Peter D. Southon

Dynamic Interplay between Spin-Crossover and Host−Guest Function in a Nanoporous Metal−Organic Framework Material

The nanoporous metal-organic framework [Fe(pz)Ni(CN)(4)], 1 (where pz is pyrazine), exhibits hysteretic spin-crossover at ambient conditions and is robust to the adsorption and desorption of a wide range of small molecular guests, both gases (N(2), O(2), CO(2)) and vapors (methanol, ethanol, acetone, acetonitrile, and toluene). Through the comprehensive analysis of structure, host-guest properties, and spin-crossover behaviors, it is found that this pillared Hofmann system uniquely displays both guest-exchange-induced changes to spin-crossover and spin-crossover-induced changes to host-guest properties, with direct dynamic interplay between these two phenomena. Guest desorption and adsorption cause pronounced changes to the spin-crossover behavior according to a systematic trend in which larger guests stabilize the high-spin state and therefore depress the spin-crossover temperature of the host lattice. When stabilizing the alternate spin state of the host at any given temperature, these processes directly stimulate the spin-crossover process, providing a chemisensing function. Exploitation of the bistability of the host allows the modification of adsorption properties at a fixed temperature through control of the host spin state, with each state shown to display differing chemical affinities to guest sorption. Guest desorption then adsorption, and vice versa, can be used to switch between spin states in the bistable temperature region, adding a guest-dependent memory effect to this system.

Dynamic Photo‐Switching in Metal–Organic Frameworks as a Route to Low‐Energy Carbon Dioxide Capture and Release

For post-combustion carbon dioxide capture technology to realize widespread viability, the energy costs must be drastically reduced. Current adsorbent technologies that rely on pressure, temperature, or vacuum swings consume as much as 40% of the production capacity of a power plant, most of which is associated with the liberation of CO2 from the capture medium. Ultimately this penalty, or parasitic energy load, must be brought closer to the thermodynamic minimum of about 4% to avoid prohibitive cost increases. Given that the triggers for release of adsorbed carbon dioxide, such as vacuum and heating, are so energy intensive, 3] requiring energy from the power plant, there is strong motivation to develop new release triggers that do not require extra energy from the plant, using renewable energy sources such as the sun. In conjunction with this, adsorbents with maximum gas sorption efficiency can further reduce the costs compared to the conventional energy-intensive CO2 gas separation process. Light, and in particular concentrated sunlight, is an extremely attractive stimulus for triggering CO2 release. If used with an adsorbent material that strongly absorbs sunlight concomitant with the desorption of large amounts of CO2, it may be possible to drastically reduce the energy costs. Perhaps the most attractive adsorbent candidates are metal–organic frameworks (MOFs), because of their large adsorption capacities, and the potential for incorporation of light-responsive organic groups within the pore structure. MOFs are an important class of 3D crystalline porous materials comprised of metal centers and organic ligands, joined periodically to establish a crystalline porous array. The large internal surface areas can be used to adsorb unprecedented quantities of gases, with particular interest in hydrogen, methane, 8] and carbon dioxide emergent. 7b,h,9] Methods for the incorporation of light-responsive groups within MOFs include the use of pendant groups pointing into the pores, and filling of pores with light-responsive guest molecules. The responsive groups within these materials may then alter their conformation when exposed to filtered light which results in a change in adsorption capacity, as reported thus far for static conditions. The responsive groups within these MOFs can be statically set to one position or another. For use in photoswing carbon dioxide capture, MOFs that can respond dynamically, or to the broadband radiation found in sunlight whilst loaded with adsorbed gas, are ideal. This will increase the speed of operation and lower the energy costs (see Figure 1)

Organosilane functionalization of halloysite nanotubes for enhanced loading and controlled release

The surfaces of naturally occurring halloysite nanotubes were functionalized with γ-aminopropyltriethoxysilane (APTES), which was found to have a substantial effect on the loading and subsequent release of a model dye molecule. APTES was mostly anchored at the internal lumen surface of halloysite through covalent grafting, forming a functionalized surface covered by aminopropyl groups. The dye loading of the functionalized halloysite was 32% greater than that of the unmodified sample, and the release from the functionalized halloysite was dramatically prolonged as compared to that from the unmodified one. Dye release was prolonged at low pH and the release at pH 3.5 was approximately three times slower than that at pH 10.0. These results demonstrate that organosilane functionalization makes pH an external trigger for controlling the loading of guest on halloysite and the subsequent controlled release.

Hierarchical Self-Assembly of a Chiral Metal–Organic Framework Displaying Pronounced Porosity†

[Extract] Significant recent attention has been devoted to the development of useful self-assembled hybrid materials.[1] This is particularly the case for metal–organic frameworks (MOFs), which display properties such as regularity, porosity, robustness, and high surface area that lead to potential applications in areas such as catalysis, gas separation, and storage.[2, 3] Our research groups and others have been developing new methods for the synthesis of both discrete and extended metal–organic materials, with particular interest in the controlled generation of increased structural complexity.[4] Herein we report a hierarchical self-assembly strategy which has been used to synthesize a new metal–organic framework. This strategy differs from the commonly employed molecular building block (MBB) and secondary building unit (SBU) approaches, where single metal ions or small inorganic clusters (polyhedra) are linked by bridging (often carboxylate) ligands in a one-pot reaction.[5] In these approaches, substantial pore volume is achieved principally through the enthalpically favorable formation of an open framework overcoming the entropic penalties associated with the entrapment of solvent guest molecules. Kinetic control over the formation of the framework is achieved largely through the trial-and-error optimization of synthetic conditions to prevent formation of unwanted kinetic intermediates.[6]

