We have used both action and photoelectron spectroscopy to study the response of isolated PdII meso-tetra(4-sulfonatophenyl)porphyrin tetraanions ([PdTPPS]4–) to electronic excitation over the 2.22–2.98 eV photon energy range. The action spectrum obtained by recording the wavelength-dependent intensity of charged decay products closely resembles the absorption spectrum of PdTPPS in aqueous solution (which shows pronounced Q and Soret absorption bands). The two main decay channels observed are sulfonate group loss and, predominantly, electron emission. To better understand the electron emission channel, we have also acquired photoelectron spectra at multiple detachment photon energies covering the range probed in action spectroscopy. Upon both Q and Soret band excitation, we find that electrons are emitted in three characteristic kinetic energy ranges. The corresponding detachment processes are identified as (delayed) tunneling emission from both excited singlet and triplet states (each of which is accessed by/after one-photon absorption) as well as resonant two-photon detachment. The first triplet state lifetime of isolated [PdTPPS]4– is significantly longer than 10 μs, possibly on the 100 μs time scale. We estimate that more than 50% of the electron emission observed upon photoexcitation occurs by way of this triplet state.

We have combined ion mobility mass spectrometry with quantum chemical calculations to investigate the gas-phase structures of multiply negatively charged oligomers of meso-tetra(4-sulfonatophenyl)metalloporphyrins comprising the divalent metal centers ZnII, CuII, and PdII. Sets of candidate structures were obtained by geometry optimizations based on calculations at both the semiempirical PM7 and density functional theory (DFT) levels. The corresponding theoretical cross sections were calculated with the projection approximation and also with the trajectory method. By comparing these collision cross sections with the respective experimental values we were able to assign oligomer structures up to the tetramer. In most cases the cross sections of the lowest energy isomers predicted by theory were found to agree with the measurements to within the experimental uncertainty (2%). Specifically, we find that for a given oligomer size the structures are independent of the metal center but depend strongly on the charge state. Oligomers in low charge states with a correspondingly larger number of sodium counterions tend to form stacked, cofacial structures reminiscent of H-aggregate motifs observed in solution. By contrast, in higher charge states, the stack opens to form coplanar structures.

Supramolecular guest–host complexes comprising various azaporphines stacked in a coordination nanoprism consisting of tris(4-pyridyl)triazines as panels, 1,4-bis(pyridyl)benzenes as pillars and (en)Pd as hinges were synthesized according to the procedure of Fujita and coworkers and characterized as ions in the gas-phase by high-resolution electrospray ionization mass spectrometry and collision induced dissociation as well as in solution by analytical ultracentrifugation. Apart from fully filled nanoprisms we have also prepared and observed partially filled as well as empty congeners in aqueous solutions. Upon mixing room temperature solutions of two types of nanoprisms, we observe that azaporphine guest exchange reactions occur on a timescale of minutes, indicating that the formation of the guest–host complexes is reversible.

We have developed a novel instrument that combines ion mobility spectrometry, mass spectro-metry, and photoelectron spectroscopy. The instrument couples an electrospray ion source, a high-transmission ion mobility cell based on ion funnels, a quadrupole mass filter, and a time-of-flight (magnetic bottle) photoelectron spectrometer operated with a pulsed detachment laser. We show that the instrument can resolve highly structured anion arrival time distributions and at the same time provide corresponding photoelectron spectra—using the DNA oligonucleotide ion [dC6 − 5H]5− as a test case. For this multianion we find at least four different, noninterconverting isomers (conformers) simultaneously present in the gas phase at room temperature. For each of these we record well-resolved and remarkably different photoelectron spectra at each of three different detachment laser wavelengths. Two-dimensional ion mobility/electron binding energy plots can be acquired with an automated data collection procedure. We expect that this kind of instrument will significantly improve the capabilities for structure determination of (bio)molecular anions in the gas phase.