Kim R. Dunbar

Anion-π interactions in supramolecular architectures.

The study of the noncovalent force between π-acidic aromatic systems and anions, referred to as the anion-π interaction, has recently emerged as a new branch of supramolecular chemistry. The anion-π contact is complementary to the cation-π interaction, a prominent noncovalent force involved in protein structure and enzyme function. Until recently, the scientific community had overlooked the anion-π interaction due to its ostensibly counterintuitive nature. Pioneering theoretical studies in 2002, however, established that anion-π interactions are energetically favorable (~20-70 kJ/mol) and prompted a flurry of reports in support of their existence. The interest in anion-π contacts was further fueled by the importance of anions in key chemical and biological processes and the involvement of π-rings in anion recognition and transport. Anion-π interactions hold great promise for the design of selective anion receptors, hosts or scaffolds, colorimetric sensors, and catalysts and may also affect biological functions. Currently, the area of anion-π research is highly topical in the scientific community and on a meteoric rise in the chemical literature. This Account highlights our leading findings in this burgeoning area. Our work has focused on comprehensive investigations of several unprecedented supramolecular systems, in which the anions and their close anion-π contacts are the driving elements of the final architectures. We surveyed several heterocyclic π-acidic aromatic systems amenable to anion-π contacts and explored the subtle interplay between ligand π-acidity, anion identity, and metal ions in mediating the ensuing self-assembled architectures. The reactions we performed between solvated first-row transition metal ions and the π-acidic ligands bptz (3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) or bmtz (3,6-bis(2-pyrimidyl)-1,2,4,5-tetrazine) resulted in unprecedented metallacycles. Our investigations revealed that the identity of the encapsulated ion dictates the metallacycle nuclearity and close anion-π contacts are critical for the metallacycle stability. Our X-ray crystallographic, NMR spectroscopic, and mass spectrometric (MS) studies demonstrated that the tetrahedral ([BF4](-), [ClO4](-)) and octahedral ([SbF6](-), [AsF6](-), [PF6](-)) anions template discrete molecular squares and pentagons, respectively. The metal ions occupy the vertices, and bptz or bmtz moieties span the edges of the metallacycles. The encapsulated anions occupy the π-acidic cavities of the metallacycles and establish multiple close directional F/O···C(tetrazine) contacts with the edges. The observation of notable (19)F solid-state NMR chemical shifts reflects the short contacts of the encapsulated anions, findings that we corroborated by DFT calculations. The solution NMR data support the conclusion that bona fide metallacycle templation and interconversion between the metallacycles in solution occurs only in the presence of the appropriate anions. The NMR, MS, and CV data underscore the remarkable metallapentacycle stability despite the angle strain inherent in pentagons formed by octahedral metal ions. The low anion activation energies of encapsulation (ΔG(‡) ~ 50 kJ/mol) suggest that anion-π contacts assist the anion templation. We also studied reactions of Ag(I)X (X(-) = [PF6](-), [AsF6](-), [SbF6](-), [BF4](-)) with bptz or bppn (3,6-bis(2-pyridyl)-1,2-pyridazine) to assess the effect of the ligand π-acidity on the preferred structures. The X-ray data revealed that the higher π-acidity of the tetrazine ring in bptz leads to propeller-type products [Ag2(bptz)3](2+) exhibiting prominent short anion-π contacts. By contrast, the less π-acidic bppn preferentially favors grids [Ag4(bppn)4](4+) which exhibit maximized π-π interactions. Finally, we explored the reactions of the extended π-acidic heterocycle HAT(CN)6 (1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile) with the Cl(-), Br(-), I(-) ions which lead to highly colored solutions/crystals. X-ray crystallographic studies of the HAT(CN)6/halide complexes revealed unprecedented multisite short peripheral charge-transfer and centroid anion-π contacts. In solution, the charge-transfer contacts were evidenced by electronic absorption, (13)C and halogen NMR, as well as MS data. The distinctly colored complex entities exhibit extraordinarily high association constants, which render them promising for anion-sensing receptor applications.

New Insight into the Nature of Cu(TCNQ): Solution Routes to Two Distinct Polymorphs and Their Relationship to Crystalline Films That Display Bistable Switching Behavior

Syntheses and characterization of two polymorphs of Cu(TCNQ) have been carried out and the results correlated to films of the materials. Reactions of CuI with TCNQ or [Cu(CH3CN)4][BF4] with TCNQ- lead to blue-purple needles of Cu(TCNQ) phase I (1). A slurry of this kinetic product in CH3CN yields a second crystalline phase of Cu(TCNQ), phase II (2), which exhibits a platelet morphology. Powder X-ray diffraction and scanning electron microscopy data revealed that both phases are present in films of Cu(TCNQ) formed by oxidation of Cu foil by TCNQ in CH3CN. X-ray photoelectron spectra of the two phases are indistinguishable from each other and are indicative of the presence of Cu(I). Single-crystal X-ray studies were undertaken on very small crystals of the two samples, the results of which reveal that subtle geometrical changes for the nitrile arrangements around the four-coordinate Cu(I) centers lead to major changes in the architectural framework of the polymers. Phase I was indexed in the tetragonal crys...

