Matthew G. Cowan

Reversible Switching of a Cobalt Complex by Thermal, Pressure, and Electrochemical Stimuli: Abrupt, Complete, Hysteretic Spin Crossover

Triply switchable [Co(II)(dpzca)(2)] shows an abrupt, reversible, and hysteretic spin crossover (T(1/2)↓ = 168 K, T(1/2)↑ = 179 K, and ΔT(1/2) = 11 K) between the high-spin (HS) and low-spin (LS) states of cobalt(II), both of which have been structurally characterized. The spin transition is also reversibly triggered by pressure changes. Moreover, in a third reversible switching mechanism for this complex, the magnetic properties can be switched between HS cobalt(II) and LS cobalt(III) by redox.

Scalable fabrication of polymer membranes with vertically aligned 1 nm pores by magnetic field directed self-Assembly

There is long-standing interest in developing membranes possessing uniform pores with dimensions in the range of 1 nm and physical continuity in the macroscopic transport direction to meet the needs of challenging small molecule and ionic separations. Here we report facile, scalabe fabrication of polymer membranes with vertically (i.e., along the through-plane direction) aligned 1 nm pores by magnetic-field alignment and subsequent cross-linking of a liquid crystalline mesophase. We utilize a wedge-shaped amphiphilic species as the building block of a thermotropic columnar mesophase with 1 nm ionic nanochannels, and leverage the magnetic anisotropy of the amphiphile to control the alignment of these pores with a magnetic field. In situ X-ray scattering and subsequent optical microscopy reveal the formation of highly ordered nanostructured mesophases and cross-linked polymer films with orientational order parameters of ca. 0.95. High-resolution transmission electron microscopy (TEM) imaging provides direct visualization of long-range persistence of vertically aligned, hexagonally packed nanopores in unprecedented detail, demonstrating high-fidelity retention of structure and alignment after photo-cross-linking. Ionic conductivity measurements on the aligned membranes show a remarkable 85-fold enhancement of conductivity over nonaligned samples. These results provide a path to achieving the large area control of morphology and related enhancement of properties required for high-performance membranes and other applications.

Thin Polymer Films with Continuous Vertically Aligned 1 nm Pores Fabricated by Soft Confinement

Membrane separations are critically important in areas ranging from health care and analytical chemistry to bioprocessing and water purification. An ideal nanoporous membrane would consist of a thin film with physically continuous and vertically aligned nanopores and would display a narrow distribution of pore sizes. However, the current state of the art departs considerably from this ideal and is beset by intrinsic trade-offs between permeability and selectivity. We demonstrate an effective and scalable method to fabricate polymer films with ideal membrane morphologies consisting of submicron thickness films with physically continuous and vertically aligned 1 nm pores. The approach is based on soft confinement to control the orientation of a cross-linkable mesophase in which the pores are produced by self-assembly. The scalability, exceptional ease of fabrication, and potential to create a new class of nanofiltration membranes stand out as compelling aspects.

Selective gas adsorption in a pair of robust isostructural MOFs differing in framework charge and anion loading.

Activation of the secondary assembly instructions in the mononuclear pyrazine imide complexes [Co(III)(dpzca)2](BF4) or [Co(II)(dpzca)2] and [Ni(II)(dpzca)2] has facilitated the construction of two robust nanoporous three-dimensional coordination polymers, [Co(III)(dpzca)2Ag](BF4)2·2(H2O) [1·2(H2O)] and [Ni(II)(dpzca)2Ag]BF4·0.5(acetone) [2·0.5(acetone)]. Despite the difference in charge distribution and anion loading, the framework structures of 1·2(H2O) and 2·0.5(acetone) are isostructural. One dimensional channels along the b-axis permeate the structures and contain the tetrafluoroborate counterions (the Co(III)-based MOF has twice as many BF4(-) anions as the Ni(II)-based MOF) and guest solvent molecules. These anions are not readily exchanged whereas the solvent molecules can be reversibly removed and replaced. The H2, N2, CO2, CH4, H2O, CH3OH, and CH3CN sorption behaviors of the evacuated frameworks 1 and 2 at 298 K have been studied, and modeled, and both show very high selectivity for CO2 over N2. The increased anion loading in the channels of Co(III)-based MOF 1 relative to Ni(II)-based MOF 2 results in increased selectivity for CO2 over N2 but a decrease in the sorption kinetics and storage capacity of the framework.

A cobalt(II) bis(salicylate)-based ionic liquid that shows thermoresponsive and selective water coordination

A metal-containing ionic liquid (MCIL) has been prepared in which the [Co(II)(salicylate)2](2-) anion is able to selectively coordinate two water molecules with a visible colour change, even in the presence of alcohols. Upon moderate heating or placement in vacuo, the hydrated MCIL undergoes reversible thermochromism by releasing the bound water molecules.

Imidazolium-Based Poly(ionic liquid)/Ionic Liquid Ion-Gels with High Ionic Conductivity Prepared from a Curable Poly(ionic liquid)

Ionic liquid (IL)-based ion-gel membranes were prepared from a curable poly(IL)-based materials platform with the free ILs 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), bis(fluorosulfonyl)imide ([EMIM][FSI]), 1-butylimidazolium bis(trifluoromethylsulfonyl)imide ([C4 IMH][TFSI]), and ethylmethylammonium nitrate [EAN][NO3 ] and evaluated for their ionic conductivity performance at ambient and elevated temperatures. The resulting cross-linked, free-standing ion-gel membranes were found to have less than 1 wt% water (with the exception of [EAN][NO3 ] which contained ≈20 wt% water). Increasing free IL content from 50 to 80 wt% produces materials with ionic conductivity values ≥10(-2) S cm(-1) at 25 °C and ≈10(-1) S cm(-1) at 110 °C. Additionally, ion-gels containing 70 wt% of the protic ILs [C4 IMH][TFSI] and [EMIM][FSI] display ionic conductivity values of ≈10(-3) to 10(-2) S cm(-1) over the temperature range of 25-110 °C.

Targeted structural modification of spin crossover complexes: pyridine vs pyrazine

Abstract 2-(Aminomethyl)pyrazine has been prepared in five steps from 2-pyrazine carboxylic acid. From this key amine, two new bis-terdentate triazole-based ligands which feature pendant pyrazine groups, PZMAT and PZMPT (4-amino- and 4-pyrrolyl-3,5-bis{[(2-pyrazylmethyl)amino]methyl}-4H-1,2,4-triazole, respectively), and two dinuclear complexes of them, [FeII2(PZMAT)2](BF4)4∙MeOH∙2H2O (1∙MeOH∙2H2O) and [FeII2(PZMPT)2](BF4)4∙3H2O (2∙3H2O), have been prepared. A structure determination at 100 K on 2∙3.5MeCN confirmed that the ligands adopt the expected binding mode, providing all twelve donors to the two iron(II) centres and two N1,N2-triazole bridges between them. Both undergo gradual incomplete spin transitions: at room temperature 1∙MeOH∙2H2O and 2∙3H2O are approximately two-thirds to three-quarters [HS-HS], dropping to mostly ‘[HS-LS]’ at 50 K. The structure determination and Mössbauer spectroscopy of 2 qualitatively support this. These findings are consistent with the pendant pyrazines providing a somewhat higher field strength than the pendant pyridines do in the analogous PMRT complexes.