Stability of high‐mass molecular libraries: the role of the oligoporphyrin core

Molecular beam techniques are a key to many experiments in physical chemistry and quantum optics. In particular, advanced matter‐wave experiments with high‐mass molecules profit from the availability of slow, neutral and mass‐selected molecular beams that are sufficiently stable to remain intact during laser heating and photoionization mass spectrometry. We present experiments on the photostability with molecular libraries of tailored oligoporphyrins with masses up to 25 000 Da. We compare two fluoroalkylsulfanyl‐functionalized libraries based on two different molecular cores that offer the same number of anchor points for functionalization but differ in their geometry and electronic properties. A pentaporphyrin core stabilizes a library of chemically well‐defined molecules with more than 1600 atoms. They can be neutrally desorbed with velocities as low as 20 m/s and efficiently analyzed in photoionization mass spectrometry. Copyright © 2015 John Wiley & Sons, Ltd.