Spontaneous Synthesis of [FeII (Atrz)3 ]SO4 and its Analogues Through Accelerated Ageing: New Insights from Small-Scale Reactions.

Accelerated ageing reactions that take place between two solid materials on contact in the absence of added solvent have been used to synthesize two spin-crossover-active 1D coordination polymers and one of their Cu(II) analogues. The hygroscopy of the ligands and the relative humidity of the reaction chamber have been shown to be particularly important factors in the rate of reaction. Small-scale reactions between a few individual crystals have allowed observation of deliquescence of the 4-aminotriazole ligand at high humidity. The metal salt does not dissolve, and the ligand diffuses into the crystal of the metal salt during the reaction. In the case of the Cu analogue, the formation of the product causes the crystal of the metal salt to deform with the formation of pseudocrystals, which have a fibrous structure.

A Reversibly Porous Supramolecular Peptide Framework.

The ability to use bio-inspired building blocks in the assembly of novel supramolecular frameworks is at the forefront of an exciting research field. Herein, we present the first polyproline helix to self-assemble into a reversibly porous, crystalline, supramolecular peptide framework (SPF). This framework is assembled from a short oligoproline, adopting the polyproline II conformation, driven by hydrogen-bonding and dispersion interactions. Thermal activation, guest-induced dynamic porosity and enantioselective guest inclusion have been demonstrated for this novel system. The principles of the self-assembly associated with this SPF will be used as a blueprint allowing for the further development of helical peptide linkers in the rational design of SPFs and metal-peptide frameworks.

Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex.

The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine (Co(diox)2(4-CN-py)2) is a very versatile compound that displays valence tautomerism (VT) in the solid state, which is induced by temperature, light, and hard X-rays, and modulated by solvent in the crystal lattice. In our work, we used single crystal X-ray diffraction as a probe for the light-induced VT in solid state and demonstrate the controlled use of hard X-rays via attenuation to avoid X-ray-induced VT interconversion. We report photoinduced VT in benzene solvated crystals of Co(diox)2(4-CN-py)2 illuminated with blue 450 nm light at 30 K with a very high yield (80%) of metastable hs-CoII states, and we also show evidence of the de-excitation of these photoinduced metastable states using red 660 nm light. Such high-yield light-induced VT had never been experimentally observed in molecular crystals of cobalt tautomers, proving that the 450 nm light illumination is triggering a chain of events that leads to the ls-CoIII to hs-CoII interconversion.

A simple strategy to overcome concentration dependence of photoswitching properties in donor-acceptor Stenhouse adducts.

Photoswitchable donor-acceptor Stenhouse adducts (DASAs) have been reported to exhibit an undesirable concentration dependence, where photoswitching is greatly inhibited with increasing photochrome concentration. Here we show that the use of piperazine-based donor moieties eliminates this concentration dependence and results in complete, rapid and reversible photoswitching behaviour for first generation DASAs, even in chlorinated solvents. Structural data and computational studies reveal proton transfer during isomerisation to the terminal amine rather than the donor amine. The improvement in photoswitching efficiency is attributed to resultant differences in supramolecular association.

Metastable 9-Fluorenone: Blueshifted Fluorescence, Single-Crystal-to-Single-Crystal Reactivity, and Evaluation as a Multimodal Fingermark Visualization Treatment.

A metastable form of 9-fluorenone (MS9F) has been characterized using Raman spectroscopy, fluorimetry, and X-ray diffraction techniques. MS9F emits blue fluorescence (λmax =495 nm) upon 365 nm irradiation and undergoes a single-crystal-to-single-crystal (SCSC) transformation to reach the ground state form (GS9F) over approximately 30 minutes, whereupon it emits the expected green fluorescence. A structure-property relationship for this fluorescent behavior has been posited. MS9F and GS9F were applied as a means of visualizing latent fingermarks on a nonporous surface. This approach identified three different modes of fluorescent fingermark visualization using 9-fluorenone.

