Homochiral Mn3+ Spin-Crossover Complexes: A Structural and Spectroscopic Study.

Structural, magnetic, and spectroscopic data on a Mn3+ spin-crossover complex with Schiff base ligand 4-OMe-Sal2323, isolated in crystal lattices with five different counteranions, are reported. Complexes of [Mn(4-OMe-Sal2323)]X where X = ClO4- (1), BF4- (2), NO3- (3), Br- (4), and I- (5) crystallize isotypically in the chiral orthorhombic space group P21212 with a range of spin state preferences for the [Mn(4-OMe-Sal2323)]+ complex cation over the temperature range 5-300 K. Complexes 1 and 2 are high-spin, complex 4 undergoes a gradual and complete thermal spin crossover, while complexes 3 and 5 show stepped crossovers with different ratios of spin triplet and quintet forms in the intermediate temperature range. High-field electron paramagnetic resonance was used to measure the zero-field splitting parameters associated with the spin triplet and quintet states at temperatures below 10 K for complexes 4 and 2 with respective values: DS=1 = +23.38(1) cm-1, ES=1 = +2.79(1) cm-1, and DS=2 = +6.9(3) cm-1, with a distribution of E parameters for the S = 2 state. Solid-state circular dichroism (CD) spectra on high-spin complex 1 at room temperature reveal a 2:1 ratio of enantiomers in the chiral conglomerate, and solution CD measurements on the same sample in methanol show that it is stable toward racemization. Solid-state UV-vis absorption spectra on high-spin complex 1 and mixed S = 1/S = 2 sample 5 reveal different intensities at higher energies, in line with the different electronic composition. The statistical prevalence of homochiral crystallization of [Mn(4-OMe-Sal2323)]+ in five lattices with different achiral counterions suggests that the chirality may be directed by the 4-OMe-Sal2323 ligand.

Photophysical Properties and DNA Binding of Two Intercalating Osmium Polypyridyl Complexes Showing Light-Switch Effects.

The synthesis and photophysical characterization of two osmium(II) polypyridyl complexes, [Os(TAP)2dppz]2+ (1) and [Os(TAP)2dppp2]2+ (2) containing dppz (dipyrido[3,2-a:2',3'-c]phenazine) and dppp2 (pyrido[2',3':5,6]pyrazino[2,3-f][1,10]phenanthroline) intercalating ligands and TAP (1,4,5,8-tetraazaphenanthrene) ancillary ligands, are reported. The complexes exhibit complex electrochemistry with five distinct reductive redox couples, the first of which is assigned to a TAP-based process. The complexes emit in the near-IR (1 at 761 nm and 2 at 740 nm) with lifetimes of >35 ns with a low quantum yield of luminescence in aqueous solution (∼0.25%). The Δ and Λ enantiomers of 1 and 2 are found to bind to natural DNA and with AT and GC oligodeoxynucleotides with high affinities. In the presence of natural DNA, the visible absorption spectra are found to display significant hypochromic shifts, which is strongly evident for the ligand-centered π-π* dppp2 transition at 355 nm, which undergoes 46% hypochromism. The emission of both complexes increases upon DNA binding, which is observed to be sensitive to the Δ or Λ enantiomer and the DNA composition. A striking result is the sensitivity of Λ-2 to the presence of AT DNA, where a 6-fold enhancement of luminescence is observed and reflects the nature of the binding for the enantiomer and the protection from solution. Thermal denaturation studies show that both complexes are found to stabilize natural DNA. Finally, cellular studies show that the complexes are internalized by cultured mammalian cells and localize in the nucleus.

Crystal structures of isotypic poly[bis-(benz-imid-azolium) [tetra-µ-iodido-stannate(II)]] and poly[bis-(5,6-di-fluoro-benzimidazolium) [tetra-µ-iodido-stannate(II)]].

