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We used stereolithography to print polymer nanocomposite samples of stimuli-responsive spin crossover materials in the commercial photo-curable printing resins DS3000 and PEGDA-250. The thermomechanical analysis of the SLA-printed objects revealed not only the expected reinforcement of the polymer resins by the introduction of the stiffer SCO particles, but also a significant mechanical damping, as well as a sizeable linear strain around the spin transition temperatures. For the highest accessible loads (ca. 13–15 vol.%) we measured transformation strains in the range of 1.2–1.5%, giving rise to peaks in the coefficient of thermal expansion as high as 10−3 °C−1, which was exploited in 3D printed bilayer actuators to produce bending movement. The results pave the way for integrating these advanced stimuli-responsive composites into mechanical actuators and 4D printing applications. [ABSTRACT FROM AUTHOR]

A series of mixed-anion Fe(NH2trz)3(BF4)2−x(SiF6)x/2 spin crossover complexes is obtained modifying the reaction time but also using an increase amount of tetraethyl orthosilicate as the source for the production and the incorporation of SiF62− competing with the BF42− anions present in the mother solution. The increase of the SiF62− anion inclusion to the detriment of the BF4− counterpart induces a shift of the temperature transition toward high temperatures leading to interesting bistability properties around room temperature with T1/2 spanning from 300 K to 325 K. Moreover, the implementation of a solid–liquid post synthetic modification approach from the Fe(NH2trz)3(BF4)2 parent complex with identical TEOS proportions and under certain experimental conditions lead systematically to the same Fe(NH2trz)3(BF4)1.2(SiF6)0.4 composition. This compound presents an abrupt spin crossover behaviour with a narrow hysteresis loop just above room temperature (320 K), which is stable under thermal cycling and along time with no specific storage conditions. Such crystalline powder sample incorporates homogeneous rod-shaped particles whose formation and physical properties can be followed simultaneously using infra-red spectroscopy, dynamic light scattering (DLS), transmission electronic microscopy (TEM) and optical reflectance. The observation of a stabilized single ca. 800 nm population of mixed-anion particles starting from insoluble various sizes (from nano- to microscale) Fe(NH2trz)3(BF4)2 particles supports the key role of the solvent (water molecules) on the separation, the reactivity and the reorganization of the 1D iron-triazole chains forming the packing of the structure. [ABSTRACT FROM AUTHOR]

A pure mixed-anion Fe(NH2trz)3(BF4)(SiF6)0.5 spin crossover complex is obtained implementing a solid–liquid post synthetic modification approach from the Fe(NH2trz)3(BF4)2 parent complex. This method allows obtaining highly crystalline powder samples incorporating homogeneous micrometric (1 μm long) rod-shaped particles. This compound presents an abrupt spin crossover behaviour with a narrow (10 K) hysteresis loop centred just above room temperature (320 K) which makes it very interesting for future integration into devices for various applications. [ABSTRACT FROM AUTHOR]

A ruthenium–nitrosyl derivative of formula [RuII(CzT)(bipy)(NO)](PF6)3 [CzT = 4′‐(N‐ethylcarbazol‐3‐yl)‐2,2′:6′,2′′‐terpyridine, bipy = 2,2′‐bipyridine] has been synthesized and fully characterized, and compared with the previously reported [RuII(FT)(bipy)(NO)](PF6)3 complex [FT = 4′‐(9,9‐dihexyl‐9H‐fluoren‐2‐yl)‐2,2′:6′,2′′‐terpyridine]. Additionally, the X‐ray crystal structure of [RuII(CzT)(bipy)(NO2)](PF6), the precursor of [RuII(CzT)(bipy)(NO)](PF6)3, is reported. The presence of a tertiary amine in the carbazole unit leads to redshifted charge‐transfer transitions towards the electron‐withdrawing Ru–NO fragment and hence enhanced two‐photon absorption (TPA) properties. In contrast, the quantum yield of the NO· photorelease process is lower for the carbazole‐containing complex. The issue of optimization of the TPA versus NO·‐release capabilities is addressed. [ABSTRACT FROM AUTHOR]