Supramolecular hydrogen-bonded networks formed from copper(II) carboxylate dimers.

The well-known copper carboxylate dimer, with four carboxylate ligands extending outwards towards the corners of a square, has been employed to generate a series of crystalline compounds. In particular, this work centres on the use of the 4-hydroxybenzoate anion (Hhba-) and its deprotonated phenolate form 4-oxidobenzoate (hba2-) to obtain complexes with the general formula [Cu2(Hhba)4-x(hba)xL2-y]x-, where L is an axial coligand (including solvent molecules), x = 0, 1 or 2, and y = 0 or 1. In some cases, short hydrogen bonds result in complexes which may be represented as [Cu2(Hhba)2(H0.5hba)2L2]-. The main focus of the investigation is on the formation of a variety of extended networks through hydrogen bonding and, in some crystals, coordinate bonds when bridging coligands (L) are employed. Crystals of [Cu2(Hhba)4(dioxane)2]·4(dioxane) consist of the expected Cu dimer with the Hhba- anions forming hydrogen bonds to 1,4-dioxane molecules which block network formation. In the case of crystals of composition [Et4N][Cu2(Hhba)2(H0.5hba)2(CH3OH)(H2O)]·2(dioxane), Li[Cu2(Hhba)2(H0.5hba)2(H2O)2]·3(dioxane)·4H2O and [Cu2(Hhba)2(H0.5hba)2(H0.5DABCO)2]·3CH3OH (DABCO is 1,4-diazabicyclo[2.2.2]octane), square-grid hydrogen-bonded networks are generated in which the complex serves as one type of 4-connecting node, whilst a second 4-connecting node is a hydrogen-bonding motif assembled from four phenol/phenolate groups. Another two-dimensional (2D) network based upon a related square-grid structure is formed in the case of [Et4N]2[Cu2(Hhba)2(hba)2(dioxane)2][Cu2(Hhba)4(dioxane)(H2O)]·CH3OH. In [Cu2(Hhba)4(H2O)2]·2(Et4NNO3), a square-grid structure is again apparent, but, in this case, a pair of nitrate anions, along with four phenolic groups and a pair of water molecules, combine to form a second type of 4-connecting node. When 1,8-bis(dimethylamino)naphthalene (bdn, `proton sponge') is used as a base, another square-grid network is generated, i.e. [Hbdn]2[Cu2(Hhba)2(hba)2(H2O)2]·3(dioxane)·H2O, but with only the copper dimer complex serving as a 4-connecting node. Complex three-dimensional networks are formed in [Cu2(Hhba)4(O-bipy)]·H2O and [Cu2(Hhba)4(O-bipy)2]·2(dioxane), where the potentially bridging 4,4'-bipyridine N,N'-dioxide (O-bipy) ligand is employed. Rare cases of mixed carboxylate copper dimer complexes were obtained in the cases of [Cu2(Hhba)3(OAc)(dioxane)]·3.5(dioxane) and [Cu2(Hhba)2(OAc)2(DABCO)2]·10(dioxane), with each structure possessing a 2D network structure. The final compound reported is a simple hydrogen-bonded chain of composition (H0.5DABCO)(H1.5hba), formed from the reaction of H2hba and DABCO.

Complexes of 2,4,6-trihydroxybenzoic acid: effects of intramolecular hydrogen bonding on ligand geometry and metal binding modes.

This article describes a series of more than 20 new compounds formed by the combination of 2,4,6-trihydroxybenzoic acid (H4thba) with metal ions in the presence of a base, with structures that include discrete molecular units, chains, and two- and three-dimensional networks. As a result of the presence of two ortho-hydroxy groups, H4thba is a relatively strong acid (pKa1 = 1.68). The carboxylate group in H3thba- is therefore considerably less basic than most carboxylates with intramolecular hydrogen bonds, conferring a rigid planar geometry upon the anion. These characteristics of H3thba- significantly impact upon the way it interacts with metal ions. In s-block metal compounds, where the interaction of the metal centres with the carboxylate O atoms is essentially ionic, the anion bonds to up to three metal centres via a variety of binding modes. In cases where the metal ion is able to form directional coordinate bonds, however, the carboxylate group tends to bond in a monodentate mode, interacting with just one metal centre in the syn mode. A dominant influence on the structures of the complexes seems to be the face-to-face stacking of the aromatic rings, which creates networks containing layers of metal-oxygen polyhedra that participate in hydrogen bonding. This investigation was undertaken, in part, by a group of secondary school students as an educational exercise designed to introduce school students to the technique of single-crystal X-ray diffraction and enhance their understanding of primary and secondary bonding.

