUMO of both HATA and HAT(CN)6 , their complexes with FeII Cl2 have a variety of closely lying excited high-spin states with multiplicity up to S=15/2.

Negatively Charged Iron-Bridged Fullerene Dimer {Fe(CO)2-µ2-η2,η2-C60}22.

The interaction of {Cryptand(K+)}(C60•-) with Fe3(CO)12 produced {Cryptand(K+)}2{Fe(CO)2-µ2-η2,η2-C60}22-·2.5C6H4Cl2 (1) as the first negatively charged iron-bridged fullerene C60 dimer. The bridged iron atoms are coordinated to two 6-6 bonds of one C60 hexagon with short and long C(C60)-Fe bonds with average lengths of 2.042(3) and 2.088(3) Å. Fullerenes are close to each other in the dimer with a center-to-center interfullerene distance of 10.02 Å. Optical spectra support the localization of negative electron density on the Fe2(CO)4 units, which causes a 50 cm-1 shift of the C≡O vibration bands to smaller wavenumbers, and the C60 cages. Dimers are diamagnetic and electron paramagnetic resonance silent and have a singlet ground state resulting from the formation of an Fe-Fe bond in the dimer with a length of 2.978(4) Å. According to density functional theory calculations, the excited triplet state is higher than the ground state by 6.5 kcal/mol. Compound 1 shows a broad near-infrared band with a maximum at 970 nm, which is attributable to the charge transfer from the orbitals localized mainly on iron atoms to the C60 ligand.

Strong Proton-Electron Coupling in π-Planar Metal Complex with Redox-Active Ligands.

Proton-coupled electron transfer (PCET) of metal complexes has been widely studied, especially in biochemistry and catalytic chemistry. Although metal complexes bearing redox-active ligands play a part in these research areas, those with π-planar structure remain entirely unexplored, which are vital for future development of iono-electronics. Here, proton-electron coupling of a π-planar nickel complex bearing redox-active N,S-ligands, Ni(itsq)2 , was investigated by combining experimental and theoretical approaches. Strong proton-electron coupling was manifested in a large potential shift, which is twice greater than that of a typical PCET-type π-planar metal complex with redox-inactive ligands, [Ni(dcpdt)2 ]2- . Theoretical calculations affirmed that the stabilization of frontier orbitals by protonation is greater in Ni(itsq)2 than that in [Ni(dcpdt)2 ]2- . These results indicate that π-planar metal complexes with redox-active ligands are promising for developing novel PCET-type materials.

Emergence of Metallic Conduction and Cobalt(II)-Based Single-Molecule Magnetism in the Same Temperature Range.

Single-molecule magnets exhibit magnetic bistabililties at the molecular level, making them promising for molecule-based spintronics due to high magnetic densities. The incorporation of SMM behavior and electrical conductivity in one compound is rare because these two physical properties often do not operate in the same temperature range, which further hinders their use in practical applications. Here we present an organic-inorganic molecular hybrid, ß″-(BEDO-TTF)3[Co(pdms)2]·(MeCN)(H2O)2 (BO3) (BEDO-TTF = bis(ethylenedioxy)tetrathiafulvalene and H2pdms = 1,2-bis(methanesulfonamido)benzene), which manifests both metallic conduction (electrical conductivity up to 1000 S cm-1 at 12 K under 2.0 gigapascal pressure) and SMM behavior in the temperature range 12-26 K for the first time.

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet-Quartet Transitions in the Dianions.

Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain MII3O clusters inside a π-extended trianionic (Hhp3-) macrocycle have been prepared. Studies of the magnetic properties of NiII3O(Hhp) and CuII3O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp3-) macrocycle and diamagnetic NiII3(O2-) or paramagnetic CuII3(O2-) tetracations. The positive charge of MII3O(Hhp) is compensated by one acetate anion {MII3O(Hhp)}+(CH3CO2-). The three-electron reduction of {MII3O(Hhp)}+ yields {cryptand(Cs+)}2{NiII2NiIO(Hhp5-)}2-·2C7H8 (1) and {cryptand(Cs+)}2{CuII3O(Hhp•6-)}2-·C7H8 (2) crystalline salts. The magnetic properties of 1 reveal the formation of Hhp5- and the reduction of nickel(II) to the paramagnetic NiI ion (S = 1/2), which is accompanied by the formation of the {NiII2NiIO(Hhp5-)}2- dianion. As a result, the magnetic moment of 1 is 1.68 µB in the 20-220 K range, and a broad EPR signal of NiI was observed. The Hhp5- macrocycle has a singlet ground state, but the increase in the magnitude of the magnetic moment of 1 above 220 K is attributed to the population of the triplet excited state in Hhp5-. The {NiII2NiIO(Hhp5-)}2- dianion is transferred from the doublet excited state to the quartet excited state with an energy gap of 1420 ± 50 K. Salt 1 also shows an unusually strong low-energy NIR absorption, which was observed at 1000-2200 nm. In 2, a highly reduced Hhp•6- radical hexaanion (S = 1/2) coexists with a CuII3(O2-) cluster (S = 1/2) in the {CuII3O(Hhp•6-)}2- dianions. The dianions have a triplet ground state with antiferromagnetic exchange between two S = 1/2 spins with J = -6.4 cm-1. The reduction of Hhp in both salts equalizes the initially alternated C-N bonds, supporting the increase in the Hhp macrocycle electron delocalization.

Solid-State Properties of Hexaazatriphenylenehexacarbonitrile HAT(CN)6 .- Radical Anions in Crystalline Salts Containing Cryptand(M+ ) and Crystal Violet Cations.

Crystalline {Cryptand[2.2.2](Na+ )}{HAT(CN)6 .- }⋅0.5C6 H4 Cl2 (1), {Cryptand[2.2.2](K+ )}{HAT(CN)6 .- } (2), (CV+ ){HAT(CN)6 .- } (3), and (CV+ ){HAT(CN)6 .- }⋅2C6 H4 Cl2 (4) salts (where CV+ is the crystal violet cation) containing hexaazatriphenylenehexacarbonitrile radical anions have been obtained. The solid-state molecular structure as well as the optical and magnetic properties of HAT(CN)6 .- are studied. The formation of HAT(CN)6 .- in 1-4 leads to the appearance of new bands in the visible range, at 694 and 740 nm. The HAT(CN)6 .- radical anions have spin state S=1/2 and are packed in one-dimensional stacks containing the {HAT(CN)6 .- }2 dimers alternated with weaker interacting pairs of HAT(CN)6 .- in 1 and nearly isolated {HAT(CN)6 .- }2 dimers in 2. The {HAT(CN)6 .- }2 dimers are diamagnetic in 1 but they effectively mediate one-dimensional antiferromagnetic coupling of spins within the stacks with moderate exchange interaction of J/kB = -80 K. The behaviour of salt 2 is described by a singlet-triplet model for the {HAT(CN)6 .- }2 dimers with an energy gap of 434(±7) K. Magnetic behaviour of both salts agree well with the data of extended Hückel calculations. Salts 3 and 4 contain isolated stacks of alternated HAT(CN)6 .- and CV+ ions, and in this case, nearly paramagnetic behaviour is observed with Weiss temperatures of -1 and -7 K, respectively. Narrow Lorentzian EPR signals with g = 2.0033-2.0039 were found for the HAT(CN)6 .- radical anions in 1 and 4 but in solution g-factor shifts to 1.9964. The electronic structure of HAT(CN)6 .- is analysed based on X-ray diffraction data for 2, showing a Jahn-Teller distortion of the radical anion that reduces the symmetry from D3h to Cs and splits the initially degenerated LUMOs.

Cleavage of the C-H Bond in Bu3MeP+ by Zinc Porphyrin Dianions: Formation of {ZnII(CH2PBu3)(TPyPH)}- Containing Zn-C(ylide) Bond and the (TPyPH)3- Macrocycle Showing Strong NIR Absorption.

Reduction of {ZnII(TPyP)} to the {ZnII(TPyP)}2- dianions (TPyP: tetra(4-pyridyl)porphyrin) in the presence of Bu3MeP+ allows one to observe the C-H bond cleavage in the methyl group of Bu3MeP+ to form (Bu3MeP+){ZnII(CH2PBu3)(TPyPH)}-·0.337C6H5CH3 (1). Salt 1 is the first coordination complex of neutral CH2PBu3 ylide and metalloporphyrin. The released hydrogen atom attacks the meso-carbon atom of TPyP4- forming a TPyPH3- macrocycle related to phlorins. Decreased symmetry of the TPyPH3- allows the observation of a strong NIR absorption. We discuss the molecular structure, optical, and magnetic properties of 1 together with its formation pathways.

