Abstract

The transfer of the inherent bistability of spin crossover compounds to surfaces has attracted considerable interest in recent years. The deposition of the complexes on surfaces allows investigating them individually and to further understand the microscopic mechanisms at play. Moreover, it offers the prospect of engineering switchable functional surfaces. We review recent progress in the field with a particular focus on the challenges and limits associated with the dominant experimental techniques used, namely near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). One of the main difficulties in NEXAFS-based experiments is to ascertain that the complexes are in direct contact with the surfaces. We show that molecular coverage determination based on the amplitude of the edge-jump of interest is challenging because the latter quantity depends on the substrate. Furthermore, NEXAFS averages the signals of a large number of molecules, which may be in different states. In particular, we highlight that the signal of fragmented molecules is difficult to distinguish from that of intact and functional ones. In contrast, STM allows investigating individual complexes, but the identification of the spin states is at best done indirectly. As quite some of the limits of the techniques are becoming apparent as the field is gaining maturity, their detailed descriptions will be useful for future investigations and for taking a fresh look at earlier reports.

Highlights

  • Spin-crossover (SCO) complexes can be switched between two states characterized by different electronic, optical, magnetic and geometric properties [1,2] making these complexes attractive for a wide range of applications [3,4,5,6], including smart pigments, actuators [7,8], and data storage [9,10,11,12,13,14]

  • We review recent progress in the field with a particular focus on the challenges and limits associated with the dominant experimental techniques used, namely near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM)

  • Since the prototypical demonstrations of single molecule switching in 2012 [30,38], the field of SCO complexes in direct contact with surfaces has gained a degree of maturity

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Summary

Introduction

Spin-crossover (SCO) complexes can be switched between two states characterized by different electronic, optical, magnetic and geometric properties [1,2] making these complexes attractive for a wide range of applications [3,4,5,6], including smart pigments, actuators [7,8], and data storage [9,10,11,12,13,14]. SCO compounds in direct contact with surfaces can be investigated in the ultimate limit of single molecules. This may, in principle, reduce the complexity of the system, which is essential for understanding in detail the physical mechanisms at play. Detailed investigations of various complexes, in particular on different substrates, along with improved quality of data allowed new discoveries and a better understanding of the mechanisms at play and challenge the interpretations of some earlier studies This brief review is intended to highlight the challenges inherent to SCO systems in direct contact with surfaces and the difficulties in interpreting corresponding STM and NEXAFS data

NEXAFS Methodology for Spin-State Determination and Related Challenges
Thickness Determination in NEXAFS Experiments
Fragmentation of SCO Complexes on Metal Substrates
Spin-State Coexistence
Distinction between Fragmentation and Spin-State Coexistence
Identification of the Spin States with STM
Findings
Conclusions
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