The crystal structures of (p-ClPh)3PO and (p-OMePh)3PO, including an analysis of the P-O bond in triarylphosphine oxides

The crystal structures of the compounds tris(para-chlorophenyl)phosphine oxide {(p-ClPh)₃PO} and tris(para-methoxyphenyl)phosphine oxide {(p-OMePh)₃PO} were determined by X-ray diffraction methods. (p-ClPh)₃PO crystallizes in the space group P-1 (no. 2) with a = 11.828(2), b = 12.645(2), c = 14.072(2) Å, = 97.90(1), = 109.45(1), = 115.43(1), V = 1692.3(2) ų and Z = 4. The mean O–P and C–P distances are 1.481(6) and 1.806(2) Å, respectively, and the mean C–P–C angle is 106.5(1.1). (p-OMePh)₃PO crystallizes in the space group P2₁/c (no. 14) with a = 18.8642 (10), b = 10.3999(5), c = 21.3462(16) Å, = 115.414(6)°, V= 3782.6(4) ų, and Z = 8. The mean O–P and C–P distances are 1.484(5) and 1.798(4) Å, respectively, and the mean C–P–C angle is 106.5(1.0). These two structures were analyzed along with the previously determined structures of triphenylphosphine oxide {Ph₃PO} and tri-p-tolylphosphine oxide {(p-MePh)₃PO}, and IR data were collected on all four compounds. Both the observed P–O distances and the IR stretching frequencies for these triarylphosphine oxides support the interpretation of the P–O bond as having substantial multiple-bond character, with a bond order between 1.7 and 1.8. The para-substituents on these triarylphosphines were shown to have a statistically insignificant effect on the P–O bond.     

In‐Transit Electroextraction of Small‐Molecule Pharmaceuticals from Blood

An electrokinetic platform was developed for extracting small‐molecule pharmaceuticals from a dried blood spot. Through the exclusion of liquid reagents and use of low field strength (6 V cm^?1), the electroextraction of a drug from a dried blood spot, deposited on a polymer inclusion membrane (PIM), could be realised while in transit in the mail. In transit sample preparation provides a potential solution to in situ sample degradation and may accelerate the workflow upon arrival of a patient sample at the analytical facility. The electroextraction method was enabled through our discovery of the use of 15–20 μm thin PIMs as electrophoretic separation medium in absence of liquid reagents. Here, a PIM consisting of cellulose triacetate as polymer base, 2‐nitrophenyl octyl ether as plasticizer and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide as carrier was used. The PIM, was packaged with two 12 V batteries to supply the separation voltage. A blood spot containing berberine chloride was deposited and dried before the applying the separation potential, allowing for the electroextraction while the packaged device was shipped in internal mail. Upon arrival in the analytical laboratory, the PIM was analysed using a fluorescence microscope with photon multiplier tube, quantifying the berberine extracted away from the sample matrix. This platform represents a new opportunity for processing clinical samples during transport to the laboratory, saving time and manual handling to accelerate the time to result.     

Intense broadband THz generation from femtosecond laser filamentation

Broadband and energetic terahertz (THz) pulses can be remotely generated in air through filamentation. We review such THz generation and detection in femtosecond Ti-sapphire laser induced remote filaments. New results are presented on the direct relationship between THz generation in a two color filament and induced N2 fluorescence through population trapping during molecular alignment and revival in air. This further supports the new technique of remote THz detection in air through the sensitive measurement of N2 fluorescence.     

Time-resolved studies of single quantum dots in magnetic fields

We present time-resolved and time-integrated spectroscopy of single InAs quantum dots grown in a GaAs matrix. We observe a number of interesting features in the spectra, including the zero field splitting of exciton and biexciton lines due to quantum dot asymmetry. By the application of an in-plane magnetic field, the normally optically active and inactive exciton states become mixed, enabling us to optically probe the normally inaccessible ‘dark’ states. Time resolved measurements on the mixed states show decay times several times longer than the exciton lifetime at zero field, which we show to be consistent with a dark exciton lifetime orders of magnitude longer than that for bright exciton.     

Synthesis,Characterization, and Non‐Volatile Memory Device Application of an N‐Substituted Heteroacene

N‐substituted heteroacenes have been widely used as electroactive layers in organic electronic devices, and only a few of them have been investigated in organic resistive memory devices. Here, a novel N‐substituted heteroacene 2‐(4′‐(diphenylamino)phenyl)‐4,11‐bis((triisopropylsilyl)ethynyl)‐1H‐imidazo[4,5‐b]phenazine ( DBIP ) has been designed, synthesized, and characterized. Sandwich‐structure memory devices based on DBIP have been fabricated and the devices show non‐volatile and stable memory character with good endurance performance.     

Divergent Chemistry Paths for 3D and 1D Metallo‐Covalent Organic Frameworks (COFs)

The marriage of dynamic covalent chemistry (DCC) and coordination chemistry is a powerful tool for assembling complex architectures from simple building units. Recently, the synthesis of woven covalent organic frameworks (COFs) with topologically fascinating structures has been achieved using this approach. However, the scope is highly limited and there is a need to discover new pathways that can assemble covalently linked organic threads into crystalline frameworks. Herein, we have identified branching pathways leading to the assembly of three‐dimensional (3D) woven COFs or one‐dimensional (1D) metallo‐COFs (mCOFs), where the mechanism is underpinned by the absence or presence of ligand exchange.     

Femtosecond laser ionization and fragmentation of molecules for environmental sensing

Recent studies have demonstrated that femtosecond laser pulses have high potential in application to environmental science. Because of the properties of ultrafast, broadband and high power, the propagation of femtosecond laser pulses in air can lead to the generation of a strong field of 10¹³–10¹⁴ W/cm² with a large distance range from meter to kilometers. The strong laser field induces ionization and fragmentation of molecules in the laser propagation path, resulting in characteristic fingerprint emissions. This paper mainly focuses on recent research advances in environmental sensing by using femtosecond laser pulses through strong‐field‐induced ionization and fragmentation of molecules. The fingerprint emissions of molecules in strong laser fields are discussed based on the understanding of strong‐field–molecule interactions in atmospheric as well as in vacuum environments. This is followed by a comprehensive review of several recently developed optical methods for coherent control of fingerprint emissions of molecules. Lastly, both current challenges and a future perspective of this dynamic field are discussed.