Reversible and Selective O2 Chemisorption in a Porous Metal–Organic Host Material

The metal-organic host material [{Co(III)(2)(bpbp)(O(2))}(2)bdc](PF(6))(4) (1·2O(2); bpbp(-) = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc(2-) = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{Co(II)(2)(bpbp)}(2)bdc](PF(6))(4) (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1·2O(2), achieved through desorption of included water guests from the as-synthesized phase 1·2O(2)·3H(2)O, consists of an ionic lattice containing discrete tetranuclear complexes, between which lie void regions that allow the migration of dioxygen and other guests. Powder X-ray diffraction analyses indicate that the host material retains crystallinity through the dioxygen desorption/chemisorption processes. Dioxygen chemisorption measurements on 1 show near-stoichiometric uptake of dioxygen at 5 mbar and 25 °C, and this capacity is largely retained at temperatures above 100 °C. Gas adsorption isotherms of major atmospheric gases on both 1 and 1·2O(2) indicate the potential suitability of this material for air separation, with a O(2)/N(2) selectivity factor of 38 at 1 atm. Comparison of oxygen binding in solution and in the solid state indicates a dramatic increase in binding affinity to the complex when it is incorporated in a porous solid.

Reversible hydrogen gas uptake in nanoporous Prussian Blue analogues

The family of dehydrated nanoporous Prussian Blue analogues, M(II)3[Co(III)(CN)6]2 (M(II) = Mn, Fe, Co, Ni, Cu, Zn, Cd), which contain coordinatively unsaturated divalent metal cations, undergoes reversible sorption of hydrogen gas up to 1.2 wt% (at 77 K, 101.3 kPa), the capacity of which depends on the metal ion.

Exploiting stable radical states for multifunctional properties in triarylamine-based porous organic polymers

Redox-active porous organic polymers (POPs) have enormous potential in applications ranging from electrocatalysis to solar energy conversion. Exploiting the different electronic states offers exciting prospects for controlling host–guest chemistry, however, this aspect of multifunctionality has to date, remained largely unexplored. Here, we present a strategy for the development of multifunctional materials with industrially sought-after properties. A series of hydrophobic POPs containing redox-active triarylamines linked by ethynyl (POP-1), 1,4-diethynylphenyl (POP-2) and 4,4′-diethynylbiphenyl (POP-3) bridges have been synthesised and characterised by NMR and EPR spectroscopy, as well as spectroelectrochemistry and computational modelling. The facile electrochemical or chemical oxidation of the POPs generate mixed-valence radical cation states with markedly enhanced adsorption properties relative to their neutral analogues, including a 3-fold improvement in the H2 uptake at 77 K and 1 bar, and an increase in the isosteric heat of adsorption for CO2.

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.

Guest Programmable Multistep Spin Crossover in a Porous 2-D Hofmann-Type Material

The spin crossover (SCO) phenomenon defines an elegant class of switchable materials that can show cooperative transitions when long-range elastic interactions are present. Such materials can show multistepped transitions, targeted both fundamentally and for expanded data storage applications, when antagonistic interactions (i.e., competing ferro- and antiferro-elastic interactions) drive concerted lattice distortions. To this end, a new SCO framework scaffold, [FeII(bztrz)2(PdII(CN)4)]·n(guest) (bztrz = (E)-1-phenyl-N-(1,2,4-triazol-4-yl)methanimine, 1·n(guest)), has been prepared that supports a variety of antagonistic solid state interactions alongside a distinct dual guest pore system. In this 2-D Hofmann-type material we find that inbuilt competition between ferro- and antiferro-elastic interactions provides a SCO behavior that is intrinsically frustrated. This frustration is harnessed by guest exchange to yield a very broad array of spin transition characters in the one framework lattice (one- (1·(H2O,EtOH)), two- (1·3H2O) and three-stepped (1·∼2H2O) transitions and SCO-deactivation (1)). This variety of behaviors illustrates that the degree of elastic frustration can be manipulated by molecular guests, which suggests that the structural features that contribute to multistep switching may be more subtle than previously anticipated.

ETS-10 as a photocatalyst

ETS-10 is a microporous titanosilicate zeolite with a framework containing linear Ti− O −Ti− O− chains. This paper describes an investigation of the photoreactivity of ETS-10 with the particular objective of evaluating the potential of this novel material as a zeolitic photocatalyst. The photoreactivity and photocat- alytic activity of ETS-10 are strongly influenced by defects in the structure. A relatively defect free material catalyses photo-polymerisation of ethene, and in the presence of oxygen catalyses the partial oxidation of ethene to acetic acid and acetaldehyde, which remain strongly adsorbed in the pores. A more defective material is photoreduced when irradiated in the presence of adsorbed ethene, and catalyses the complete oxidation of ethene to carbon dioxide and water in the presence of oxygen. These differences are attributed to differences in the concentrations of exposed titanium sites associated with defects in the ETS-10 structure.