Multi-Redox Responsive Behavior in a Mixed-Valence Semiconducting Framework Based on Bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane.

The two-dimensional (2-D) framework, [Cu(BTDAT)(MeOH)] {BTDAT = bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane}, possesses remarkable multi-step redox properties, with electrochemical studies revealing six quasi-stable redox states in the solid state. In situ electron paramagnetic resonance and visible-near infrared spectroelectrochemistry elucidated the mechanism for these multi-step redox processes, as well as the optical and electrochromic behavior of the BTDAT ligand and framework. In studying the structural, spectroscopic, and electronic properties of [Cu(BTDAT)(MeOH)], the as-synthesized framework was found to exist in a mixed-valence state with thermally-activated semiconducting behavior. In addition to pressed pellet conductivity measurements, single-crystal conductivity measurements using a pre-patterned polydimethylsiloxane layer on a silicon substrate provide important insights into the anisotropic conduction pathways. As an avenue to further understand the electronic state of [Cu(BTDAT)(MeOH)], computational band structure calculations predicted delocalized electronic transport in the framework. On the balance of probabilities, we propose that [Cu(BTDAT)(MeOH)] is a Mott insulator (i.e., electron correlations cause a metal-insulator transition). This implies that the conductivity is incoherent. However, we are unable to distinguish between activated transport due to Coulombically bound electron-hole pairs and a hopping mechanism. The combined electrochemical, electronic, and optical properties of [Cu(BTDAT)(MeOH)] shine a new light on the experimental and theoretical challenges for electroactive framework materials, which are implicated as the basis of advanced optoelectronic and electrochromic devices.

Mixed valency in a neutral 1D Fe-chloranilate coordination polymer.

The syntheses and structures of a pair of neutral one-dimensional (1D) Fe-anilate based coordination polymers, Fe(Fan)(4,4'-bipy)2 (Fann- = deprotonated 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone; 4,4'-bipy = 4,4'-bipyridine) and Fe(Clan)(OPPh3)2 (Clann- = deprotonated 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone; OPPh3 = triphenylphosphine oxide), are reported. In the case of Fe(Fan)(4,4'-bipy)2, the Fe centre is in the +2 oxidation state and the Fan ligand is present in its quinoidal, dianionic form. In contrast, the structurally similar Fe(Clan)(OPPh3)2 chain contains Fe centres and chloranilate ligands in oxidation states close to +3 and -3 respectively at low temperature. It is suggested that intrachain π-π interactions aid electron transfer from the Fe centres to the bridging ligands.

Multifunctional Coordination Polymer Exhibiting Reversible Mechanical Motion Allowing Selective Uptake of Guests and Leading to Enhanced Electrical Conductivity.

