Quantum tunneling in real space: Tautomerization of single porphycene molecules on the (111) surface of Cu, Ag, and Au

Tautomerization in single porphycene molecules is investigated on Cu(111), Ag(111), and Au(111) surfaces by a combination of low-temperature scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations. It is revealed that the trans configuration is the thermodynamically stable form of porphycene on Cu(111) and Ag(111), whereas the cis configuration occurs as a meta-stable form. The trans → cis or cis → trans conversion on Cu(111) can be induced in an unidirectional fashion by injecting tunneling electrons from the STM tip or heating the surface, respectively. We find that the cis → cis tautomerization on Cu(111) occurs spontaneously via tunneling, verified by the negligible temperature dependence of the tautomerization rate below ∼23 K. Van der Waals corrected DFT calculations are used to characterize the adsorption structures of porphycene and to map the potential energy surface of the tautomerization on Cu(111). The calculated barriers are too high to be thermally overcome at cryogenic temperatures used in the experiment and zero-point energy corrections do not change this picture, leaving tunneling as the most likely mechanism. On Ag(111), the reversible trans → cis conversion occurs spontaneously at 5 K and the cis → cis tautomerization rate is much higher than on Cu(111), indicating a significantly smaller tautomerization barrier on Ag(111) due to the weaker interaction between porphycene and the surface compared to Cu(111). Additionally, the STM experiments and DFT calculations reveal that tautomerization on Cu(111) and Ag(111) occurs with migration of porphycene along the surface; thus, the translational motion couples with the tautomerization coordinate. On the other hand, the trans and cis configurations are not discernible in the STM image and no tautomerization is observed for porphycene on Au(111). The weak interaction of porphycene with Au(111) is closest to the gas-phase limit and therefore the absence of trans and cis configurations in the STM images is explained either by the rapid tautomerization rate or the similar character of the molecular frontier orbitals of the trans and cis configurations

Searching for correlations between geometric and spectroscopic parameters of intramolecular hydrogen bonds in porphyrin-like macrocycles

Chemical bond lengths and angles are characteristic structural parameters of a molecule. Similarly, the frequencies of the vibrational modes and the NMR chemical shifts are unique "chemical fingerprints" specific to a compound. These are the basic parameters describing newly obtained compounds and enabling their identification. Intramolecular hydrogen bonding significantly influences the physicochemical properties of macrocyclic compounds with a porphyrin-like structure. This work presents the verification for correlations between geometric and spectroscopic parameters related to hydrogen bonds in this type of macrocyclic compounds. In particular, such relationships were investigated for a large group of porphyrin, porphycene, and dibenzotetraaza[14]annulene derivatives and a group of other macrocycles with similar structure. A very strong linear correlation was found only between the vibrational frequencies of the NH groups involved in a hydrogen bond and the length of this bond, which applied to all macrocyclic compounds of this type. Several other relationships were found between spectroscopic (IR, Raman, NMR) and geometric (X-ray) parameters, highlighting differences and similarities between different families of macrocycles. Apart from providing a better understanding of the nature of hydrogen bonds and their characteristics in porphyrin-like macrocyclic compounds, these relationships will facilitate the identification of new macrocycles and the extrapolation of their spectroscopic properties

Towards the detection limit of electrochemistry: Studying anodic processes with a fluorogenic reporting reaction

Recently, shot noise has been shown to be an inherent part of all charge transfer processes, leading to a practical limit of quantification of 2100 electrons (~0.34 fC) (Curr. Opin. Electrochem. 2020, 22, 170177). Attainable limits of quantification are made much larger by greater background currents and insufficient instrumentation, which restricts progress in sensing and single-entity applications. This limitation can be overcome by converting electrochemical charges into photons, which can be detected with much greater sensitivity, even down to a single-photon level. In this work, we demonstrate the use of fluorescence, induced through a closed-bipolar set-up, to monitor charge transfer processes below the detection limit of electrochemical workstations. During this process, the oxidation of ferrocenemethanol (FcMeOH) in one cell is used to concurrently drive the oxidation of Amplex Red (AR), a fluorogenic redox molecule, in another cell. The spectroelectrochemistry of AR is investigated and new insights on the commonplace practise of using deprotonated glucose to limit AR photooxidation are presented. The closed-bipolar set-up was used to produce fluorescent signals corresponding to the steady-state voltammetry of FcMeOH on a microelectrode. Chronopotentiometry is then used to show a linear relationship between the charge passed through FcMeOH oxidation and the integrated AR fluorescence signal. The sensitivity of the measurements obtained at different timescales varies between 2200 - 500 electrons per detected photon. The electrochemical detection limit is approached using a diluted FcMeOH solution in which no current signal is observed. Nevertheless, a fluorescence signal corresponding to FcMeOH oxidation is still seen, and detection of charges down to 300 fC is demonstrated