ß-Ketoiminato Iridium(III) Organometallic Complexes: Selective Cytotoxicity towards Colorectal Cancer Cells HCT116 p53-/.

This report presents a new library of organometallic iridium(III) compounds of the type [Cp*IrCl(L)] (Cp*=pentamethylcyclopentadienyl and L=a functionalized ß-ketoiminato ligand) showing moderate to high cytotoxicity against a range of cancer cell lines. All compounds show increased activity towards colorectal cancer, with preferential activity observed against the immortalized p53-null colorectal cell line, HCT116 p53-/-, with sensitivity factors (SF) up to 26.7. Additionally, the compounds have excellent selectivity for cancerous cells when tested against normal cell types, with selectivity ratios (SR) up to 35.6, contrary to that of cisplatin, which is neither selective nor specific for cancerous cells (SF=0.43 and SR=0.7-2.3). This work provides a preliminary understanding of the cytotoxicity of iridium compounds in the absence of p53 and has potential applications in treatment of cancers for which the p53 gene is absent or mutant.

Complete Set of Elastic Moduli of a Spin-Crossover Solid: Spin-State Dependence and Mechanical Actuation.

Molecular spin crossover complexes are promising candidates for mechanical actuation purposes. The relationships between their crystal structure and mechanical properties remain, however, not well understood. In this study, combining high pressure synchrotron X-ray diffraction, nuclear inelastic scattering, and micromechanical measurements, we assessed the effective macroscopic bulk modulus ( B = 11.5 ± 1.5 GPa), Young's modulus ( Y = 10.9 ± 1.0 GPa), and Poisson's ratio (ν = 0.34 ± 0.04) of the spin crossover complex [FeII(HB(tz)3)2] (tz = 1,2,4-triazol-1-yl). Crystal structure analysis revealed a pronounced anisotropy of the lattice compressibility, which was correlated with the difference in spacing between the molecules as well as by the distribution of the stiffest C-H···N interactions in different crystallographic directions. Switching the molecules from the low spin to the high spin state leads to a remarkable drop of the Young's modulus to 7.1 ± 0.5 GPa both in bulk and thin film samples. The results highlight the application potential of these films in terms of strain (ε = -0.17 ± 0.05%), recoverable stress (σ = -21 ± 1 MPa), and work density ( W/V = 15 ± 6 mJ/cm3).

Towards the Prediction of Global Solution State Properties for Hydrogen Bonded, Self-Associating Amphiphiles.

Through this extensive structure-property study we show that critical micelle concentration correlates with self-associative hydrogen bond complex formation constant, when combined with outputs from low level, widely accessible, computational models. Herein, we bring together a series of 39 structurally related molecules related by stepwise variation of a hydrogen bond donor-acceptor amphiphilic salt. The self-associative and corresponding global properties for this family of compounds have been studied in the gas, solid and solution states. Within the solution state, we have shown the type of self-associated structure present to be solvent dependent. In DMSO, this class of compound show a preference for hydrogen bonded dimer formation, however moving into aqueous solutions the same compounds are found to form larger self-associated aggregates. This observation has allowed us the unique opportunity to investigate and begin to predict self-association events at both the molecular and extended aggregate level.

Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes.

Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.

Influencing the Optoelectronic Properties of a Heteroleptic Iridium Complex by Second-Sphere H-Bonding Interactions.

The use of a new second-sphere coordination methodology for emission color tuning of iridium complexes is presented. We demonstrate that a complementary H-bonding guest molecule binding through contiguous triple H-bonding interactions can induce a shift in the emission of the iridium complex from green to blue without the need to alter the ligand structure around the metal center, while simultaneously increasing the photoluminescence quantum yield in solution. The association constant for this host-guest interaction was determined to be Ka = 4.3 × 103 M-1 in a solution of 2% dimethyl sulfoxide in chloroform by UV-vis titration analysis and the impact of the hydrogen bonding interaction further probed by photoluminescence, electrochemical, and computational methods. Our findings suggest that directed self-assemblies are an effective approach to influencing emission properties of phosphorescent iridium(III) complexes.

