Focused electron beam induced deposition (FEBID) is a versatile tool for the direct-write fabrication of nanostructures on surfaces. However, FEBID nanostructures are usually highly contaminated by carbon originating from the precursor used in the process. Recently, it was shown that platinum nanostructures produced by FEBID can be efficiently purified by electron irradiation in the presence of water. If such processes can be transferred to FEBID deposits produced from other carbon-containing precursors, a new general approach to the generation of pure metallic nanostructures could be implemented. Therefore this study aims to understand the chemical reactions that are fundamental to the water-assisted purification of platinum FEBID deposits generated from trimethyl(methylcyclopentadienyl)platinum(IV) (MeCpPtMe3). The experiments performed under ultrahigh vacuum conditions apply a combination of different desorption experiments coupled with mass spectrometry to analyse reaction products. Electron-stimulated desorption monitors species that leave the surface during electron exposure while post-irradiation thermal desorption spectrometry reveals products that evolve during subsequent thermal treatment. In addition, desorption of volatile products was also observed when a deposit produced by electron exposure was subsequently brought into contact with water. The results distinguish between contributions of thermal chemistry, direct chemistry between water and the deposit, and electron-induced reactions that all contribute to the purification process. We discuss reaction kinetics for the main volatile products CO and CH4 to obtain mechanistic information. The results provide novel insights into the chemistry that occurs during purification of FEBID nanostructures with implications also for the stability of the carbonaceous matrix of nanogranular FEBID materials under humid conditions.

A series of {V12}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties via V–O–Ln bonds were prepared and fully characterized for paramagnetic Ln = SmIII–ErIII and diamagnetic Ln = LuIII, including YIII. The LnPc-functionalized {V12O32} cages with fully oxidized vanadium centers in the ground state were isolated as (nBu4N)3[HV12O32Cl(LnPc)] and (nBu4N)2[HV12O32Cl(LnPc)2] compounds. As corroborated by a combined experimental (EPR, DC and AC SQUID, laser photolysis transient absorption spectroscopy, and electrochemistry) and computational (DFT, MD, and model Hamiltonian approach) methods, the compounds feature intra- and intermolecular electron transfer that is responsible for a partial reduction at V(3d) centers from VV to VIV in the solid state and at high sample concentrations. The effects are generally Ln dependent and are clearly demonstrated for the (nBu4N)3[HV12O32Cl(LnPc)] representative with Ln = LuIII or DyIII. Intramolecular charge transfer takes place for Ln = LuIII and occurs from a Pc ligand via the Ln center to the {V12O32} core of the same molecule, whereas for Ln = DyIII, only intermolecular charge transfer is allowed, which is realized from Pc in one molecule to the {V12O32} core of another molecule usually via the nBu4N+ countercation. For all Ln but DyIII, two of these phenomena may be present in different proportions. Besides, it is demonstrated that (nBu4N)3[HV12O32Cl(DyPc)] is a field-induced single molecule magnet with a maximal relaxation time of the order 10–3 s. The obtained results open up the way to further exploration and fine-tuning of these three modular molecular nanocomposites regarding tailoring and control of their Ln-dependent charge-separated states (induced by intramolecular transfer) and relaxation dynamics as well as of electron hopping between molecules. This should enable us to realize ultra-sensitive polyoxometalate powered quasi-superconductors, sensors, and data storage/processing materials for quantum technologies and neuromorphic computing.

Nitric oxide plays multiple pathophysiological roles in breast cancer and regulates the apoptosis and migration of tumour cells according to its gradients. Hence, the modulation of its levels by selective scavenging can effectively treat the fast-growing triple-negative breast cancer (TNBC). Here, we report the modification and full characterization of the hemin (Fe(III)-protoporphyrin IX) structure to minimize the levels of its aggregation and protect against physiological oxidative degradation. The affinity of the final hemin conjugates towards ●NO was studied experimentally and theoretically using quantum mechanics calculations with the further testing of the downstream effects on TNBC cell migration. These compounds represent model hemin derivatives, which showed differential binding to ●NO with different levels of resistance towards the oxidative degradation and aggregation. Moreover, that was accompanied by their efficiency at stopping the ●NO-induced migration of cells, suggesting the promising application of some of them for the further treatment of TNBC.

Nitro-functionalized undecahalogenated closo-dodecaborates [B 12 X 11 (NO 2)] 2À were synthesized in high purities and characterized by NMR, IR, and Ramans pectroscopy, single crystal X-diffraction, mass spectrometry,a nd gasphase ion vibrational spectroscopy.T he NO 2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B 12 X 12 ] 2À (X = F-I) dianions evidenced by photoelectron spectroscopy,c yclic voltammetry,a nd quantum-chemical calculations. The stabilizing effect decreasesf rom X = Ft oX= I. Thermogravimetric measurementso ft he salts indicate the loss of the nitric oxide radical(NOC). The homolytic NOC eliminationf rom the dianion under very soft collisionale xcitation in gas-phase ion experiments results in the formation of the radical [B 12 X 11 O] 2À C.T heoretical investigations suggest that the loss of NOC proceeds via the rearrangementp roduct [B 12 X 11 (ONO)] 2À .T he O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formationb yr adicalr ecombination of [B 12 X 11 O] 2À C andN OC is demonstrated.