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions.

Rational control of the molecular arrangement in solids has been the subject of intense research for many years. In particular, the structural control of bis(ethylenedithio)tetrathiafulvalene (ET) radical cations has attracted special interest because of the primary effect on the electronic properties of the salts. In this study, we obtained the first ET cation radical salts formed with nonuniform silver(I) complex polyanions, which involve multiple kinds of openings in the anionic layer, by an electrocrystallization method. θ-(ET)2Ag2(CN)[N(CN)2]2 (1) with a θ-type ET packing motif contains double helical chains composed of AgN(CN)2, whereas α″-(ET)2Ag2(CN)(SCN)2 (2) with an α″-type ET packing motif contains zigzag ladders composed of AgSCN. Both silver(I)-based tube-like assemblies are connected to each other by a cyano group, affording nonuniform polyanionic structures. Although both salts show semiconducting behavior, there is a distinct difference in their spin geometry, with an S = 1/2 Heisenberg antiferromagnetic square lattice in 1, which is associated with charge disproportionation or dynamical charge fluctuation in the ET layers, and an S = 1/2 Heisenberg anisotropic triangular lattice in 2, which results in spin frustration in the ET layers. The ability of the nonuniform polymeric structures in the anionic layers to act as templates for various arrangements of ET radical cations is demonstrated.

Effect of One- and Two-Electron Reduction of Terbium(III) Double-Decker Phthalocyanine on Single-Ion Magnet Behavior and NIR Absorption.

Reduction of terbium(III) double-decker phthalocyanine, TbIIIPc2 (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN+){TbIII(Pc2-)2}-·2.5C6H4Cl2 (2) containing the dianionic Pc2- macrocycles, whereas a stronger NaCpCo(CO)2 reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na+)}2{(Pc2-)TbIII(Pc•3-)}2- (3) containing the Pc•3- radical trianionic macrocycle. Isolated pairs of the {TbIII(Pc2-)2}- anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak π-orbitals overlapping in all three directions. This is the first example of the two-electron-reduced lanthanide double-decker containing Pc•3- radical trianion studied in solid state. Compound 2 manifests single-ion magnet (SIM) behavior with a large effective spin-reversal energy barrier of Ueff = 538 cm-1 in comparison with previously studied (Bu4N+){TbIII(Pc2-)2}- ( Ueff = 230 cm-1). Thus, changes in cation size and shape affect the molecular packing of {TbIII(Pc2-)2}- and increase the spin-reversal energy barrier. At the same time, two-electron-reduced species 3 containing TbIII and Pc•3- show no signs of SIM such as hysteresis loop at 1.9 K, and no peaks are observed on the temperature dependencies of in-phase (χ') and out-of-phase (χ″) signals. In contrast to EPR silent 2, both compounds 1 and 3 manifest broad signals from paramagnetic TbIII ions. Narrower signals attributed to Pc•3- are of high intensity only in 3. In addition to the absorption bands of Pc in the UV and visible spectral range, compound 3 manifests the lowest energy absorption band in solid-state spectra even in the near IR range at 4700 cm-1 (2130 nm), whereas such bands are not observed in the spectrum of 2. These data show that the reduction of the Pc macrocycles in the lanthanide double-deckers leads to the appearance of new very low-energy new transitions associated with Pc•3- whose energy is the lowest among known reduced metal phthalocyanines.

Fullerene and endometallofullerene Kagome lattices with symmetry-forced spin frustration.

Salts of fullerene C60˙- and endometallofullerene Sc3N@Ih-C80˙- radical anions with Bu3MeP+ cations ((Bu3MeP+)3(C60˙-)3·C6H4Cl2 (1) and (Bu3MeP+)3(Sc3N@Ih-C80˙-)3·C6H4Cl2 (2)) have been obtained. The C3 symmetry of the Bu3MeP+ cation provides 2D Kagome lattices with an equilateral triangle arrangement of fullerenes in accordance with trigonal crystal symmetry P31m. The C60˙- and Sc3N@Ih-C80˙- radical anions preserve their monomeric forms in 1 and 2 with the S = 1/2 spin state down to 1.9 K. The close packing of the fullerene radical anions results in strong antiferromagnetic coupling of the spins with Weiss temperatures of -108 K for 1 and -43 K for 2. Compound 1 is a rare example of a magnetic system in which in spite of the strong magnetic coupling of spins no long-range ordering is observed down to 1.9 K. The 13C NMR spectra of the 13C enriched sample of 1 support the absence of the antiferromagnetic ordering of spins down to 1.5 K. Thus, the crystals of 1 preserve large spin frustration forced by the trigonal symmetry. Therefore, compound 1 is a promising candidate for the first observation of a quantum spin liquid (QSL) state in a fullerene-based system. Isostructural salt 2 is the first compound that contains monomeric paramagnetic Sc3N@Ih-C80˙- radical anions stable down to 1.9 K, which show strong spin frustration. These data indicate the ability of endometallofullerenes to give exotic magnetic systems such as QSLs.