A remarkably flexible, multifunctional, 2D coordination polymer exhibiting an unprecedented mode of reversible mechanical motion, enabling pores to open and close, is reported. Such multifunctional materials are highly sought after, owing to the potential to exploit coexisting electronic and mechanical functionalities that underpin useful technological applications such as actuators and ultrasensitive detectors. The coordination polymer, of composition Mn(F4TCNQ)(py)2 (F4TCNQ = 2,3,5,6-tetrafluoro-7,7,8,8-tetracycanoquinodimethane; py = pyridine), consists of Mn(II) centers bridged by F4TCNQ dianions and coordinated by py molecules that extend above and below the 2D network. Exposure of Mn(F4TCNQ)(py)2, in its collapsed state, to carbon dioxide results in a pore-opening process at a threshold pressure for a given temperature. In addition to carbon dioxide, a variety of volatile guests may be incorporated into the pores, which are lined with electron-rich F4TCNQ dianions. The inclusion of electron-deficient guests such as 1,4-benzoquinone, nitrobenzene, maleic anhydride, and iodine into the pores is accompanied by a striking color change associated with a new host-guest charge-transfer interaction and an improvement in the semiconductor behavior, with the iodine adduct showing an increase in conductivity of almost 5 orders of magnitude. Experimental and density functional theory calculations on this remarkable multifunctional material demonstrate a reduction in the optical band gap with increasing electron affinity of the guest.

Alkali metal salts of 4-hydroxybenzoic acid: a structural and educational study.

As part of an educational exercise designed to introduce school students to the technique of single-crystal X-ray diffraction and enhance their understanding of primary and secondary bonding, a group of nine secondary school students was given the opportunity to prepare new compounds and to solve and refine data collected on the crystalline materials they had prepared. Their investigation of the alkali metal salts of 4-hydroxybenzoic acid (H2hba) yielded nine new compounds and their structures are described in this article. Whilst the salts might be expected to have similar atomic arrangements, there are significant differences in their structures. Although H2hba is a relatively simple organic molecule, it displays remarkable coordinative flexibility, forming ionic solids containing the uncharged molecule, the monoanion Hhba- or the dianion hba2-. A common feature of the structures is their layered arrangement: alternating hydrophilic layers made up of closely packed metal-oxygen polyhedra separated by the hydrophobic component of the hydroxybenzoate linking units. Close packing of these units seems to be a dominant influence in determining the overall structure. The hydroxybenzoate units are usually both parallel and antiparallel with their immediate neighbours, with packing that can be edge-to-face, face-to-face or a mixture of the two. Hydrogen bonding plays a key role in the structure of most compounds and a short strong hydrogen bond (SSHB) is observed in two of the networks. The compounds of 4-hydroxybenzoic acid, C7H6O3, described here are: poly[di-µ-aqua-µ-4-oxidobenzoato-dilithium], [Li2(C7H4O3)(H2O)2]n, 1, poly[triaqua-µ-4-oxidobenzoato-dilithium], [Li2(C7H4O3)(H2O)3]n, 2, poly[µ-4-hydroxybenzoato-lithium], [Li(C7H5O3)]n, 3, catena-poly[4-hydroxybenzoate [[diaquasodium]-di-µ-aqua]], {[Na(H2O)4](C7H5O3)}n, 4, poly[di-µ-aqua-aqua-µ-4-hydroxybenzoato-potassium], [K(C7H5O3)(H2O)3]n, 5, poly[µ-aqua-µ-4-hydroxybenzoato-potassium], [K(C7H5O3)(H2O)]n, 6, poly[aqua-µ-4-hydroxybenzoato-rubidium], [Rb(C7H5O3)(H2O)]n, 7, poly[aqua-µ-4-hydroxybenzoato-caesium], [Cs(C7H5O3)(H2O)]n, 8, poly[[µ-aqua-aqua(µ-4-hydroxybenzoato)(4-hydroxybenzoic acid)sodium] monohydrate], {[Na(C7H5O3)(C7H6O3)(H2O)2]·H2O}n, 9, poly[[(µ-4-hydroxybenzoato)(µ-4-hydroxybenzoic acid)rubidium] monohydrate], {[K(C7H5O3)(C7H6O3)]·H2O}n, 10, and poly[[(µ-4-hydroxybenzoato)(µ-4-hydroxybenzoic acid)rubidium] monohydrate], {[Rb(C7H5O3)(C7H6O3)]·H2O}n, 11.

The Effect of Sterically Active Ligand Substituents on Gas Adsorption within a Family of 3D Zn-Based Coordination Polymers.