The isostructural title compounds, {(C7H7N2)2[SnI4]} n , (1), and {(C7H5F2N2)2[SnI4]} n , (2), show a layered perovskite-type structure composed of anionic {[SnI4](2-)} n sheets parallel to (100), which are decorated on both sides with templating benzimidazolium or 5,6-di-fluoro-benzimidazolium cations, respectively. These planar organic heterocycles mainly form N-H⋯I hydrogen bonds to the terminal I atoms of the corner-sharing [SnI6] octa-hedra (point group symmetry 2) from the inorganic layer, but not to the bridging ones. This is in contrast to most of the reported structures of related compounds where ammonium cations are involved. Here hydrogen bonding to both types of iodine atoms and thereby a distortion of the inorganic layers to various extents is observed. For (1) and (2), all Sn-I-Sn angles are linear and no out-of-plane distortions of the inorganic layers occur, a fact of relevance in view of the material properties. The arrangement of the aromatic cations is mainly determined through the direction of the N-H⋯I hydrogen bonds. The coherence between organic bilayers along [100] is mainly achieved through van der Waals inter-actions.

Crystal structure and Hirshfeld surface of a penta-amine-copper(II) complex with urea and chloride.

The reaction of copper(II) oxalate and hexa-methyl-ene-tetra-mine in a deep eutectic solvent made of urea and choline chloride produced crystals of penta-amine-copper(II) dichloride-urea (1/1), [Cu(NH3)5]Cl2·CO(NH2)2, which was characterized by single-crystal X-ray diffraction. The complex contains discrete penta-amine-copper(II) units in a square-based pyramidal geometry. The overall structure of the multi-component crystal is dictated by hydrogen bonding between urea mol-ecules and amine H atoms with chloride anions.

Physicochemical Modeling of Electrochemical Impedance in Solid-State Supercapacitors.

Solid-state supercapacitors (SSCs) consist of porous carbon electrodes and gel-polymer electrolytes and are used in novel energy storage applications. The current study aims to simulate the impedance of SSCs using a clearly defined equivalent circuit (EC) model with the ultimate goal of improving their performance. To this end, a conventional mathematical and a physicochemical model were adapted. The impedance was measured by electrochemical impedance spectroscopy (EIS). An EC consisting of electrical elements was introduced for each modeling approach. The mathematical model was purely based on a best-fit method and utilized an EC with intuitive elements. In contrast, the physicochemical model was motivated by advanced theories and allowed meaningful associations with properties at the electrode, the electrolyte, and their interface. The physicochemical model showed a higher approximation ability (relative error of 3.7%) due to the interface impedance integration in a more complex circuit design. However, this model required more modeling and optimization effort. Moreover, the fitted parameters differed from the analytically calculated ones due to uncertainties in the SSC's microscale configuration, which need further investigations. Nevertheless, the results show that the proposed physicochemical model is promising in simulating EIS data of SSCs with the additional advantage of utilizing well-reasoned property-based EC elements.

[V16O38(CN)]9­: a soluble mixed-valence redox-active building block with strong antiferromagnetic coupling.

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.

Crystal structure and halogen-hydrogen bonding of a Delépine reaction inter-mediate.

The reaction of 1,5-di-bromo-pentane with urotropine results in crystals of the title mol-ecular salt, 5-bromo-urotropinium bromide [systematic name: 1-(5-bro-mo-pent-yl)-3,5,7-tri-aza-1-azoniatri-cyclo-[3.3.1.13,7]decane bromide], C11H22BrN4 +·Br- (1), crystallizing in space group P21/n. The packing in compound 1 is directed mainly by H⋯H van der Waals inter-actions and C-H⋯Br hydrogen bonds, as revealed by Hirshfeld surface analysis. Comparison with literature examples of alkyl-urotropinium halides shows that the inter-actions in 1 are consistent with those in other bromides and simple chloride and iodide species.

All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer.

The role of ligand basicity in complex formation has been investigated using monodentate pyridyls or benzimidazole (mP) in combination with a solution-stable species derived form a coordination polymer, [Cu(L)] (where L = 2-(2-hydroxybenzylidene-amino)phenol). The 12 [Cu(L)(mP)n] complexes generated, combined with the {[Cu(L)]2(pP)} complexes from our previous work (where pP is a polypyridyl ligand), allow us to gauge the likelihood of complex formation based on the pKa of the conjugate acid of the pyridyl ligands and Hammett parameter, σ. Above pKa ≈ 4.5, complexes are formed where the only ligands are L2- and mP or pP and the packing interactions are predominantly van der Waals. Below this value, complex formation is unlikely unless there are additional oxygen ligands in the Jahn-Teller axis of the Cu(ii) ion. The structures of two literature [Cu(L)(bP)] complexes, where bP is a chelating bidentate pyridyl ligand are also re-examined to resolve the positional disorder in the [Cu(L)] moiety.