Chain Compounds Based on Transition Metal Backbones: New Life for an Old Topic

A new link in the chain: After a long period of inactivity, research into one-dimensional compounds based on linear arrays of transition metals is experiencing a renaissance. Recently, oligomeric and polymeric chains have been reported for a variety of transition metals. One such compound of a particularly exotic variety is depicted here, in which a {Pd 4 } 2+ unit is surrounded by a “π-electron sheath” of conjugated polyene ligands.

Reversible switching from antiferro- to ferromagnetic behavior by solvent-mediated, thermally-induced phase transitions in a trimorphic MOF-based magnetic sponge system.

Hydrothermal reactions of copper(II) acetate, tetrazolate-5-carboxylate (tzc), and the neutral N-donor spacer ligand 1,3-di(4-pyridyl)propane (dpp) lead in a single reaction vial to the simultaneous formation of three different single-crystalline solvates [Cu(tzc)(dpp)]n·0.5C6H14·0.5H2O (1), [Cu(tzc)(dpp)]n·4.5H2O (2), and [Cu(tzc)(dpp)]n·1.25C6H14 (3). All three structures were characterized by single crystal X-ray diffraction. None of these solvates can be prepared as phase-pure bulk materials, but reaction conditions similar to those used for single crystal synthesis yield a phase-pure polycrystalline bulk material of an additional forth solvate phase [Cu(tzc)(dpp)]n·2H2O (4). Investigations of its thermal properties by in situ temperature-dependent synchrotron-based powder diffraction experiments have shown interesting phase transitions upon heating in a helium stream. Initially, the precursor dihydrate 4 transforms to an anhydrous phase [Cu(tzc)(dpp)]n (6I) via the intermediate monohydrate phase [Cu(tzc)(dpp)]n·H2O (5). Upon further heating, phase 6I transforms to a new anhydrous polymorph 6II, which transforms upon cooling to a further new phase 6III. Thermogravimetric measurements performed in tandem with differential scanning calorimetry as well as infrared spectroscopic investigations are in agreement with these findings. The de/resolvation behavior is accompanied by a dramatic change in their magnetic properties: The dihydrate phase shows antiferromagnetic exchange interactions, whereas ferromagnetic properties are observed for the trimorphic anhydrate system. This magnetic sponge-like behavior can be reversibly cycled upon de/resolvation of the material.

A Thermally and Hydrolytically Stable Microporous Framework Exhibiting Single‐Chain Magnetism: Structure and Properties of [Co2(H0.67bdt)3]⋅20 H2O

Fixing a hole: Hydrothermal chemistry has been exploited in the preparation of a 3D framework material exhibiting 48% accessible void volume and 1.5% hydrogen uptake by weight at 120 kPa (see picture). The title compound also exhibits single-chain magnetic behavior and reversible changes in magnetic properties upon solvation and desolvation.

A One-Pot, High-Yield Synthesis of a Paramagnetic Nickel Square from Divergent Precursors by Anion Template Assembly**

A paramagnetic Ni-containing molecular square has been synthesized in high yield from divergent precursors. An X-ray structure (shown in the picture) reveals the presence of an encapsulated tetrafluoroborate anion, which appears to be a requisite condition for the formation of the cyclic oligomer.

Control of Charge Transfer in a Series of Ru2II,II/TCNQ Two-Dimensional Networks by Tuning the Electron Affinity of TCNQ Units: A Route to Synergistic Magnetic/Conducting Materials