An investigation of the adsorption properties of two structurally related, 3D coordination polymers of composition Zn(2-Mehba) and Zn(2,6-Me2hba) (2-Mehba = the dianion of 2-methyl-4-hydroxybenzoic acid and 2,6-Me2hba = the dianion of 2,6-dimethyl-4-hydroxybenzoic acid) is presented. A common feature of these structures are parallel channels that are able to accommodate appropriately sized guest molecules. The structures differ with respect to the steric congestion within the channels arising from methyl groups appended to the bridging ligands of the network. The host network, Zn(2-Mehba), is able to take up appreciable quantities of H2 (77 K) and CO2 and CH4 (298 K) in a reversible manner. In regard to the adsorption of N2 by Zn(2-Mehba), there appears to be an unusual temperature dependence for the uptake of the gas such that when the temperature is increased from 77 to 298 K the uptake of N2 increases. The relatively narrow channels of Zn(2,6-Me2hba) are too small to allow the uptake of N2 and CH4, but H2 molecules can be adsorbed. A pronounced step at elevated pressures in CO2 and N2O isotherms for Zn(2,6-Me2hba) is noted. Calculations indicate that rotation of phenolate rings leads to a change in the available intraframework space during CO2 dosing.

Effects of Mixed Valency in an Fe-Based Framework: Coexistence of Slow Magnetic Relaxation, Semiconductivity, and Redox Activity.

A 2-D coordination framework, (NEt4)2[Fe2(fan)3] (1·5(acetone); H2fan = 3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone), was synthesized and structurally characterized. The compound is structurally analogous to a formerly elucidated framework, (NEt4)2[Fe2(can)3] (H2can = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone), and adopts a 2-D (6,3) topology with the symmetrical stacking of [Fe2(fan)3]2- sheets that are held in position by the NEt4+ cations between the sheets. The investigation of the dc and ac magnetic properties of 1·5(acetone) revealed ferromagnetic ordering behavior and slow magnetization relaxation, as evinced from ac susceptibility measurements. Furthermore, the exposure of 1·5(acetone) to air led to the formation of a heptahydrate 1·7H2O which displayed distinct magnetic properties. The study of the redox state and extent of delocalization in 1·5(acetone) was undertaken via crystallography, in combination with Mössbauer and vis-NIR spectroscopy, to reveal the mixed-valence and delocalized nature of the as-synthesized material. As a result, the conductivity studies conducted on a pressed pellet showed a relatively high conductivity of 1.8 × 10-2 S cm-1 (300 K). In order to compare structurally related anilate-based structures, a relationship among the redox state, spectroscopic properties, and electronic properties was elucidated in this work. A preliminary investigation of 1·5(acetone) as a candidate anode material in lithium ion batteries revealed a high reversible capacity of 676.6 mAh g-1 and high capacity retention.

Square Grid Metal-Chloranilate Networks as Robust Host Systems for Guest Sorption.

Reaction of the chloranilate dianion with Y(NO3 )3 in the presence of Et4 N+ in the appropriate proportions results in the formation of (Et4 N)[Y(can)2 ], which consists of anionic square-grid coordination polymer sheets with interleaved layers of counter-cations. These counter-cations, which serve as squat pillars between [Y(can)2 ] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size-shape complementarity leading to a strong interaction between host and guest for CO2 and CH4 . Single-crystal X-ray diffraction experiments indicate significant interactions between the host framework and discrete I2 or Br2 molecules. A series of isostructural compounds (cat)[MIII (X-an)2 ] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et4 N, Me4 N and X-an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et4 N)[Gd(can)2 ] and (Et4 N)[Dy(can)2 ] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et4 N)[Gd(can)2 ].

Self-assembly of a Si-based cage by the formation of 24 equivalent covalent bonds.

A robust, nano-sized covalent cage, of composition, [(PhSi)6(ctc)4]6- (H6ctc = cyclotricatechylene) has been prepared in a simple reaction in good yield. The tetrahedral anionic cage is stable in both the solid and solution state and exhibits an affinity for Cs+ ions which bind to the internal surface of the cage.

