A Porous Chalcogen-Bonded Organic Framework.

The manner of bonding between constituent atoms or molecules invariably influences the properties of materials. Perhaps no material family is more emblematic of this than porous frameworks, wherein the namesake modes of connectivity give rise to discrete subclasses with unique collections of properties. However, established framework classes often display offsetting advantages and disadvantages for a given application. Thus, there exists no universally applicable material, and the discovery of alternative modes of framework connectivity is highly desirable. Here we show that chalcogen bonding, a subclass of σ-hole bonding, is a viable mode of connectivity in low-density porous frameworks. Crystallization studies with the triptycene tris(1,2,5-selenadiazole) molecular tecton reveal how chalcogen bonding can template high-energy lattice structures and how solvent conditions can be rationalized to obtain molecularly programmed porous chalcogen-bonded organic frameworks (ChOFs). These results provide the first evidence that σ-hole bonding can be used to advance the diversity of porous framework materials.

New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties.

Interactions between well-mixed fine powders of As2O3, P2O5, MoO3, WO3 and Nb2O5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N2 and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals' electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids' practical usefulness are discussed.

Hydrating the Bispropionate Notch in Malaria Pigment: A New Structural Motif in the Iron(III)(deuteroporphyrin) Dimer.

Treating deuterohemin, chloro(deuteroporphyrinato)iron(III), with a non-coordinating base in DMSO/methanol allows for the isolation of [(deuteroporphyrinato)iron(III)]2 , deuterohematin anhydride (DHA), an analogue of malaria pigment, the natural product of heme detoxification by malaria. The structure of DHA obtained from this solvent system has been solved by X-ray powder diffraction analysis and displays many similarities, yet important structural differences, to malaria pigment. Most notably, a water molecule of solvation occupies a notch created by the propionate side chains and stabilizes a markedly bent propionate ligand coordinated with a long Fe-O bond, and a carboxylate cluster associated with water molecules is generated. Together, these features account for its increased solubility and more open structure, with an increased porphyrin-porphyrin separation. The IR spectroscopic signature associated with this structure also accounts for the strong IR band at 1587 cm-1 seen for many amorphous preparations of synthetic malaria pigment, and it is proposed that stabilizing these structures may be a new objective for antimalarial drugs. The important role of the vinyl substituents in this biochemistry is further demonstrated by the structure of deuterohemin obtained by single-crystal X-ray diffraction analysis.

Hydrogen-Bonding Effects in Five-Coordinate High-Spin Imidazole-Ligated Iron(II) Porphyrinates.

The influence of hydrogen binding to the N-H group of coordinated imidazole in high-spin iron(II) porphyrinates has been studied. The preparation and characterization of new complexes based on [Fe(TPP)(2-MeHIm)] (TPP is the dianion of tetraphenylporphyrin) are reported. The hydrogen bond acceptors are ethanol, tetramethylene sulfoxide, and 2-methylimidazole. The last acceptor, 2-MeHIm, was found in a crystalline complex with two [Fe(TPP)(2-MeHIm)] sites, only one of which has the 2-methylimidazole hydrogen bond acceptor. This latter complex has been studied by temperature-dependent Mössbauer spectroscopy. All new complexes have also been characterized by X-ray structure determinations. The Fe-NP and Fe-NIm bond lengths, and displacement of the Fe atom out of the porphyrin plane are similar to, but marginally different than, those in imidazole-ligated species with no hydrogen bond. All the structural and Mössbauer properties suggest that these new hydrogen-bonded species have the same electronic configuration as imidazole-ligated species with no hydrogen bond. These new studies continue to show that the effects of hydrogen bonding in five-coordinate high-spin iron(II) systems are subtle and challenging to understand.

Chemical Stabilization and Electrochemical Destabilization of the Iron Keggin Ion in Water.

The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular, nonclassical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated as [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2]3+ (Kegg-1) and [Bi6FeO4Fe12O12(OH)12(CF3COO)12]1+ (Kegg-2). Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pH 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi3+ cations and the trifluoroacetate ligands that, respectively, bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster to metal oxide conversion processes in detail.

Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical.

Properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF4(-) anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ∼0.1 V upon going from 1 to 1a. Unsuccessful attempts to prepare several other aryl substituted derivatives of 1 by the classical synthetic route are described in the Supporting Information .

C(sp3 )-H Oxidative Addition and Transfer Hydrogenation Chemistry of a Titanium(II) Synthon: Mimicry of Late-Metal Type Reactivity.