Bis-picolinamide Ruthenium(III) Dihalide Complexes: Dichloride-to-Diiodide Exchange Generates Single trans Isomers with High Potency and Cancer Cell Selectivity.

A library of new bis-picolinamide ruthenium(III) dihalide complexes of the type [RuX2 L2 ] (X=Cl or I, L=picolinamide) have been synthesised and characterised. The complexes exhibit different picolinamide ligand binding modes, whereby one ligand is bound (N,N) and the other bound (N,O). Structural studies revealed a mixture of cis and trans isomers for the [RuCl2 L2 ] complexes but upon a halide exchange reaction to yield [RuI2 L2 ], only single trans isomers were detected. High cytotoxic activity against human cancer cell lines was observed, with the potencies of some complexes similar to or better than cisplatin. The conversion to [RuI2 L2 ] substantially increased the activity towards cancer cell lines by more than twelvefold. The [RuI2 L2 ] complexes displayed potent activity against the A2780cis (cisplatin-resistant human ovarian cancer) cell line, with a more than fourfold higher potency than cisplatin. Equitoxic activity was observed against normoxic and hypoxic cancer cells, which indicates the potential to eradicate both the hypoxic and aerobic fractions of solid tumours with similar efficiency. The activity of selected complexes against non-cancer ARPE-19 cells was also tested. The [RuI2 L2 ] complexes were found to be more potent than the [RuCl2 L2 ] analogues and also more selective towards cancer cells with a selectivity factor in excess of sevenfold.

An Iodine-Vapor-Induced Cyclization in a Crystalline Molecular Flask.

A vapor-induced cyclization has been observed in the host environment of a crystalline molecular flask (CMF), within which 1,8-bis(2-phenylethynyl)naphthalene (bpen), a diarenynyl system primed for cyclization, was exposed to iodine vapor to yield the corresponding indeno[2,1-α]phenalene species. The cyclization process, unique in its vapor-induced, solvent-free nature, was followed spectroscopically, and found to occur concurrently with the displacement of lattice solvent for molecular iodine in CMF⋅0.75 bpen⋅2.25 CHCl3 ⋅H2 O. The cyclization occurred under mild conditions and without the need to suspend the crystals in solvent. The ability of CMFs to host purely gas-induced reactions is further highlighted by the subsequent sequential oxidation reaction of cyclized 7-iodo-12-phenylindeno[2,1-α]phenalene (ipp) with molecular oxygen derived from air, yielding 12-hydroxy-7-iodo-2-phenylindeno[2,1-α]phenalen-1(12H)-one (hipp).

Decoupled spin crossover and structural phase transition in a molecular iron(II) complex.

Crystalline [Fe(bppSMe)2][BF4]2 (1; bppSMe = 4-(methylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine) undergoes an abrupt spin-crossover (SCO) event at 265±5 K. The crystals also undergo a separate phase transition near 205 K, involving a contraction of the unit-cell a axis to one-third of its original value (high-temperature phase 1; Pbcn, Z = 12; low-temperature phase 2; Pbcn, Z = 4). The SCO-active phase 1 contains two unique molecular environments, one of which appears to undergo SCO more gradually than the other. In contrast, powder samples of 1 retain phase 1 between 140-300 K, although their SCO behaviour is essentially identical to the single crystals. The compounds [Fe(bppBr)2][BF4]2 (2; bppBr = 4-bromo-2,6-di(pyrazol-1-yl)pyridine) and [Fe(bppI)2][BF4]2 (3; bppI = 4-iodo-2,6-di(pyrazol-1-yl)-pyridine) exhibit more gradual SCO near room temperature, and adopt phase 2 in both spin states. Comparison of 1-3 reveals that the more cooperative spin transition in 1, and its separate crystallographic phase transition, can both be attributed to an intermolecular steric interaction involving the methylsulfanyl substituents. All three compounds exhibit the light-induced excited-spin-state trapping (LIESST) effect with T(LIESST = 70-80 K), but show complicated LIESST relaxation kinetics involving both weakly cooperative (exponential) and strongly cooperative (sigmoidal) components.

