A variety of different three-dimensional metal-organic container molecules have recently been prepared using subcomponent self-assembly, which relies upon metal template effects to generate complex structures from simple molecular... more
A variety of different three-dimensional metal-organic container molecules have recently been prepared using subcomponent self-assembly, which relies upon metal template effects to generate complex structures from simple molecular precursors and metal salts. Many of these structures have well defined internal pockets, allowing guest species to be bound and the chemical reactivity of these guests to be modified. Such host molecules have potential applications ranging from the protection of sensitive chemical species to the separation and purification of substrates as diverse as gases, gold compounds, and fullerenes.
The behaviour of metal-organic cages upon guest encapsulation can be difficult to elucidate in solution. Paramagnetic metal centres introduce additional dispersion of signals that is useful for characterisation of host-guest complexes in... more
The behaviour of metal-organic cages upon guest encapsulation can be difficult to elucidate in solution. Paramagnetic metal centres introduce additional dispersion of signals that is useful for characterisation of host-guest complexes in solution using nuclear magnetic resonance (NMR). However, paramagnetic centres also complicate spectral assignment due to line broadening, signal integration error, and large changes in chemical shifts, which can be difficult to assign even for known compounds. Quantum chemical predictions can provide information that greatly facilitates the assignment of NMR signals and identification of species present. Here we explore how the prediction of paramagnetic NMR spectra may be used to gain insight into the spin crossover (SCO) properties of iron(II)-based metal organic coordination cages, specifically examining how the structure of the local metal coordination environment affects SCO. To represent the tetrahedral metal-organic cage, a model system is generated by considering an isolated metal-ion vertex: fac-ML3(2+) (M = Fe(II), Co(II); L = N-phenyl-2-pyridinaldimine). The sensitivity of the (1)H paramagnetic chemical shifts to local coordination environments is assessed and utilised to shed light on spin crossover behaviour in iron complexes. Our data indicate that expansion of the metal coordination sphere must precede any thermal SCO. An attempt to correlate experimental enthalpies of SCO with static properties of bound guests shows that no simple relationship exists, and that effects are likely due to nuanced dynamic response to encapsulation.
To prepare new functional covalent architectures that are difficult to synthesize using conventional organic methods, we developed a strategy that employs metal-organic assemblies as precursors, which are then reduced and demetalated. The... more
To prepare new functional covalent architectures that are difficult to synthesize using conventional organic methods, we developed a strategy that employs metal-organic assemblies as precursors, which are then reduced and demetalated. The host-guest chemistry of the larger receptor thus prepared was studied using NMR spectroscopy and fluorescence experiments. This host was observed to strongly bind aromatic polyanions in water, including the fluorescent dye molecule pyranine with nanomolar affinity, thus allowing for the design of an indicator-displacement assay.
How much should we switch? Two FeII₄L₄ tetrahedral capsules were shown to undergo thermally induced spin crossover (SCO). Guest binding to one of these capsules was observed to affect the thermodynamics of its SCO in solution, leading to... more
How much should we switch? Two FeII₄L₄ tetrahedral capsules were shown to undergo thermally induced spin crossover (SCO). Guest binding to one of these capsules was observed to affect the thermodynamics of its SCO in solution, leading to different spin transition temperatures between the empty host (blue) and the host-guest complex (red). HS: high spin; LS: low spin.
Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) (1), [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) (2),... more
Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt(13)(CO)(12){Cd(5)(μ-Br)(5)Br(2)(dmf)(3)}(2)](2-) (1), [Pt(19)(CO)(17){Cd(5)(μ-Br)(5)Br(3)(Me(2)CO)(2)}{Cd(5)(μ-Br)(5)Br(Me(2)CO)(4)}](2-) (2), [H(2)Pt(26)(CO)(20)(CdBr)(12)](8-) (3) and [H(4)Pt(26)(CO)(20)(CdBr)(12)(PtBr)(x)](6-) (4) (x = 0-2), have been obtained from the reactions between [Pt(3n)(CO)(6n)](2-) (n = 2-6) and CdBr(2)·H(2)O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt(26)Cd(12) metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.
To prepare new functional covalent architectures that are difficult to synthesize using conventional organic methods, we developed a strategy that employs metal-organic assemblies as precursors, which are then reduced and demetalated. The... more
To prepare new functional covalent architectures that are difficult to synthesize using conventional organic methods, we developed a strategy that employs metal-organic assemblies as precursors, which are then reduced and demetalated. The host-guest chemistry of the larger receptor thus prepared was studied using NMR spectroscopy and fluorescence experiments. This host was observed to strongly bind aromatic polyanions in water, including the fluorescent dye molecule pyranine with nanomolar affinity, thus allowing for the design of an indicator-displacement assay.
In this paper, we replicate a study of collaborative mobile phone use to share personal photos in groups of collocated people. The replication study was conducted in a different cultural context to check the generalizability of the... more
In this paper, we replicate a study of collaborative mobile phone use to share personal photos in groups of collocated people. The replication study was conducted in a different cultural context to check the generalizability of the findings from the original study in terms of the proposed interaction techniques, current photo sharing practices, and privacy. Our results confirm and expand the original findings. We report our main findings by comparing them to the key findings of the original study. Finally, we discuss possible reasons for some variance in the results.