Two-electron reduction of the TiIV compound (ket guan)(ImDipp N)Ti(OTf)2 (3) gives the arene-masked complex (ket guan)(η6 -ImDipp N)Ti (1) in excellent yield. Upon standing in solution, 1 converts to a TiIV metallacycle (4) through dehydrogenation of a pendant isopropyl group. Spectroscopic evidence shows this transformation initially proceeds via the oxidative addition of a C(sp3 )-H bond and can be reversed upon exposure of 4 to H2 . Interestingly, treatment of 1 with cyclohexene gives cyclohexane and 4 via a titanium-mediated transfer hydrogenation reaction, a process that can be extended to catalytically hydrogenate other unsaturated hydrocarbons under mild conditions. These results, rare for the early-metals, suggest 1 possesses chemical characteristics reminiscent of noble, late-metals.

Au133(SPh-tBu)52 nanomolecules: X-ray crystallography, optical, electrochemical, and theoretical analysis.

Crystal structure determination has revolutionized modern science in biology, chemistry, and physics. However, the difficulty in obtaining periodic crystal lattices which are needed for X-ray crystal analysis has hindered the determination of atomic structure in nanomaterials, known as the "nanostructure problem". Here, by using rigid and bulky ligands, we have overcome this limitation and successfully solved the X-ray crystallographic structure of the largest reported thiolated gold nanomolecule, Au133S52. The total composition, Au133(SPh-tBu)52, was verified using high resolution electrospray ionization mass spectrometry (ESI-MS). The experimental and simulated optical spectra show an emergent surface plasmon resonance that is more pronounced than in the slightly larger Au144(SCH2CH2Ph)60. Theoretical analysis indicates that the presence of rigid and bulky ligands is the key to the successful crystal formation.

Bis(cyano) Iron(III) Porphyrinates: What Is the Ground State?

The synthesis of six new bis(cyano) iron(III) porphyrinate derivatives is reported. The anionic porphyrin complexes utilized tetraphenylporphyrin, tetramesitylporphyrin, and tetratolylporphyrin as the porphyrin ligand. The potassium salts of Kryptofix-222 and 18-C-6 were used as the cations. These complexes have been characterized by X-ray structure analysis, solid-state Mössbauer spectroscopy, and EPR spectroscopy, both in frozen CH2Cl2 solution and in the microcrystalline state. These data show that these anionic complexes can exist in either the (dxz,dyz)(4)(dxy)(1) or the (dxy)(2)(dxz,dyz)(3) electronic configuration and some can clearly readily interconvert. This is a reflection that these two states can be very close in energy. In addition to the effects of varying the porphyrin ligand, subtle effects of the cyanide ligand environment in the solid state and in solution are sufficient to shift the balance between the two electronic states.

Santal monohydrate, an isoflavone isolated from Wye-thia mollis.

THE TITLE COMPOUND [SYSTEMATIC NAME: 3-(3,4-di-hydroxy-phen-yl)-5-hy-droxy-7-meth-oxy-4H-chromen-4-one monohydrate], C16H12O6·H2O, is a monohydrate of a natural product santal isolated from Wye-thia mollis. In the santal mol-ecule, the dihedral angle between the benzo-quinone and di-hydroxy-phenyl fragments is 53.9 (1)° and an intra-molecular O-H⋯O hydrogen bond occurs. In the crystal, O-H⋯O hydrogen bonds link the components into corrugated layers parallel to the ac plane. The short distance of 3.474 (5) Šbetween the centroids of the benzene rings in neighbouring santal mol-ecules reveals then existence of π-π inter-actions within the layers.

A tetrameric cage with D2h symmetry through alkyne metathesis.

Shape-persistent covalent organic polyhedrons (COPs) with ethynylene linkers are usually prepared through kinetically controlled cross-coupling reactions. The high-yielding synthesis of ethynylene-linked rigid tetrameric cages via one-step alkyne metathesis from readily accessible triyne precursors is presented. The tetrameric cage contains two macrocyclic panels and exhibits D2h symmetry. The assembly of such a COP is a thermodynamically controlled process, which involves the initial formation of macrocycles as key intermediates followed by the connection of two macrocycles with ethynylene linkages. With a large internal cavity, the cage exhibits a high binding selectivity toward C70 (K = 3.9×10(3) L mol(-1)) over C60 (no noticeable binding).

Correlated ligand dynamics in oxyiron picket fence porphyrins: structural and Mössbauer investigations.