Mixed Valency in a 3D Semiconducting Iron-Fluoranilate Coordination Polymer.

A pair of coordination polymers of composition (NBu4)2[M2(fan)3] (fan = fluoranilate; M = Fe and Zn) were synthesized and structurally characterized. In each case the compound consists of a pair of interpenetrating three-dimensional, (10,3)-a networks in which metal centers are linked by chelating/bridging fluoranilate ligands. Tetrabutylammonium cations are located in the spaces between the two networks. Despite the structural similarity, significant differences exist between (NBu4)2[Fe2(fan)3] and (NBu4)2[Zn2(fan)3] with respect to the oxidation states of the metal centers and ligands. For (NBu4)2[Fe2(fan)3] the structure determination as well as Mössbauer spectroscopy indicate the oxidation state for the Fe is close to +3, which contrasts with the +2 state for the Zn analogue. The differences between the two compounds extends to the ligands, with the Zn network involving only fluoranilate dianions, whereas the average oxidation state for the fluoranilate in the Fe network lies somewhere between -2 and -3. Magnetic studies on the Fe compound indicate short-range ordering. Electrochemical and spectro-electrochemical investigations indicate that the fluoranilate ligand is redox-active in both complexes; a reduced form of (NBu4)2[Fe2(fan)3] was generated by chemical reduction. Conductivity measurements indicate that (NBu4)2[Fe2(fan)3] is a semiconductor, which is attributed to the mixed valency of the fluoranilate ligands.

Tunable Porous Coordination Polymers for the Capture, Recovery and Storage of Inhalation Anesthetics.

The uptake of inhalation anesthetics by three topologically identical frameworks is described. The 3D network materials, which possess square channels of different dimensions, are formed from the relatively simple combination of ZnII centres and dianionic ligands that contain a phenolate and a carboxylate group at opposite ends. All three framework materials are able to adsorb N2 O, Xe and isoflurane. Whereas the framework with the widest channels is able to adsorb large quantities of the various guests from the gas phase, the frameworks with the narrower channels have superior binding enthalpies and exhibit higher levels of retention. The use of ligands in which substituents are bound to the aromatic rings of the bridging ligands offers great scope for tuning the adsorption properties of the framework materials.

An indirect generation of 1D M(II)-2,5-dihydroxybenzoquinone coordination polymers, their structural rearrangements and generation of materials with a high affinity for H2, CO2 and CH4.

A series of solid-state structural transformations are found to accompany desolvation of relatively simple coordination polymers to yield materials that exhibit unexpected gas sorbing properties. Reaction of 1,2,4,5-tetrahydroxybenzene with M(II) salts (M = Mg, or Zn) in an alcohol/water solution in the presence of air affords cis-M(II)(C6H2O4(-II))(H2O)2·2H2O·xROH, (M = Mg, or Zn), crankshaft-like chains in which the absolute configurations of the chiral metal centres follow the pattern Δ Δ Λ Λ Δ Δ Λ Λ, and are hydrogen bonded together to generate spacious channels. When crystals of the crankshaft chain are air dried the crystals undergo a single crystal-to-powder rearrangement to form linear trans-M(II)(C6H2O4(-II))(H2O)2 chains. Further dehydration yields microporous solids that reversibly sorb H2, CH4 and CO2 with high sorption enthalpies.

Lightweight Ionic Networks Composed of Li+ or Mg2+ Centres Linked Together by Dicarboxylate Ligands.

