Neutron diffraction of tri(3,5-tert-butylphenyl)methane at 20 K reveals an intermolecular C-H···H-C distance of only 1.566(5) Å, which is the shortest reported to date. The compound crystallizes as a C-symmetric dimer in an unusual head-to-head fashion. Quantum chemical computations of the solid state at the HSE-3c level of theory reproduce the structure and the close contact well (1.555 Å at 0 K) and emphasize the significance of packing effects; the gas-phase dimer structure at the same level shows a 1.634 Å C-H···H-C distance. Intermolecular London dispersion interactions between contacting tert-butyl substituents surrounding the central contact deliver the decisive energetic contributions to enable this remarkable bonding situation.

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH(2)(CH(3))(2)](n)[Fe(III)Fe(II)(HCOO)(6)](n). The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities of the [Fe(III)Fe(II)(HCOO)(6)](n) framework. In the low-temperature phase, a change in space group from P31c to R3c occurs, involving a tripling of the c-axis due to the ordering of the dimethylammonium counterion. The occurrence of this nuclear phase transition is associated with an electric transition, from paraelectric to antiferroelectric. A combination of powder and single crystal neutron diffraction measurements below the magnetic order transition (ca. 37 K) has been used to determine unequivocally the magnetic structure of this Néel N-Type ferrimagnet, proving that the ferrimagnetic behavior is due to a noncompensation of the different Fe(II) and Fe(III) magnetic moments.

Two new cobalt(II) complexes of formula [Co(2)(bta)(H(2)O)(6)](n) x 2nH(2)O (1) and [Co(phda)(H(2)O)](n) x nH(2)O (2) [H(4)bta = 1,2,4,5-benzenetetracarboxylic acid, H(2)phda = 1,4-phenylenediacetic acid] have been characterized by single crystal X-ray diffraction. Compound 1 is a one-dimensional compound where the bta(4-) ligand acts as 2-fold connector between the cobalt(II) ions through two carboxylate groups in para-conformation. Triply bridged dicobalt(II) units occur within each chain, a water molecule, a carboxylate group in the syn-syn conformation, and an oxo-carboxylate with the mu(2)O(1);kappa(2)O(1),O(2) coordination mode acting as bridges. Compound 2 is a three-dimensional compound, where the phda(2-) group acts as a bridge through its two carboxylate groups, one of them adopting the mu-O,O' coordination mode in the syn-syn conformation and the other exhibiting the single mu(2)-O'' bridging mode. As in 1, chains of cobalt(II) ions occur in 2 with a water molecule, a syn-syn carboxylate group, and an oxo-carboxylate constitute the triply intrachain bridging skeleton. Each chain is linked to other four ones through the phda(2-) ligand, giving rise to the three-dimensional structure. The values of the intrachain cobalt-cobalt separation are 3.1691(4) (1) and 3.11499(2) A (2) whereas those across the phenyl ring of the extended bta(4-) (1) and phda(2-) (2) groups are 10.1120(6) and 11.4805(69 A, respectively. The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9-300 K, and their analysis has revealed the occurrence of moderate intrachain ferromagnetic couplings [J = +5.4 (1) and +2.16 cm(-1) (2), J being the isotropic magnetic coupling parameter], the magnetic coupling through the extended bta(4-) and phda(2-) with cobalt-cobalt separations larger than 10 A being negligible. The nature and magnitude of the magnetic interactions between the high-spin cobalt(II) ions in 1 and 2 are compared to those of related systems and discussed as a function of the complementarity-countercomplementarity effects of the triple bridges.

Four gadolinium(III) complexes with dicarboxylate ligands of formulas [Gd2(mal)3(H2O)5]n.2nH2O (1), [Gd2(mal)3(H2O)6]n (2), [NaGd(mal)(ox)(H2O)3]n (3), and [Gd2(ox)3(H2O)6]n.2.5nH2O (4) (mal = malonate; ox = oxalate) have been prepared, and their magnetic properties have been investigated as a function of the temperature. The structures of 1-3 have been determined by X-ray diffraction methods. The crystal structure of 4 was already known, and it is made of hexagonal layers of Gd atoms that are bridged by bis-bidentate oxalate. Compound 1 is isostructural with the europium(III) malonate complex [Eu2(mal)3(H2O)5]n.2nH2O,1 whose structure was reported elsewhere. The Gd atoms in 1 define a two-dimensional network where a terminal bidentate and bridging bidentate/bis-monodentate and tris-bidentate coordination modes of malonate occur. Compound 2 has a three-dimensional structure with a structural phase transition at 226 K, which involves a change of the space group from I2/a to Ia. Although its structure at room temperature was already known, that below 226 K was not. Pairs of Gd atoms with a double oxo-carboxylate bridge occur in both phases, and the main differences between both structures deal with the Gd environment and the H-bond pattern. 3 is also a three-dimensional compound, and it was obtained by reacting Gd(III) ions with malonic acid in a silica gel medium. Oxalic acid results as an oxidized product of the malonic acid, and single crystals of the heteroleptic complex were produced. The Gd atoms in 3 are connected through bis-bidentate oxalate and carboxylate-malonate bridges in the anti-anti and anti-syn coordination modes. Compounds 1 and 2 exhibit weak but significant ferromagnetic couplings between the Gd(III) ions through the single (1) and double (2) oxo-carboxylate bridges, whereas antiferromagnetic interactions across the bis-bidentate oxalate account for the overall antiferromagnetic behavior observed in 3 and 4.