Tunable trimers: using temperature and pressure to control luminescent emission in gold(I) pyrazolate-based trimers.

A systematic investigation into the relationship between the solid-state luminescence and the intermolecular Au⋅⋅⋅Au interactions in a series of pyrazolate-based gold(I) trimers; tris(µ2 -pyrazolato-N,N')-tri-gold(I) (1), tris(µ2 -3,4,5- trimethylpyrazolato-N,N')-tri-gold(I) (2), tris(µ2 -3-methyl-5-phenylpyrazolato-N,N')-tri-gold(I) (3) and tris(µ2 -3,5-diphenylpyrazolato-N,N')-tri-gold(I) (4) has been carried out using variable temperature and high pressure X-ray crystallography, solid-state emission spectroscopy, Raman spectroscopy and computational techniques. Single-crystal X-ray studies show that there is a significant reduction in the intertrimer Au⋅⋅⋅Au distances both with decreasing temperature and increasing pressure. In the four complexes, the reduction in temperature from 293 to 100 K is accompanied by a reduction in the shortest intermolecular Au⋅⋅⋅Au contacts of between 0.04 and 0.08 Å. The solid-state luminescent emission spectra of 1 and 2 display a red shift with decreasing temperature or increasing pressure. Compound 3 does not emit under ambient conditions but displays increasingly red-shifted luminescence upon cooling or compression. Compound 4 remains emissionless, consistent with the absence of intermolecular Au⋅⋅⋅Au interactions. The largest pressure induced shift in emission is observed in 2 with a red shift of approximately 630 cm(-1) per GPa between ambient and 3.80 GPa. The shifts in all the complexes can be correlated with changes in Au⋅⋅⋅Au distance observed by diffraction.

A homologous series of [Fe(H2Bpz2)2(L)] spin-crossover complexes with annelated bipyridyl co-ligands.

Four new iron(II) complexes [Fe(H2Bpz2)2(L)] were prepared (pz = pyrazolyl), where L is dipyrido[3,2-f:2',3'-h]quinoxaline (dpq), dipyrido[3,2-a:2'3'-c]phenazine (dppz), dipyrido[3,2-a:2'3'-c]benzo[i]-phenazine (dppn), and dipyrido[3,2-a:2',3'-c](6,7,8,9-tetrahydro)phenazine (dppc). Crystal structures of [Fe(H2Bpz2)2(dpq)], [Fe(H2Bpz2)2(dppz)], and [Fe(H2Bpz2)2(dppn)] all reveal stacks of complex molecules formed through π-π stacking between interdigitated bipyridyl chelate ligands, often with additional intercalated toluene or uncoordinated bipyridyl ligand (dpq). Molecules of [Fe(H2Bpz2)2(dppc)] form a different stacking motif in the crystal, with weaker contacts between individual molecules. Many of the structures also contain channels of disordered solvent, running between the molecular stacks. Despite their different stacking motifs, all these compounds exhibit very gradual thermal spin-crossover (SCO) on cooling, which occur over different temperature ranges but are otherwise quite similar in form. Weak thermal hysteresis in one of these spin equilibria can be attributed to the effects of a change in bipyridyl ligand conformation in the molecular stacks around 150 K, which was observed crystallographically. These results demonstrate that strong mechanical coupling between molecules in a crystal is not sufficient to engineer cooperative SCO switching, if other regions of the lattice are less densely packed.

Tunable spin-crossover behavior of the Hofmann-like network {Fe(bpac)[Pt(CN)4]} through host-guest chemistry.