The combination of lightweight metal cations with a range of dicarboxylate ligands has led to the generation of ionic network materials that possess channels occupied by solvent molecules. The compounds [Li2 (2,2-bpdc)(DMF)2 ] and [Mg(2,2-bpdc)(DMF)2 ] (2,2-bpdc=2,2-dipyridyl-4,4-dicarboxylate) adopt a similar structure in which parallel metal-carboxylate chains are linked to four equivalent chains to generate a 3 D network in which DMF molecules occupy channels. [Li4 (3,5-pdc)2 (DMF)]⋅solvate (3,5-pdc=3,5-pyridine dicarboxylate) adopts a similar structure but the chains are more complex. As with the other structures, coordinated DMF molecules occupy network channels. [Li4 (3,5-pdc)2 (DMF)]⋅solvate is able to adsorb carbon dioxide at elevated pressures with the adsorption following a type V isotherm; hysteresis is apparent upon desorption. The final compound, Li[Mg3 OH(2,2-bqdc)3 (DMF/H2 O)3 ]⋅solvate (2,2-bqdc=2,2-biquinoline-4,4-dicarboxylate) has a distinctly different structure in which a trio of magnesium centres bound to a central µ3 -hydroxide ion serves as a 6-connecting, trigonal prismatic node within a 3 D network that has the point symbol, 49 66 . Solvent-filled intraframework spaces represent over 50 % of the crystal volume and are occupied by highly disordered solvent and Li+ ions. Immersion of Li[Mg3 OH(2,2-bqdc)3 (DMF/H2 O)3 ]⋅solvate in a solution of Fe(2,2-bipyridine)3 2+ results in the incorporation of the FeII complex into the large channels of the anionic network.

A New Structural Family of Gas-Sorbing Coordination Polymers Derived from Phenolic Carboxylic Acids.

The structure of Li(inox)⋅2/3 DMF (inox(-) =the N-oxide of the isonicotinate anion) consists of a 3D framework with solvent-filled, square cross-section channels of approximate dimensions 5.5×5.5 Å. Unfortunately, the Li(inox) framework is unstable upon removal of DMF from the channels. When the structurally related 4-hydroxybenzoic acid (H2 hba) was used in place of Hinox, and Zn(2+) in place of the Li(+) , a structurally similar but more robust network, Zn(hba), was obtained; the isostructural compound, Co(hba), may also be prepared. Longer ligands with phenolate and carboxylate functional groups at opposite ends, such as the dianions of 4-coumaric acid (H2 cma) and 4'-hydroxy-4-biphenylcarboxylic acid (H2 hbpc), in combination with Zn(2+) yield Zn(cma) and Zn(hbpc) frameworks, respectively, with the same PtS topology but with larger channels. The coordination polymers remain intact after desolvation and exhibit microporosity, showing the ability to sorb significant quantities of CO2 , CH4 , and H2 .

Isomeric ionic lithium isonicotinate three-dimensional networks and single-crystal-to-single-crystal rearrangements generating microporous materials.

Reaction between LiOH and isonicotinic acid (inicH) in the appropriate solvent or mixture of solvents affords a family of variously solvated forms of a simple ionic lithium salt, viz., Li(+)inic(-)·S (where S = 0.5 morpholine, 0.5 dioxane, 0.25 n-hexanol, 0.5 N-methylpyrrolidinone, 0.5 N,N-dimethylformamide, 0.5 n-propanol, 0.5 cyclohexanol, 0.5 pyridine, 0.5 t-butanol, 0.5 ethanol, and 0.5 methanol). Three-dimensional Li(+)inic(-) frameworks containing solvent-filled channels are present in all of these except for the MeOH and EtOH solvates. The nondirectional character of the electrostatic interactions between the Li(+) and inic(-) ions bestows an element of "plasticity" upon the framework, manifested in the observation of no less than five different framework structures within the family. Unusual single-crystal-to-single-crystal transformations accompany desolvation of Li(+)inic(-)·S in which the Li(+)inic(-) framework undergoes a major rearrangement (from a structure containing "8484 chains" to one with "6666 chains"). The "before and after" structures are strongly suggestive of the mechanism and the driving force for these solid state framework rearrangements: processes which further demonstrate the "plasticity" of the ionic Li(inic) framework. A solid-state mechanism for these desolvation processes that accounts very satisfactorily for the formation of the channels and for the diverse geometrical/topological aspects of the transformation is proposed. The reverse process allows the regeneration of the solvated 8484 form. When the 6666 Li(+)inic(-) form is immersed in carbon disulfide, a single-crystal-to-single-crystal transformation occurs to generate Li(+)inic(-)·0.25CS2. The hydrate, Li(+)inic(-)·2H2O which consists of discrete Li(inic)·H2O chains obtained by recrystallizing the salt from water, can also be obtained by hydration of the 6666 form. A dense 3D network with the formula, Li(inic) can be obtained in a reversible process by the removal of the water from the hydrated form and also by crystallization from a t-amyl alcohol solution.

