A pi-extended, redox-active tetradentate tetrathiafulvalene-fused salphen [salphen = N,N'-phenylenebis(salicylideneimine)] compound (L) was prepared via a direct Schiff-base condensation of the corresponding diamine-tetrathiafulvalene (TTF) precursor with salicylaldehyde. Its chelating coordination ability has been demonstrated by the formation of the corresponding transition metal complexes in the presence of M(OAc)2.nH2O (M = Co(II), Ni(II), Cu(II)) and FeCl3.6H2O. Three complexes have been characterized by single-crystal X-ray diffraction analysis showing that the TTF-salphen ligand coordinates to the metal ions in a planar mode through the nitrogen and oxygen atoms in a N2O2 cis-configuration. In the case of Fe(III), a dinuclear oxo-bridged Fe(III) complex is formed. These paramagnetic complexes are promising building blocks for the construction of dual functional materials due to their unique structural features (planarity and rigidity) as well as their inherent redox properties.

The synthesis, crystal structures and magnetic properties of five new manganese compounds are reported. These include a linear trinuclear cluster [Mn(II)(3)(O(2)CCHMe(2))(6)(dpa)(2)].2MeCN (1) (dpa = 2,2'-dipyridylamine), a tetranuclear cluster [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpy)(2)] (3) (bpy = 2,2'-bipyridine), and chain coordination polymers composed of cluster blocks such as Mn(3), Mn(3)O, and Mn(4)O(2) bridged by 2,2'-bipyrimidine (bpm) or hexamethylentetramine (hmta) ligands to give ([Mn(II)(3)(O(2)CCHMe(2))(6)(bpm)].2EtOH)(n) (2), [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCHMe(2))(6)(bpm)(EtOH)(4)](n) (4), and (([Mn(II)Mn(III)(2)O(O(2)CCHMe(2))(6)(hmta)(2)].EtOH)(n) (5). The magnetic analysis of the compounds was achieved using a combination of vector coupling and full-matrix diagonalization methods. Susceptibility data for compound 1 was fitted using a vector coupling model to give g = 2.02(1) and 2J/k(B) = -5.38(2) K. To model the trimer chain, we used vector coupling for initial values of J(1) and then diagonalization techniques to estimate J(2) to give g = 1.98(1), 2J(1)/k(B) = -3.3(1) K and 2J(2)/k(B) = -1.0(1) K by approximating the system to a dimer of trimers. The analysis of 3 was made difficult by the mixture of polymorphs and the difficulties of a three-J model, while for 4 an analysis was not possible because of the size of the computation and the relative magnitudes of the three couplings. Compound 5 was modeled using the same techniques as 2 to give g = 1.99(1), 2J(1)/k(B) = +32.5(2) K, 2J(2)/k(B) = -16.8(1) K, and 2J(3)/k(B) = +0.4(1) K. The combination of techniques has worked well for compounds 2 and 5 and thus opens up a method of modeling complex chains.

A new discrete [V(16)O(38)(CN)](9-) cluster, which displays the hitherto unknown 8- charge on the cluster shell and is the first to encapsulate the cyanide anion, has been synthesized and characterized by IR and UV/vis/near-IR spectroscopy, electrochemistry, and magnetic susceptibility measurements. Bond valence sum calculations conducted on the basis of the crystal structure analysis of K(9)[V(16)O(38)(CN)]·13H(2)O confirm that this new member of the polyoxovanadate series is a mixed-valence complex. The intervalence charge transfer bands arising from intrametal interactions reveal that a localized (class II) assignment is appropriate for the cluster; however, a small degree of electronic delocalization is present. Interesting possibilities exist for the incorporation of this unit into higher dimensionality framework structures, where the redox, optical, and magnetic properties can be exploited and tuned.

High resolution friction force maps of the benzylammonium terminated crystalline surface of a layer compound are presented. The lateral force map acquired with an atomic force microscope, reveals a significant contrast between different molecular orientations yielding molecular rows which differ from their neighboring ones. The single crystals are formed by stacks of copper oxalate sheets sandwiched between stereoregular organic cations, resulting in highly organized surface structures. Single molecular defects are observed at small loads. The experimental results are compared with numerical calculations which indicate a transition from an unperturbed state at small loads to a distorted state at higher loads.

Figure S1Asymmetric unit and selected symmetry equivalents of 2. Thermal ellipsoids are at the 70 % probability level. Hydrogen atom labels are omitted for clarity. Symmetry operators: i) x, 2−y, z; ii) 1−x, 2−y, −z; iii) 1−x, y, −z; iv) 2−x, y, 1−z; v) x, y, −1+z; vi) 1+x, y, z.

The properties of atmospheric CO2 fixation, metamagnetism, reversible guest adsorption and zero thermal expansion have been combined in a single robust MOF, [Cu3(bpac)3(CO3)2](ClO4)2·H2O (·H2O). This compound is a ditopically-bridged copper carbonate kagome lattice where desolvation of the MOF allows subtle tuning of the metamagnetic and uniaxial ZTE behaviour.

Two new coordination network materials with the composition M(pip)(ox) ( pip = piperazine; ox = oxalate; M = Ni, Cu) have been synthesised under ambient and hydrothermal conditions. These compounds adopt related structures, both consisting of intersecting [M(pip)] ϱ and [M(ox)] ϱ chains, which result in layered structures. The nickel compound crystallises in P1 . The metal ions are octahedrally coordinated and are linked by symmetric chelating bridging oxalate ions. In contrast, the copper compound crystallises in the chiral space group P2 1 2 1 2 1 . Here the copper atom displays square pyramidal coordination geometry and the oxalate ions bridge metals in an unsymmetric fashion resulting in a polar metal-oxalate chain structure. The magnetic behaviour is determined by the nature of the exchange-coupled net-

We report here two series of coordination polymer chains: the first being [M(II)(ox)(bnz)(2)](n) (M = Mn 1, Fe 2, Co 3, Ni 4, Cu 5 and Zn 6; ox = oxalate C(2)O(4)(2-); bnz = benzimidazole) and the second [M(II)(ox)(btz)(2)](n) (M = Mn 7, Fe 8, Co 9, Ni 10, Cu 11 and Zn 12; btz = benzotriazole). The first series displays an unusual homometallic [-M(i)-M(ii)-M(ii)-](n) chain topology and the second series is isostructural to [Fe(II)(ox)(btz)(2)](n), originally reported by Jia et al. (Collect. Czech. Chem. Commun., 2002, 67, 1609-1615). These two series allow us to make comparisons between the spin state of each metal and the magnetic coupling interaction within an isostructural series spanning the full range of spin states available in 3d metals and to investigate which models are the best to use in each case. Compound 8 is a single-chain magnet, the behaviour through spin-canting arising from a Dzyaloshinskii-Moriya interaction. Additionally, we have synthesised a two-dimensional coordination polymer {[Zn(II)(bnz)(4)][Zn(II)(2)(ox)(3)]}(n) (13), in which distorted hexagonal [Zn(II)(2)(ox)(3)](n)(2n-) layers are hydrogen bonded by [Zn(II)(bnz)(4)](2+) cations to give an interlayer separation of 12.001(2) Å.