To investigate the ability for spin-state switching of spin-crossover (SCO) complexes adsorbed to solid substrates, the SCO complex [Fe­(H2B­(pz)2)2(phenme4)] (pz = pyrazole, phenme4 = 3,4,7,8-tetramethyl-1,10-phenanthroline) is prepared. The new complex is investigated by magnetic susceptibility measurements and Mößbauer spectroscopy in the solid state and by temperature-dependent UV/vis spectroscopy in a thin film deposited by physical vapor deposition (PVD) on quartz glass. Thermal- and light-induced SCO is observed in the bulk and the film on glass. Submonolayers of this complex obtained by PVD are studied by temperature-dependent near-edge X-ray absorption fine structure (NEXAFS) on Au(111) as well as Bi(111) and by scanning tunneling microscopy (STM) on Au(111). NEXAFS shows thermal- and light-induced spin-state switching of the complex on Bi(111), however, with a large temperature-independent high-spin fraction (∼50%). On the other hand, combined evidence from NEXAFS and STM indicates that on Au(111) the complex dissociates into [Fe­(H2B­(pz)2)2] and phenme4. Similar observations are made with the parent complex [Fe­(H2B­(pz)2)2(phen)], which on Bi(111) stays intact and exhibits thermal-induced as well as light-induced SCO, but on Au(111) dissociates into [Fe­(H2B­(pz)2)2] and phen.

Cooperative effects determine the spin-state bistability of spin-crossover molecules (SCMs). Herein, the ultimate scale limit at which cooperative spin switching becomes effective is investigated in a complex [Fe(H2B(pz)2)2(bipy)] deposited on a highly oriented pyrolytic graphite surface, using x-ray absorption spectroscopy. This system exhibits a complete thermal- and light-induced spin transition at thicknesses ranging from submonolayers to multilayers. On increasing the coverage from 0.35(4) to 10(1) monolayers, the width of the temperature-induced spin transition curve narrows significantly, evidencing the buildup of cooperative effects. While the molecules at the submonolayers exhibit an apparent anticooperative behavior, the multilayers starting from a double-layer exhibit a distinctly cooperative spin switching, with a free-molecule-like behavior indicated at around a monolayer. These observations will serve as useful guidelines in designing SCM-based devices.

Two polymorphic modifications (1-I and 1-II) of the new spin crossover (SCO) complex [Fe{H 2 B(pz)(pypz)} 2 ] (pz = pyrazole, pypz = pyridylpyrazole; 1) were prepared and investigated by differential scanning calorimetry (DSC), magnetic measurements, Moßbauer, vibrational, and absorption spectroscopy as well as single-crystal and X-ray powder diffraction. DSC measurements reveal that upon heating the thermodynamically metastable form 1-II to ∼178 °C it transforms into 1-I in an exothermic reaction, which proves that these modifications are related by monotropism. Both forms show thermal SCO with T 1/2 values of 390 K (1-II) and 270 K (1-I). An analysis of the crystal structures of 1-II and the corresponding Zn(II) (2) and Co(II) (3) complexes that are isotypic with 1-I reveals that form II consists of dimers coupled by strong intramolecular π•••π interactions, which is not the case for 1-I. In agreement with these findings, investigations of thin films of 1, where significant π•••π interactions should be absent, reveal SCO behavior similar to that of 1-I. These results underscore the importance of cooperativity for the spin-transition behavior of this class of complexes.

X-ray absorption spectroscopy investigations of the spin-state switching of spin-crossover (SCO) complexes adsorbed on a highly-oriented pyrolytic graphite (HOPG) surface have shown so far that HOPG is a promising candidate to realize applications such as spintronic devices because of the stability of SCO complexes on HOPG and the possibility of highly efficient thermal and light-induced spin-state switching. Herein, we present the spin switching of several Fe(II) SCO complexes adsorbed on an HOPG surface with particular emphasis on the thermally induced spin transition behaviour with respect to different structural modifications. The complexes of the type [Fe(bpz)2(L)] (bpz  =  dihydrobis(pyrazolyl)borate, L  =  1,10-phenanthroline, 2,2′-bipyridine) and their methylated derivatives exhibit SCO in the solid state with some differences regarding cooperative effects. However, in the vacuum-deposited thick films on quartz, complete and more gradual spin transition behavior is observable via UV/vis spectroscopy. In contrast to that, all complexes show large differences upon direct contact with HOPG. Whereas the unmodified complexes show thermal and light-induced SCO, the addition of e.g. two or four methyl groups leads to a partial or a complete loss of the SCO on the surface. The angle-dependent measurement of the N K-edge compared to calculations indicates that the complete SCO and HS-locked molecules on the surface exhibit a similar preferential orientation, whereas complexes undergoing an incomplete SCO exhibit a random orientation on the surface. These results are discussed in the light of molecule-substrate interactions.

The vibrational properties of spin-crossover complexes [Fe­(H2B­(pz)2)2(L)] (pz = pyrazole) containing L = 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) ligands are investigated by temperature-dependent infrared and Raman spectroscopy. For comparison, the analogous cobalt­(II) complexes [Co­(H2B­(pz)2)2(L)] (L = bipy and phen) and iron­(II) compounds with L = 4,4′-dimethyl-2,2′-bipyridine and 4,7-dimethyl-1,10-phenanthroline coligands are studied. Highly intense, structured bands (giant Raman features, GRFs) are observed in the resonance Raman spectra of all Fe­(II) complexes between 400 and 500 cm–1 at low temperatures in the HS state which, for the SCO complexes, is excited by the Raman laser. On the basis of magnetic field Mössbauer and saturation magnetization data electronic Raman effects are excluded to account for these features. Furthermore, detailed vibrational analysis also allows excluding a vibrational resonance Raman effect involving one of the modes of the individual complexes as a possible origin of the GRFs. Consequently, these features are attributed to coherent two-phonon excitation of metal–ligand stretching vibrations in molecular dimers coupled by π–π stacking interactions.