One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and 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.

Di-µ-acetato-µ-aqua-bis-[acetatobis(1H-benzimidazole)cobalt(II)].

In the title compound, [Co(2)(C(2)H(3)O(2))(4)(C(7)H(6)N(2))(4)(H(2)O)], the half-mol-ecule in the asymmetric unit is completed by a crystallographic twofold rotation axis to give the full mol-ecule. The Co(II) ions are approximately octahedrally coordinated with a cis-N(2)O(4) coordination sphere. The compound features intra-molecular O-H⋯O hydrogen bonds between the non-bridging acetate groups and the bridging water mol-ecule, and inter-molecular N-H⋯O hydrogen bonds between the acetates and amine H atoms of the benzimidazoles which determine the mol-ecular packing in the crystal structure.

Hydrogen-bonding chain and dimer motifs in pyridinium and morpholinium hydrogen oxalate salts.

We present here three compounds consisting of pyridinium or morpholinium hydrogen oxalates, each displaying different hydrogen-bonding motifs, resulting in chains for 4-(di-methyl-amino)-pyridinium hydrogen oxalate 0.22-hydrate, C7H11N2 +·C2HO4 -·0.22H2O (1), dimers for 4-tert-butyl-pyridinium hydrogen oxalate, C9H14N+·C2HO4 - (2), and chains for morpholin-ium hydrogen oxalate, C4H10NO+·C2HO4 - (3).

Crystal structure and hydrogen bonding in the hydrated cocrystalline salt tryptaminium-3,5-dinitrobenzoate-quinoline-water (3/3/2/2).

The study of ternary systems is interesting because it introduces the concept of molecular preference/competition into the system where one molecule may be displaced because the association between the other two is significantly stronger. Current definitions of a tertiary system indicate that solvent molecules are excluded from the molecule count of the system and some of the latest definitions state that any molecule that is not a solid in the parent form at room temperature should also be excluded from the molecule count. In the structure of the quinoline adduct hydrate of tryptaminium 3,5-dinitrobenzoate, 3C10H13N2+·3C7H3N2O6-·2C9H7N·2H2O, the asymmetric unit comprises multiple cation and anion species which are conformationally similar among each type set. In the crystal, a one-dimensional hydrogen-bonded supramolecular structure is generated through extensive intra- and inter-unit aminium N-H...O and N-H...N, and water O-H...O hydrogen bonds. Within the central-core hydrogen-bonding associations, conjoined cyclic R44(10), R53(10) and R44(12) motifs are generated. The unit is expanded into a one-dimensional column-like polymer extending along [010]. Present also in the crystal packing of the structure are a total of 19 π-π interactions involving both cation, anion and quinoline species [ring-centroid separation range = 3.395 (3)-3.797 (3) Å], as well as a number of weak C-H...O hydrogen-bonding associations. The presence of the two water molecules in the crystal structure is considered to be the principal causative factor in the low symmetry of the asymmetric unit.

Molecular Pac-Man and Tacos: layered Cu(II) cages from ligands with high binding site concentrations.