Two new digadolinium(III) complexes with monocarboxylate ligands, [Gd2(pac)6(H2O)4] (1) and [Gd2(tpac)6(H2O)4] (2) (Hpac = pentanoic acid and Htpac = 3-thiopheneacetic acid), have been prepared and their structures determined by X-ray diffraction on single crystals. Their structures consist of neutral and isolated digadolinium(III) units, containing six monocarboxylate ligands and four coordinated water molecules, the bridging skeleton being built by a muO(1):kappa2O(1)O(2) framework. This structural pattern has already been observed in the parent acetate-containing compound [Gd2(ac)6(H2O)4] x 4 H2O (3) whose structure and magnetic properties were reported elsewhere (L. Cañadillas-Delgado, O. Fabelo, J. Cano, J. Pasán, F. S. Delgado, M. Julve, F. Lloret and C. Ruiz-Pérez, CrystEngComm, 2009, 11, 2131). Each gadolinium(III) ion in 1 and 2 is nine-coordinated with seven carboxylate-oxygen atoms from four pac (1)/tpac (2) ligands and two water molecules (1 and 2) building a distorted monocapped square antiprism. The values of the intramolecular gadolinium-gadolinium separation are 4.1215(5) (1), 4.1255(6) (2) and 4.1589(3) A (3) and those of the angle at the oxo-carboxylate bridge (theta) are 113.16(13) (1), 112.5(2) (2) and 115.47(7) degrees (3). Magnetic susceptibility measurements in the temperature range 1.9-300 K reveal the occurrence of a weak intramolecular antiferromagnetic interaction [J = -0.032(1) (1) and -0.012(1) cm(-1) (2), the Hamiltonian being defined as H = -JS(A) x S(B)] in contrast with the intramolecular ferromagnetic coupling which occurs in 3 (J = +0.031(1) cm(-1)). The magneto-structural data of 1-3 show the relevance of the geometrical parameters at the muO(1):kappa2O(1)O(2) bridge on the nature of the magnetic coupling between two gadolinium(III) ions.

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Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2](4-) have been prepared by the Cu(II)-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N'-para-phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N'-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N'-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation with a smaller deviation from perpendicularity between the two benzene rings and the basal planes of the square planar Cu(II) ions when increasing the number of methyl substituents (average dihedral angles (ϕ) of 58.72(7) and 73.67(5)° for 1 a and 3 c, respectively). Variable-temperature (2.0-300 K) magnetic-susceptibility measurements show an overall increase of the intramolecular antiferromagnetic coupling with the number of methyl substituents onto the para-phenylene spacers (-J=75-95, 100-124, and 128-144 cm(-1) for 1 a-c, 2 a-c, and 3 a-c, respectively; H=-JS1×S2). Cyclic voltammetry (CV) measurements show a reversible one-electron oxidation of the double polymethyl-substituted para-phenylenediamidate bridging skeleton at a relatively low formal potential that decreases with the number of methyl substituents (E1=+0.33, +0.24, and +0.15 V vs. SCE for 1-3, respectively). The monooxidized dicopper(II) π-radical cation species 3' prepared by the chemical oxidation of 3 with bromine exhibits intense metal-to-ligand charge-transfer (MLCT) transitions in the visible and near-IR (λmax=595 and 875 nm, respectively) regions together with a rhombic EPR signal with a seven-line splitting pattern due to hyperfine coupling with the nuclear spin of the two Cu(II) ions. Density functional (DF) calculations for 3' evidence a characteristic iminoquinonoid-type short-long-short alternating sequence of C-N and C-C bonds for both tetramethyl-para-phenylenediamidate bridges and a large amount of spin density of negative sign mainly delocalized along each of the four benzene C atoms directly attached to the amidate N atoms, which is in agreement with a fully delocalized π-stacked monoradical ligand description. Hence, the spins of the two Cu(II) ions (SCu=1/2) that are antiparallel aligned in 3 (OFF state) become parallel in 3' (ON state). Further developments may be then envisaged for this new permethylated dicopper(II) paracyclophane with a redox noninnocent ligand as a prototype for molecular magnetic electroswitch.

In this article, we describe the synthesis and single-crystal X-ray structural studies of two new lanthanide complexes of formula [M I Ln III (bta)(H 2 O) 3 ]‚nH 2 O, (M ) Na (1), K (2); Ln ) Gd; H 4 bta ) 1,2,4,5-benzenetetracarboxylic acid) to check the ability of rare earth ions to lead to high-dimensional materials. The crystal structures of 1 and 2 can be described as a succession of layers made up of chains with regular alternation of pairs of Gd 3+ and Na + or K + ions that are connected by bta 4groups. Both structures contain a nine-coordinated gadolinium(III) cation ion and fully deprotonated bta 4anion. However, the alkaline cations exhibit different coordination numbers, seven (Na + ) and nine (K + ). The structures accommodate crystallization and coordination water molecules, and it was observed that the water molecules have a significant influence on the coordination geometry and on the overall extended structure. These compounds may be considered as novel nanocomposites of unusual structures within the benzenetetracarboxylate frameworks.