Mapping molecular motions leading to charge delocalization with ultrabright electrons.

Ultrafast processes can now be studied with the combined atomic spatial resolution of diffraction methods and the temporal resolution of femtosecond optical spectroscopy by using femtosecond pulses of electrons or hard X-rays as structural probes. However, it is challenging to apply these methods to organic materials, which have weak scattering centres, thermal lability, and poor heat conduction. These characteristics mean that the source needs to be extremely bright to enable us to obtain high-quality diffraction data before cumulative heating effects from the laser excitation either degrade the sample or mask the structural dynamics. Here we show that a recently developed, ultrabright femtosecond electron source makes it possible to monitor the molecular motions in the organic salt (EDO-TTF)2PF6 as it undergoes its photo-induced insulator-to-metal phase transition. After the ultrafast laser excitation, we record time-delayed diffraction patterns that allow us to identify hundreds of Bragg reflections with which to map the structural evolution of the system. The data and supporting model calculations indicate the formation of a transient intermediate structure in the early stage of charge delocalization (less than five picoseconds), and reveal that the molecular motions driving its formation are distinct from those that, assisted by thermal relaxation, convert the system into a metallic state on the hundred-picosecond timescale. These findings establish the potential of ultrabright femtosecond electron sources for probing the primary processes governing structural dynamics with atomic resolution in labile systems relevant to chemistry and biology.

Solid State Structure, and Optical and Magnetic Properties, of Free Base Tetra(4-pyridyl)porphyrin {H2T(4-Py)P}•- Radical Anions.

A crystalline {cryptand[2.2.2.](K+)}{H2T(4-Py)P•-}·C6H4Cl2 (1) salt with tetra(4-pyridyl)porphyrin radical anions was obtained, enabling the effect of reduction on a metal-free porphyrin macrocycle to be studied. In contrast to pristine H2T(4-Py)P, the H2T(4-Py)P•- radical anions have altered C-C(meso) bonds due to partial loss of aromaticity from the porphyrin macrocycle. Short and long bonds have average lengths of 1.396(3) and 1.426(3) Å, which thus differ by 0.03 Å. Reduction affects the positions of the Soret and Q-bands of porphyrin observed in the spectrum of 1 at 439 and 512, 583, and 614 nm, and new bands of the radical anion appear at 684, 755, and 900 nm. The H2T(4-Py)P•- radical anions have a spin state of S = 1/2 and a magnetic moment of 1.64 µB at 300 K. Salt 1 shows a narrow asymmetric EPR signal fitted with two Lorentzian lines, with g⊥ = 2.0031 and a line width (ΔH) of 0.186 mT, and g∥ = 2.0019 (ΔH = 0.284 mT) at 295 K, and this signal splits into three components below 39 K. Salt 1 shows antiferromagnetic spin coupling with a Weiss temperature of -2 K.

Interligand Charge Transfer in a Complex of Deprotonated cis-Indigo Dianions and Tin(II) Phthalocyanine Radical Anions with Cp*IrIII.

A diamagnetic complex, {(cis-indigo-N,N)2-(Cp*IrIII)} (1), in which deprotonated cis-indigo dianions coordinate an iridium center through two nitrogen atoms was obtained. By employment of the ability of the iridium center in 1 to coordinate an additional ligand, the complex [(Bu4N+)2{[SnII(Pc•3-)](cis-indigo-N,N)2-Cp*IrIII}•-2·0.5(H2Indigo)·2.5C6H4Cl2 (2), which has two functional ligands coordinating an IrIII center, was obtained. This complex has a magnetic moment of 1.71 µB at 300 K, in accordance with an S = 1/2 spin state. The spin density is mainly delocalized over the Pc•3- macrocycle and partially on (cis-indigo-N,N)2-. Due to an effective π-π interaction, a thermally activated charge transfer from [SnII(Pc•3-)]•- to (cis-indigo-N,N)2- is observed, with an estimated Gibbs energy (-ΔG°) of 9.27 ± 0.18 kJ/mol. The deprotonation of indigo associated with the coordination of IrIII by the indigo releases H+ ions, which protonate noncoordinating indigo molecules to produce leuco cis-indigo (H2Indigo). One H2indigo links two (cis-indigo-N,N)2- dianions in 2 to produce strong N-H···O═C and O-H···O═C hydrogen-bonding interactions.