A study of the spin-crossover (SCO) behavior of the tridimensional porous coordination polymer {Fe(bpac)[Pt(CN)4]} (bpac=bis(4-pyridyl)acetylene) on adsorption of different mono- and polyhalobenzene guest molecules is presented. The resolution of the crystal structure of {Fe(bpac)[Pt(CN)4]}⋅G (G=1,2,4-trichlorobenzene) shows preferential guest sites establishing π⋅⋅⋅π stacking interactions with the host framework. These host-guest interactions may explain the relationship between the modification of the SCO behavior and both the chemical nature of the guest molecule (electronic factors) and the number of adsorbed molecules (steric factors).

Supramolecular Self-Assembly of Engineered Polyproline Helices.

The ability to rationally design biomaterials to form desired supramolecular constructs presents an ever-growing research field, with many burgeoning works within recent years providing exciting results; however, there exists a broad expanse of promising avenues of research yet to be investigated. As such we have set out to make use of the polyproline helix as a rigid, tunable, and chiral ligand for the rational design and synthesis of supramolecular constructs. In this investigation, we show how an oligoproline tetramer can be specifically designed and functionalized, allowing predictable tuning of supramolecular interactions, to engineer the formation of supramolecular peptide frameworks with varying properties and, consequently, laying the groundwork for further studies utilizing the polyproline helix, with the ability to design desired supramolecular structures containing these peptide building blocks, having tunable structural features and functionalities.

Controlling the structure of supramolecular fibre formation for benzothiazole based hydrogels with antimicrobial activity against methicillin resistant Staphylococcus aureus.

Antimicrobial resistance is one of the greatest threats to human health. Gram-positive methicillin resistant Staphylococcus aureus (MRSA), in both its planktonic and biofilm form, is of particular concern. Herein we identify the hydrogelation properties for a series of intrinsically fluorescent, structurally related supramolecular self-associating amphiphiles and determine their efficacy against both planktonic and biofilm forms of MRSA. To further explore the potential translation of this hydrogel technology for real-world applications, the toxicity of the amphiphiles was determined against the eukaryotic multicellular model organism, Caenorhabditis elegans. Due to the intrinsic fluorescent nature of these supramolecular amphiphiles, material characterisation of their molecular self-associating properties included; comparative optical density plate reader assays, rheometry and widefield fluorescence microscopy. This enabled determination of amphiphile structure and hydrogel sol dependence on resultant fibre formation.

Photomagnetism of a sym-cis-dithiocyanato iron(II) complex with a tetradentate N,N'-bis(2-pyridylmethyl)1,2-ethanediamine ligand.

A comprehensive study of the magnetic and photomagnetic behaviors of cis-[Fe(picen)(NCS)(2) ] (picen = N,N'-bis(2-pyridylmethyl)1,2-ethanediamine) was carried out. The spin-equilibration was extremely slow in the vicinity of the thermal spin-transition. When the cooling speed was slower than 0.1 K min(-1), this complex was characterized by an abrupt thermal spin-transition at about 70 K. Measurement of the kinetics in the range 60-70 K was performed to approach the quasi-static hysteresis loop. At low temperatures, the metastable HS state was quenched by a rapid freezing process and the critical T(TIESST) temperature, which was associated with the thermally induced excited spin-state-trapping (TIESST) effect, was measured. At 10 K, this complex also exhibited the well-known light-induced excited spin-state-trapping (LIESST) effect and the T(LIESST) temperature was determined. The kinetics of the metastable HS states, which were generated from the freezing effect and from the light-induced excitation, was studied. Single-crystal X-ray diffraction as a function of speed-cooling and light conditions at 30 K revealed the mechanism of the spin-crossover in this complex as well as some direct relationships between its structural properties and its spin state. This spin-crossover (SCO) material represents a fascinating example in which the metastability of the HS state is in close vicinity to the thermal spin-transition region. Moreover, it is a beautiful example of a complex in which the metastable HS states can be generated, and then compared, either by the freezing effect or by the LIESST effect.

Synergetic effect of host-guest chemistry and spin crossover in 3D Hofmann-like metal-organic frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni).

The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN)(4)] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN)(4)]}(n) planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Mössbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the π-π stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the nature and the amount of guest molecules in the lattice.