Spectroscopy and dynamics of isolated anions: Versatile instrumentation for photodetachment and photoelectron spectroscopy.

Molecular anions are appealing targets for study because, compared with their neutral and cationic counterparts, they can be probed with conventional laboratory lasers without the need for multiphoton ionization schemes, and they provide spectroscopic details on the corresponding neutral molecules. Here, we describe a section of a modular instrument designed to perform high-throughput photoelectron and photodetachment spectroscopy of gas-phase anions, with future provision for time-resolved and isomer-selective spectroscopy. The instrument framework allows for the incorporation and adaptation of several ion sources, as demonstrated here with plasma (electric) discharge sources providing variable hard to soft ion generation conditions. The generated anions are separated according to their mass-to-charge ratio through time-of-flight mass spectrometry (m/zΔm/z = 500-600) and are focused into a set of perpendicular velocity-map imaging electrodes (ΔEE≈4%), where mass-selected anions are probed using laser light and the ejected electrons are velocity-map imaged. Instrument performance is demonstrated through the acquisition of photodetachment and photoelectron spectra for CH2CN-, showing sharp resonances in the vicinity of the detachment threshold assigned to rovibrational states of a dipole-bound anion and broader lifetime-limited spectral features at photon energies well above the threshold assigned to prompt autodetachment from a temporary anion resonance. Similar measurements could be performed on any molecular anions generated in the sources.

Fixing the Conformation of Calix[4]arenes: When Are Three Carbons Not Enough?

Calix[4]arenes are unique macrocycles that through judicious functionalisation at the lower rim can be either fixed in one of four conformations or remain conformationally flexible. Introduction of propynyl or propenyl groups unexpectedly provides a new possibility; a unidirectional conformational switch, with the 1,3-alternate and 1,2-alternate conformers switching to the partial cone conformation, whilst the cone conformation is unchanged, under standard experimental conditions. Using 1 H NMR kinetic studies, rates of switching have been shown to be dependent on the starting conformation, upper-rim substituent, where reduction in bulk enables faster switching, solvent and temperature with 1,2-alternate conformations switching fastest. Ab initio calculations (DFT) confirmed the relative stabilities of the conformations and point towards the partial cone conformer being the most stable of the four. The potential impact on synthesis through the "click" reaction has been investigated and found not to be significant.

The photochemistry and photophysics of a series of alpha octa(alkyl-substituted) silicon, zinc and palladium phthalocyanines.

Photophysical and photochemical measurements have been made on a series of novel alpha octa(alkyl-substituted) silicon, zinc and palladium phthalocyanines for which the synthesis is outlined. Fluorescence quantum yields and lifetimes, triplet quantum yields and lifetimes and singlet delta oxygen quantum yields were measured in 1% v/v pyridine in toluene. The effects of varying central atom and addition of alkyl substituents relative to unsubstituted parent molecules, zinc phthalocyanine (ZnPc) and silicon phthalocyanine (SiPc), are discussed. All phthalocyanines studied exhibit absorption and emission maxima in the region of 680-750 nm with molar absorptivity of the Q-band ~10(5) M(-1) cm(-1). The series of compounds also exhibited triplet quantum yields of 0.65-0.95 and singlet oxygen quantum yields of 0.49-0.93.

The photochemistry and photophysics of a series of non-peripherally substituted zinc phthalocyanines.

Photophysical and photochemical measurements have been made on a series of novel non-peripherally octa(alkyl-substituted) zinc phthalocyanines. Fluorescence quantum yields and lifetimes, triplet quantum yields and lifetimes and singlet delta oxygen quantum yields were measured in 1% v/v pyridine in toluene. The effects of alkyl substituents and increasing chain length relative to the unsubstituted parent molecule, zinc phthalocyanine (ZnPc), are discussed. ZnPc with alkyl substituents of chain length 5-15 carbons exhibited similar absorption and emission maxima (704 nm and 718 nm respectively) with the molar absorptivity of the Q-band approximately 10(5) M(-1) cm(-1). The series of compounds also exhibited triplet quantum yields of 0.78-0.84 and singlet oxygen quantum yields of 0.67-0.71.

Room-temperature metal-hydride discharge source, with observations on NiH and FeH.

A metal sputtering source suitable for laboratory production of metal hydrides is described. Sputtering from pure nickel or iron in an Ar/H(2) discharge is analyzed at low resolution. High resolution laser excitation and dispersed fluorescence spectra of NiH have also been recorded. The source has been designed to operate with a ferromagnetic circuit for Zeeman spectroscopy. Signals from the source are strong enough to record dispersed fluorescence from NiH by Fourier transform interferometry in magnetic fields up to 1 T. We establish that FeH can also be formed in this source.