Electrochemically directed synthesis of Cu2(I)(TCNQF4(II-))(MeCN)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane): voltammetry, simulations, bulk electrolysis, spectroscopy, photoactivity, and X-ray crystal structure of the Cu2(I)(TCNQF4(II-))(EtCN)2 analogue.

The new compound Cu2(I)(TCNQF4(II-))(MeCN)2 (TCNQF4(2-) = dianion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) has been synthesized by electrochemically directed synthesis involving reduction of TCNQF4 to TCNQF4(2-) in acetonitrile containing [Cu(MeCN)4](+)(MeCN) and 0.1 M Bu4NPF6. In one scenario, TCNQF4(2-) is quantitatively formed by reductive electrolysis of TCNQF4 followed by addition of [Cu(MeCN)4](+) to form the Cu2(I)(TCNQF4(II-))(MeCN)2 coordination polymer. In a second scenario, TCNQF4 is reduced in situ at the electrode surface to TCNQF4(2-), followed by reaction with the [Cu(MeCN)4](+) present in the solution, to electrocrystallize Cu2(I)(TCNQF4(II-))(MeCN)2. Two distinct phases of Cu2(I)(TCNQF4(II-))(MeCN)2 are formed in this scenario; the kinetically favored form being rapidly converted to the thermodynamically favored Cu2(I)(TCNQF4(II-))(MeCN)2. The postulated mechanism is supported by simulations. The known compound Cu(I)TCNQF4(I-) also has been isolated by one electron reduction of TCNQF4 and reaction with [Cu(MeCN)4](+). The solubility of both TCNQF4(2-)- and TCNQF4(•-)-derived solids indicates that the higher solubility of Cu(I)TCNQF4(I-) prevents its precipitation, and thus Cu2(I)(TCNQF4(II-))(MeCN)2 is formed. UV-visible and vibrational spectroscopies were used to characterize the materials. Cu2(I)(TCNQF4(II-))(MeCN)2 can be photochemically transformed to Cu(I)TCNQF4(I-) and Cu(0). Scanning electron microscopy images reveal that Cu(I)TCNQF4(I-) and Cu2(I)(TCNQF4(II-))(MeCN)2 are electrocrystallized with distinctly different morphologies. Thermogravimetric and elemental analysis data confirm the presence of CH3CN, and single-crystal X-ray diffraction data for the Cu2(I)(TCNQF4(II-))(EtCN)2 analogue shows that this compound is structurally related to Cu2(I)(TCNQF4(II-))(MeCN)2.

Synthesis, structure and cation-binding properties of some [4 + 4] metallocyclic MO2(2+) (M = Mo or W) derivatives of 9-phenyl-2,3,7-trihydroxyfluor-6-one.

The trianion Z(3-) obtained from 9-phenyl 2,3,7-trihydroxyfluor-6-one, ZH3, affords dioxomolybdenum and dioxotungsten derivatives which contain [4 + 4] metallocycles of composition [(MO2)4Z4](4-) (M = Mo, W) in combination with a variety of counter cations. The syntheses, structures and ESMS of the following compounds are presented: compound 1, (MePPh3)3(NBu4)[(MoO2)4Z4]; compound 2, (MePPh3)3(NBu4)[(WO2)4Z4]; compound 3, (MePPh3)4[(WO2)4Z4]; compound 4, (PPh4)2(NBu4)2[(MoO2)4Z4]; compound 5, (AsPh4)3(NBu4)[(MoO2)4Z4]; compound 6, (AsPh4)2(NBu4)2[(WO2)4Z4]; compound 7, (Ph3PNPPh3)(NBu4)3[(MoO2)4Z4]; compound 8, (Ph3PNPPh3)(NBu4)3[(WO2)4Z4]; compound 9, (NEt4)(NBu4)3[(MoO2)4Z4]. The metallocycles in all of these compounds have similar structures, with the four metal centers located at the corners of a square slightly distorted, to varying degrees, toward a rhombus and also toward a tetrahedron. Various cations are bound inside the anionic metallocycles. ESI mass spectrometry shows that the metallocycles remain intact in the gas phase, forming [(MO2)4Z4](4-), {X-[(MO2)4Z4]}(3-) and in some cases {X2-[(MO2)4Z4]}(2-) where X(+) is an organic cation.