The in situ formation and subsequent Cu(ii) ligation of the polydentate pro-ligands o-[(E)-(2-hydroxy-3-methoxyphenyl)methylideneamino]benzohydroxamic acid (L1H3), o-[(E)-(2-hydroxy-3-methoxy-5-bromophenyl)methylideneamino]benzohydroxamic acid (L2H3) and o-[(E)-(2-hydroxyphenyl)methylideneamino]benzohydroxamic acid (L3H3), leads to the self-assembly of the cages [Cu(ii)10(L1)4(2-aph)2(H2O)2](ClO4)4·5MeOH (), [Cu(ii)14(L1)8(MeOH)2.5(H2O)7.5](NO3)4·3MeOH·7H2O (), [Cu(ii)14(L2)8(MeOH)4(H2O)6](NO3)4·6H2O (), [Cu(ii)14(L3)8(MeOH)6(H2O)2](NO3)4·4MeOH·8H2O () and [Cu(ii)30O(OH)4(OMe)2(L1)16(MeOH)4(H2O)2](ClO4)4·2MeOH·30H2O (). Each member comprises a highly unusual topology derived from off-set, stacked, near planar layers of polynuclear subunits connected through long Cu(ii)-O contacts. The exact topology observed is dependent on the specific reaction conditions and methodologies employed. Dc magnetic susceptibility studies on , , and reveals strong antiferromagnetic exchange between the Cu(ii) centres in all siblings. We also present the 1D coordination polymer {[Cu(ii)(L4)]·H2O}n () comprising the pseudo macrocyclic ligand [[2-[(E)-(2-hydroxy-3-methoxy-phenyl)methyleneamino]benzoyl]amino]ethanimidate (L4H2), which is formed upon the incorporation of an MeCN unit at the hydroxamate group of precursor ligand L1H3.

Multifunctional MOFs through CO2 fixation: a metamagnetic kagome lattice with uniaxial zero thermal expansion and reversible guest sorption.

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.

Solvent-modified dynamic porosity in chiral 3D kagome frameworks.

Dynamically porous metal-organic frameworks (MOFs) with a chiral quartz-based structure have been synthesized from the multidentate ligand 2,2'-dihydroxybiphenyl-4,4'-dicarboxylate (H2diol). Compounds [Ni(II)(H2diol)(S)2]·xS (where S = DMF or DEF) show marked changes in 77 K N2 uptake between partially desolvated [Ni(II)(H2diol)(S)2] (only the pore solvent is removed) and fully desolvated [Ni(II)(H2diol)] forms. Furthermore, [Ni(II)(H2diol)(DMF)2] displays additional solvent-dependent porosity through the rotation of DMF molecules attached to the axial coordination sites of the Ni(II) centre. A unique feature of the four coordinate Ni(II) centre in [Ni(II)(H2diol)] is the dynamic response to its chemical environment. Exposure of [Ni(II)(H2diol)] to H2O and MeOH vapour leads to coordination of both axial sites of the Ni centres and to the generation of a solvated framework, whereas exposure to EtOH, DMF, acetone, and MeCN does not lead to any change in metal coordination or structure metrics. MeOH vapour adsorption was able to be tracked by time-dependent magnetometry as the solvated and desolvated structures have different magnetic moments. Solvated and desolvated forms of the MOF show remarkable differences in their thermal expansivities; [Ni(II)(H2diol)(DMF)2]·DMF displays marked positive thermal expansion (PTE) in the c-axis, yet near to zero thermal expansion, between 90 and 450 K, is observed for [Ni(II)(H2diol)]. These new MOF architectures demonstrate a dynamic structural and colourimetric response to selected adsorbates via a unique mechanism that involves a reversible change in the coordination environment of the metal centre. These coordination changes are mediated throughout the MOF by rotational mobility about the biaryl bond of the ligand.

Laboratory-based separation techniques for insoluble compound mixtures: methods for the purification of metal-organic framework materials.

In this article, techniques for separating mixtures of insoluble compounds are discussed with respect to the small quantities found in laboratory preparations, as opposed to industrial quantities. The techniques include separations based on density, surface area and differences in particle size. Also discussed are simple apparatus, readily available in the laboratory or from commercial suppliers, for achieving these techniques.

Structure and magnetism of new hybrid cobalt hydroxide materials built from decorated brucite layers.