Multifunctional Compound Combining Conductivity and Single-Molecule Magnetism in the Same Temperature Range.

We report the first highly conducting single-molecule magnet, (BEDO)4[ReF6]·6H2O [1; BEDO = bis(ethylenedioxo)tetrathiafulvalene], whose conductivity and single-molecule magnetism coexist in the same temperature range. The compound was synthesized by BEDO electrocrystallization in the presence of (Ph4P)2[ReF6]·2H2O and characterized by crystallography and measurements of the conductivity and alternating-current magnetic susceptibility.

Magnetic-Nonmagnetic Phase Transition with Interlayer Charge Disproportionation of Nb3 Trimers in the Cluster Compound Nb3Cl8.

We grew large single crystals of the cluster magnet Nb3Cl8 with a magnetic triangular lattice and investigated its magnetic properties and crystal structure. In Nb3Cl8, the [Nb3]8+ cluster has a single unpaired spin, making it an S = 1/2 triangular lattice anti-ferromagnet. At low temperatures, Nb3Cl8 exhibits a magnetic-nonmagnetic phase transition driven by a charge disproportionation, in which the paramagnetic [Nb3]8+ clusters transform into alternating layers of nonmagnetic [Nb3]7+ and [Nb3]9+ clusters. The observed exotic phenomenon with the strong correlation between the magnetism and structure are based on the nature of the cluster magnetism.

The Salts of Copper Octafluoro- and Hexadecafluorophthalocyanines Containing [CuII(F8Pc)4-]2- Dianions and [CuF16Pc]- Monoanions.

Crystalline anionic salts with copper octafluoro- and hexadecafluorophthalocyanines, (Bu4N+)2[CuII(F8Pc)4-]2-·2C6H4Cl2 (1) and (PPN+)3[CuF16Pc]33-·2C6H5CN (2), where PPN+ is bis(triphenylphosphoranylidene)ammonium and Pc is phthalocyanine, have been obtained. The absence of noticeable absorption in the NIR range and DFT calculations for 1 indicate that both negative charges are mainly localized on the Pc ligand, and that the [CuII(F8Pc)4-]2- dianions are formed without reduction of CuII. The magnetic moment of 1.60 µB corresponds to the contribution of one S = 1/2 spin per dianion. The spin is localized on the CuII atom, which shows an EPR signal characteristic of CuII. Dianions are isolated in 1, providing only weak magnetic coupling of spins with a Weiss temperature of -4 K. Salt 2 contains closely packed π-π stacks built of [CuF16Pc]- anions of types I and II, and the interplanar distances are 3.187 and 3.275 Å. According to the DFT calculations, the [CuF16Pc]- anions of types I and II can have different charge distributions, with localization of an extra electron on the copper atoms to form diamagnetic [CuI(F16Pc)2-]- monoanions or delocalization of an extra electron on the F16Pc ligand to form [CuII(F16Pc)•3-]•- having an S = 1/2 (CuII) + 1/2 (F16Pc•3-) spin state. In fact, at 300 K, the magnetic moment of 2 of 3.25 µB per formula unit is rather close to the contribution from two [CuII(F16Pc)•3-]•- (calculated µeff is 3.46 µB). The Weiss temperature of -21.5 K indicates antiferromagnetic coupling of spins, which can be modeled by stronger intermolecular coupling between (F16Pc)•3- with J1/kB = -23.5 K and weaker intramolecular coupling between CuII and (F16Pc)•3- with J2/kB = -8.1 K. This interaction is realized in the {[CuII(F16Pc)•3-]•-}2 dimers separated by diamagnetic [CuI(F16Pc)2-]- species. In spite of the stacking arrangement of phthalocyanine macrocycles in 2, the inhomogeneous charge distribution and nonuniform distances between the macrocycles should suppress electrical conductivity.