The isostructural series of two-dimensional (2-D) fishnet-type network compounds, [{Ru(2)(O(2)CCF(3))(4)}(2)(TCNQR(x))] x n(solv) (R(x) = H(4), 1; Br(2), 2; Cl(2), 3; F(2), 4; F(4), 5), has been synthesized from the reactions of a paddlewheel diruthenium(II, II) complex, [Ru(2)(II,II)(O(2)CCF(3))(4)], and neutral TCNQ derivatives (TCNQR(x) = 2,3,5,6- or 2,5-halogen-substituted 7,7,8,8-tetracyanoquinodimethane) under anaerobic conditions. Corresponding Rh compounds 1-Rh-5-Rh, which are diamagnetic and redox-inactive, were also synthesized for the purpose of comparison with 1-5. According to the electron affinity of TCNQR(x), which is related to its first reduction potential, the Ru(2) series (1-5) has the requisite driving force for charge transfer from [Ru(2)(II,II)(O(2)CCF(3))(4)] to TCNQR(x), which can lead to a mixed-valence state of [{Ru(2)(4.5+)}-(TCNQR(x)(*-))-{Ru(2)(4.5+)}] for the 2-D network. Such a charge (or electron) transfer results in magnetic exchange interactions between [Ru(2)] units (S = 1 for [Ru(2)(II,II)] and S = 3/2 for [Ru(2)(II,III)](+)) via TCNQR(x)(*-) S = 1/2 radicals that lead to long-range magnetic ordering in the layer. In the present series, only 5 demonstrated the full electron transfer (1-e(-) transfer) to the mixed-valence state, whereas other members are essentially in the state [{Ru(2)(4+)}-(TCNQR(x)(0))-{Ru(2)(4+)}]. Whereas 1-4 are paramagnetic, 5 is a metamagnet undergoing 3-D long-range antiferromagnetic ordering at 95 K (= T(N)) and reverts to a magnetic-field-induced ferromagnetic state exhibiting coercivity up to 60 K. This result is consistent with the fact that TCNQF(4) has the strongest electron affinity among the TCNQR(x) molecules. Even in neutral forms, however, 1-4 can be observed to undergo thermally and/or field-activated charge transfers from [Ru(2)(II,II)] to TCNQR(x) to give semiconductors with an activation energy of 200-300 meV, which is a driving force to transport electrons over the lattice. As determined by their conducting properties, the ease of thermally and/or field-activated charge transfers is on the order of 1 < 4 < 2 approximately = 3 << 5, which is in agreement with the order of electron affinity of TCNQR(x). Indeed, a magnetic anomaly with short-range order associated with the localization of charge-transferred electrons was revealed in the low-temperature susceptibility data for 2 and 3. Finally, 5 was subjected to terahertz time-domain spectroscopy, the data from which revealed that transport hopping electrons scattered at high temperatures interact with magnetically ordered spins with the scattering being suppressed at T(N), at which temperature the real part of the complex electronic conductivity (sigma(1)) and dielectric permeability (epsilon(1)) are dramatically altered. From these collective data, we conclude that molecular design based on an interunit charge transfer in a paramagnetic lattice is an efficient route to the design of materials with synergism between magnetic and conducting properties.

A Highly Anisotropic Cobalt(II)-Based Single-Chain Magnet: Exploration of Spin Canting in an Antiferromagnetic Array

In this article we report for the first time experimental details concerning the synthesis and full characterization (including the single-crystal X-ray structure) of the spin-canted zigzag-chain compound [Co(H2L)(H2O)]infinity [L = 4-Me-C6H4-CH2N(CPO3H2)2], which contains antiferromagnetically coupled, highly magnetically anisotropic Co(II) ions with unquenched orbital angular momenta, and we also propose a new model to explain the single-chain magnet behavior of this compound. The model takes into account (1) the tetragonal crystal field and the spin-orbit interaction acting on each Co(II) ion, (2) the antiferromagnetic Heisenberg exchange between neighboring Co(II) ions, and (3) the tilting of the tetragonal axes of the neighboring Co units in the zigzag structure. We show that the tilting of the anisotropy axes gives rise to spin canting and consequently to a nonvanishing magnetization for the compound. In the case of a strong tetragonal field that stabilizes the orbital doublet of Co(II), the effective pseudo-spin-1/2 Hamiltonian describing the interaction between the Co ions in their ground Kramers doublet states is shown to be of the Ising type. An analytical expression for the static magnetic susceptibility of the infinite spin-canted chain is obtained. The model provides an excellent fit to the experimental data on both the static and dynamic magnetic properties of the chain.

An Electron‐Transfer Ferromagnet with Tc=107 K Based on a Three‐Dimensional [Ru2]2/TCNQ System

The design of dp–pp molecular systems with efficient electronic communication is a long-standing goal in the field of inorganic chemistry. Guiding principles for this research are provided by the seminal studies on the Creutz–Taube ion, [(H3N)5Ru(m-pyz)Ru(NH3)5] 5+ (pyz= pyrazine), discovered in 1969, as well as subsequent related compounds that undergo charge-transfer interactions between mixed-valent metal ions through an organic bridging ligand. Various experimental investigations to evaluate the electron-transfer dynamics were undertaken and theoretical interpretations from kinetic and, thermodynamic approaches were developed by Hush, Marcus and Sutin, and others. In the context of the current work, we also note the important contributions of Crutchley and co-workers, who explored electron-transfer processes in dinuclear ruthenium(III) complexes bridged by the 1,4-dicyanamidobenzene dianion (Dicyd ) or one of its substituted derivatives. Interestingly, this class of compounds demonstrated strong intramolecular magnetic coupling between Ru S= 1/2 spins via the pp orbital of the Dicyd bridge with J exceeding 400 cm 1 closely associated with a highly conjugated p–d network, classified as Class II or III behavior on the Robin– Day scale. A crucial design ingredient for such systems is a 1:2 ratio of the one-electron donor (D, i.e., Dicyd) to the oneelectron acceptor (A, i.e., a Ru ion) that can lead to an electron-transfer resonance of type [A –D–A

Supramolecular architectures with π-acidic 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine cavities: role of anion-π interactions in the remarkable stability of Fe(II) metallacycles in solution.

A–D– A