The structure, synthesis and magnetic properties of three new complex cobalt hydroxyl oxalates are presented, showing a modification of the 2-D double layer hydroxide structure. Co(12)(OH)(18)(ox)(3)(pip) [ox = oxalate, C(2)O(4)(2-); pip = piperazine, C(4)N(2)H(10)] (1), is essentially built from brucite-like layers with a one ninth depletion of the octahedral sites and a preservation of a trigonal crystallographic symmetry. ACo(28)(OH)(43)(ox)(6)Br(2)(H(2)O)(2) [A = Na (2), K (3)] are similarly composed of a brucite-like layer with three nineteenths depletion of octahedral sites, again preserving a trigonal symmetry. Both 2 and 3 show a small degree of structural disorder within the framework. All of these compounds have alternating layers of a mineral-like metal hydroxide structure and a metal oxalate coordination network, with the depletion in the hydroxyl layers being templated by the coordination network. Magnetic studies of 1 reveal a metamagnetic character, with the onset of an antiferromagnetic phase below T(c) = 23.5 K (H = 0 G), and a first order antiferromagnet to metamagnet transition at H(c) = 500-1000 G (T = 20-6 K). Compound 3 shows a more conventional ferrimagnetic ordering below 33(±1) K with a small coercive field of 107(±5) G at 10 K.

A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups.

Cyanidometallate complexes are highly versatile building units for the generation of functional porous materials. Here we report five new pillared Hofmann layer compounds incorporating the tetracyanidometallates [MoO(CN)(4)](2-) and [MnN(CN)(4)](2-). These metalloligands, which are new to this class of materials, have been combined with divalent 1st-row transition metals to produce Hofmann layers that are linked into three-dimensional frameworks by ditopic bridging dipyridyls. We report the structures and anomalous thermal expansion properties of five new materials: [Mn(H(2)O)(bpy)(½){MoO(CN)(4)(bpy)(½)}]·2H(2)O (1), [Mn(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (2), [Fe(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (3), [Co(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (4) and [{Mn(H(2)O)(2)}(½){Mn(bpa)(2)}(½){MoO(CN)(4)(bpa)(½)}]·MeOH (5), (where bpy = 4,4'-bipyridine and bpa = 4,4'-bipyridylacetylene).

Self-assembled Co(II) molecular squares incorporating the bridging ligand 4,7-phenanthrolino-5,6:5',6'-pyrazine.

Three high-spin tetranuclear cobalt(II) complexes have been prepared with the bridging ligand 4,7-phenanthrolino-5,6:5',6'-pyrazine (ppz) through metal-ion directed self-assembly. The complexes differ by the incorporation of three different coordinating anions: chloride, thiocyanide and selenocyanide. The physical properties of these complexes have been investigated in detail.

Half a grid is better than no grid: competition between 2,2':6',2''-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(II).

The reaction between Cu(NO(3))(2).3H(2)O, 2,2':6',2''-terpyridine (tpy) and 3,6-di(pyrid-2-yl)pyridazine (1) in a 2 : 2 : 1 molar equivalent ratio in aqueous MeCN in the presence of excess NH(4)PF(6) leads to competition between the assembly of the dinuclear half-grid [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O and the mononuclear complex [Cu(1)(2)(OH(2))][PF(6)](2). The yield of [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O has been optimized using microwave conditions. [Cu(1)(2)(OH(2))][PF(6)](2) can be selectively produced by treating Cu(NO(3))(2).3H(2)O with 1 (1 : 2 molar equivalents) in aqueous MeCN in the presence of NH(4)PF(6). The single crystal structures of [Cu(2)(1)(tpy)(2)][PF(6)](4).4MeNO(2) and [Cu(1)(2)(OH(2))][PF(6)](2) are presented. In the [Cu(2)(1)(tpy)(2)](4+) cation, ligand 1 bridges the two copper(II) centres, each of which is further coordinated by a tpy ligand. The copper(II) coordination geometry is closely associated with the arrangement of the two tpy ligands which engage in efficient face-to-face pi-stacking. Magnetic data for crystalline [Cu(2)(1)(tpy)(2)][PF(6)](4).4MeNO(2) are consistent with a weak antiferromagnetic interaction between the two copper(II) centres. EPR spectroscopic data for a powder sample of [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O are consistent with the dinuclear structure, but in frozen DMF and DMSO solutions, the data indicate that the dinuclear structure of [Cu(2)(1)(tpy)(2)](4+) is not preserved.