Nanoparticle‐based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface‐to‐volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle‐based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle‐based aerogel‐ or xerogel‐coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle‐based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro‐electrochemical measurements are recorded to investigate the charge–carrier mobility within these 3D semiconductor‐based xerogel networks.

Am ononuclear Fe II complex, prepared with aB rønsted diacid ligand, H 2 L( H 2 L = 2-[5-phenyl-1H-pyrazole-3-yl] 6-benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states.T he spin crossover (SCO) complex, [Fe II (H 2 L) 2 ](BF 4 ) 2 (1 A ), exhibits abrupt spin transition at T 1/2 = 258 K, and treatment with base yields ad eprotonated analogue [Fe II -(HL) 2 ](1 B ), which shows gradual SCO above 350 K. Arange of Fe III analogues were also characterized.[ Fe III (HL)(H 2 L)]-(BF 4 )Cl (1 C )h as an S = 5/2 spin state,w hile the deprotonated complexes [Fe III (L)(HL)],( 1 D ), and (TEA)[Fe III (L) 2 ], (1 E ) exist in the low-spin S = 1/2 state.T he electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state.T he versatility of this simple mononuclear system illustrates howproton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices.

A hydrogen‐bonding donor–acceptor system, [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2⋅2ABA⋅4BN⋅2PE (1 solv), was prepared by co‐crystallization of an external stimuli‐responsive cyanide‐bridged tetranuclear [Co2Fe2] complex and bifunctional hydrogen‐bonding donors, p‐aminobenzoic acid. Compound 1 solv exhibited a gradual electron‐transfer‐coupled spin transition (ETCST), and the removal of solvent molecules led to an abrupt thermal ETCST behavior with increased transition temperature. X‐ray structural analysis revealed that the modification of ETCST was caused by a significant alteration of a hydrogen‐bonding mode between the tetranuclear [Co2Fe2]2+ cations and ABA molecules. Variable temperature IR measurements indicated that the desolvated form, 1 desolv, showed dynamic alteration of hydrogen‐bonding interactions coupled with thermal ETCST behavior. These results suggested that the tetranuclear [Co2Fe2] complex shows solid‐state modulations of hydrogen‐bond strengths by external stimuli.

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