Disorder in the position of the dioxygen ligand is a well-known problem in dioxygen complexes and, in particular, those of picket fence porphyrin species. The dynamics of Fe-O2 rotation and tert-butyl motion in three different picket fence porphyrin derivatives has been studied by a combination of multitemperature X-ray structural studies and Mössbauer spectroscopy. Structural studies show that the motions of the dioxygen ligand also require motions of the protecting pickets of the ligand binding pocket. The two motions appear to be correlated, and the temperature-dependent change in the O2 occupancies cannot be governed by a simple Boltzmann distribution. The three [Fe(TpivPP)(RIm)(O2)] derivatives studied have RIm = 1-methyl-, 1-ethyl-, or 2-methylimidazole. In all three species there is a preferred orientation of the Fe-O2 moiety with respect to the trans imidazole ligand and the population of this orientation increases with decreasing temperature. In the 1-MeIm and 1-EtIm species the Fe-O2 unit is approximately perpendicular to the imidazole plane, whereas in the 2-MeHIm species the Fe-O2 unit is approximately parallel. This reflects the low energy required for rotation of the Fe-O2 unit and the small energy differences in populating the possible pocket quadrants. All dioxygen complexes have a crystallographically required 2-fold axis of symmetry that limits the accuracy of the determined Fe-O2 geometry. However, the 80 K structure of the 2-MeHIm derivative allowed for resolution of the two bonded oxygen atom positions and provided the best geometric description for the Fe-O2 unit. The values determined are Fe-O = 1.811(5) Å, Fe-O-O = 118.2(9)°, O-O = 1.281(12) Å, and an off-axis tilt of 6.2°. Demonstration of the off-axis tilt is a first. We present detailed temperature-dependent simulations of the Mössbauer spectra that model the changing value of the quadrupole splitting and line widths. Residuals to fits are poorer at higher temperature. We believe that this is consistent with the idea that population of the two conformers is related to the concomitant motions of both Fe-O2 rotations and motions of the protecting tert-butyl pickets.

Use of silver carbonate in the Wittig reaction.

An efficient synthesis of olefins by the coupling of stabilized, semistabilized, and nonstabilized phosphorus ylides with various carbonyl compounds in the presence of silver carbonate is reported. Wittig olefination of aromatic, heteroaromatic, and aliphatic aldehydes (yields >63%) and a ketone (yield 42%) are demonstrated. These reactions proceed overnight at room temperature, under weakly basic conditions, and as such extend the applicability of the Wittig reaction to base-sensitive reactants.

5-Benz-yloxy-3-methyl-1-tosyl-1H-indole.

The title compound, C23H21NO3S, represents one of the few examples of a 5-substituted indole with a toluene-sulfonyl group bonded to the N atom. The benzyl group adopts a synclinal geometry with respect to the indole ring [dihedral angle = 59.95 (4)°], while the tolyl ring is oriented close to perpendicular to the indole ring, making a dihedral angle of 81.85 (3)°. The indole N atom exhibits a slight pyramidalization.

(2R,2'S)-2,2'-Bi-piperidine-1,1'-diium dibromide.

The title compound, C10H22N2 (2+)·2Br(-), was synthesized via reduction of 2,2'-dipyridyl with Ni-Al alloy/KOH, followed by separation of diastereoisomers (meso and rac) by recrystallization from ethanol. Although the two bridging C atoms are optically active, these two chiral centers adopt an (S,R) configuration; thus, the title compound contains an achiral meso form of 2,2'-bi-piperidine. Both of the piperidinium rings adopt chair conformations, and the two N atoms are trans to each other; an inversion center is located in the mid-point of the central C-C bond. The conformation of the organic moiety resembles that of 1,1'-bi(cyclo-hexa-ne). The organic di-ammonium cations are linked to each other through hydrogen bonding with bromide counter-ions, each of which forms two hydrogen bonds (N-H⋯Br) with two adjacent organic cations, thus linking the latter together in sheets parallel to (100).

Tenulin 0.25-hydrate, a sesquiterpene lactone isolated from Helenium amarum.

The asymmetric unit of the title compound, C17H22O5·0.25H2O [systematic name: 2-hy-droxy-2,2a,6,9a-tetra-methyl-2a,4a,5,6,6a,9a,9b,9c-octa-hydro-2H-1,4-dioxadi-cyclo-pent[cd,f]azulene-3,9-dione 0.25-hydrate], a natural product isolated from Helenium amarum, contains two independent tenulin mol-ecules and half a water mol-ecule of crystallization situated on a twofold rotation axis. The hy-droxy group of the hemiketal moiety is in a ß-position. In the crystal, each water mol-ecule inter-acts with four tenulin mol-ecules via O-H⋯O hydrogen bonds. The two independent tenulin mol-ecules (A and B) differ only in the character of their participation in hydrogen bonding. Specifically, while A is an acceptor of Owater-H⋯O A and a donor of O A -H⋯O B hydrogen bonds, mol-ecule B is an acceptor of the latter hydrogen bond and the donor of an O B -H⋯Owater hydrogen bond. In the crystal, these O-H⋯O hydrogen bonds link the tenulin and water mol-ecules into layers parallel to the ac plane.

Structural insights into ligand dynamics: correlated oxygen and picket motion in oxycobalt picket fence porphyrins.