3d-Metal derivatives of the [Cu(I)(SO3)4]7- ion: structure and magnetism.

The Cu(SO(3))(4)(7-) anion, which consists of a tetrahedrally coordinated Cu(I) centre coordinated to four sulfur atoms, is able to act as a multidentate ligand in discrete and infinite supramolecular species. The slow oxidation of an aqueous solution of Na(7)Cu(SO(3))(4) yields a mixed oxidation state, 2D network of composition Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O. The addition of Cu(II) and 2,2'-bipyridine to an aqueous Na(7)Cu(SO(3))(4) solution leads to the formation of a pentanuclear complex of composition {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(+); a combination of hydrogen bonding and π-π stacking interactions leads to the generation of infinite parallel channels that are occupied by disordered nitrate anions and water molecules. A pair of Cu(SO(3))(4)(7-) anions each act as a tridentate ligand towards a single Mn(II) centre when Mn(II) ions are combined with an excess of Cu(SO(3))(4)(7-). An anionic pentanuclear complex of composition {[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)} is formed when Fe(II) is added to a Cu(+)/SO(3)(2-) solution. Hydrated ferrous [Fe(H(2)O)(6)(2+)] and sodium ions act as counterions for the complexes and are responsible for the formation of an extensive hydrogen bond network within the crystal. Magnetic susceptibility studies over the temperature range 2-300 K show that weak ferromagnetic coupling occurs within the Cu(II) containing chains of Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O, while zero coupling exists in the pentanuclear cluster {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(NO(3))·H(2)O. Weak Mn(II)-O-S-O-Mn(II) antiferromagnetic coupling occurs in Na(H(2)O)(6){[Cu(I)(SO(3))(4)][Mn(II)(H(2)O)(2)](3)}, the latter formed when Mn was in excess during synthesis. The compound, Na(3)(H(2)O)(6)[Fe(II)(H(2)O)(6)](2){[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)}·H(2)O, contained trace magnetic impurities that affected the expected magnetic behaviour.

Synthesis, structure and host-guest properties of (Et4N)2[Sn(IV)Ca(II)(chloranilate)4], a new type of robust microporous coordination polymer with a 2D square grid structure.

Reaction of chloranilic acid with SnCl(4), Ca(NO(3))(2) and Et(4)NBF(4) in aqueous acetone yields (Et(4)N)(2)[Sn(IV)Ca(II)(can)(4)]. 2 Me(2)CO which contains 2D coordination polymer sheets of composition [Sn(IV)Ca(II)(can)(4)](2-). Both metals are 8-coordinate and act as 4-connecting nodes to form a square grid containing "square" holes. The anionic sheets are electrostatically bound together by Et(4)N(+) cations, which align the sheets so that holes are arranged directly above and below each other, generating channels perpendicular to the sheets. The acetone is easily removed, after which single crystal character is retained. Crystallographic studies indicate that (Et(4)N)(2)[Sn(IV)Ca(II)(can)(4)] is able to sorb one molecule per square hole of either acetonitrile, or CS(2). Gas sorption measurements indicate that at a pressure of 2000 kPa each square cavity sorbs two CO(2) molecules at 273 K, approximately one molecule of N(2) at 195 K and approximately 2.4 molecules of H(2) at 77 K.