Two different oxygen-ligated cobalt porphyrins have been synthesized and the solid-state structures have been determined at several temperatures. The solid-state structures provide insight into the dynamics of Co-O(2) rotation and correlation with protecting group disorder. [Co(TpivPP)(1-EtIm)(O(2))] (TpivPP = picket fence porphyrin) is prepared by oxygenation of [Co(TpivPP)(1-EtIm)(2)] in benzene solution. The structure at room temperature has the oxygen ligand within the ligand binding pocket and disordered over four sites and the trans imidazole is disordered over two sites. The structure at 100 K, after the crystal has been carefully annealed to yield a reversible phase change, is almost completely ordered. The phase change is reversed upon warming the crystal to 200 K, whereupon the oxygen ligand is again disordered but with quite unequal populations. Further warming to 300 K leads to greater disorder of the oxygen ligands with nearly equal O(2) occupancies at all four positions. The disorder of the tert-butyl groups of the protecting pickets is correlated with rotation of the O(2) around the Co-O(O(2)) bond. [Co(TpivPP)(2-MeHIm)(O(2))] is synthesized by a solid-state oxygenation reaction from the five-coordinate precursor [Co(TpivPP)(2-MeHIm)]. Exposure to 1 atm of O(2) leads to incomplete oxygenation, however, exposure at 5 atm yields complete oxygenation. Complete oxygenation leads to picket disorder whereas partial (40%) oxygenation does not. Crystallinity is retained on complete degassing of oxygen in the solid, and complete ordering of the pickets is restored. The results should provide basic information needed to better model M-O(2) dynamics in protein environments.

Semiquinone-bridged bisdithiazolyl radicals as neutral radical conductors.

Semiquinone-bridged bisdithiazolyls 3 represent a new class of resonance-stabilized neutral radical for use in the design of single-component conductive materials. As such, they display electrochemical cell potentials lower than those of related pyridine-bridged bisdithiazolyls, a finding which heralds a reduced on-site Coulomb repulsion U. Crystallographic characterization of the chloro-substituted derivative 3a and its acetonitrile solvate 3a·MeCN, both of which crystallize in the polar orthorhombic space group Pna2(1), revealed the importance of intermolecular oxygen-to-sulfur (CO···SN) interactions in generating rigid, tightly packed radical π-stacks, including the structural motif found for 3a·MeCN in which radicals in neighboring π-stacks are locked into slipped-ribbon-like arrays. This architecture gives rise to strong intra- and interstack overlap and hence a large electronic bandwidth W. Variable-temperature conductivity measurements on 3a and 3a·MeCN indicated high values of σ(300 K) (>10(-3) S cm(-1)) with correspondingly low thermal activation energies E(act), reaching 0.11 eV in the case of 3a·MeCN. Overall, the strong performance of these materials as f = ½ conductors is attributed to a combination of low U and large W. Variable-temperature magnetic susceptibility measurements were performed on both 3a and 3a·MeCN. The unsolvated material 3a orders as a spin-canted antiferromagnet at 8 K, with a canting angle φ = 0.14° and a coercive field H(c) = 80 Oe at 2 K.

2-(Thio-phen-2-yl)-1-(thio-phen-2-ylmeth-yl)-1H-benzimidazole.

In the title compound, C(16)H(12)N(2)S(2), the thio-phene groups are rotationally disordered over two sets of sites, by approximately 180°, with occupancy ratios of 0.916 (2):0.084 (2) and 0.903 (2):0.097 (2). The major components of the thio-phene and methyl-ene substituted thio-phene rings are canted by 24.06 (12) and 85.07 (10)°, respectively, from the benzimidazole ring system plane and the dihedral angle between the major component thio-phene ring planes is 84.90 (14)°. In the crystal, there is a weak C-H⋯N hydrogen bond which links mol-ecules into chains.

Bis(1,4,7-trithia-cyclo-nona-ne)nickel(II) bis-(tetra-fluorido-borate) nitro-methane disolvate.

The homoleptic thio-ether title complex, [Ni(C(6)H(12)S(3))(2)](BF(4))(2)·2CH(3)NO(2), shows the expeced hexa-kis-(thio-ether) octa-hedral environment around the Ni(II) atom. It crystallized as two crystallographically independent complex cations, [Ni(9S3)(2)](2+) (9S3 = 1,4,7-trithia-cyclo-nona-ne), within the unit cell where each Ni(II) lies on an inversion center. In addition to the complex cations, there are two crystallographically independent BF(4) (-) anions present to balance the charge, and each shows disorder along a pseudo-C(3) axis with ratios of 0.53 (2):0.47 (2) and 0.55 (2):0.45 (2). Two nitro-methane solvent mol-ecules per complex cation are also present in the unit cell.