IntroductionObtaining real-world data from routine clinical care is of growing interest for scientific research and personalized medicine. Despite the abundance of medical data across various facilities — including hospitals, outpatient clinics, and physician practices — the intersectoral exchange of information remains largely hindered due to differences in data structure, content, and adherence to data protection regulations. In response to this challenge, the Medical Informatics Initiative (MII) was launched in Germany, focusing initially on university hospitals to foster the exchange and utilization of real-world data through the development of standardized methods and tools, including the creation of a common core dataset. Our aim, as part of the Medical Informatics Research Hub in Saxony (MiHUBx), is to extend the MII concepts to non-university healthcare providers in a more seamless manner to enable the exchange of real-world data among intersectoral medical sites.MethodsWe investigated what services are needed to facilitate the provision of harmonized real-world data for cross-site research. On this basis, we designed a Service Platform Prototype that hosts services for data harmonization, adhering to the globally recognized Health Level 7 (HL7) Fast Healthcare Interoperability Resources (FHIR) international standard communication format and the Observational Medical Outcomes Partnership (OMOP) common data model (CDM). Leveraging these standards, we implemented additional services facilitating data utilization, exchange and analysis. Throughout the development phase, we collaborated with an interdisciplinary team of experts from the fields of system administration, software engineering and technology acceptance to ensure that the solution is sustainable and reusable in the long term.ResultsWe have developed the pre-built packages “ResearchData-to-FHIR,” “FHIR-to-OMOP,” and “Addons,” which provide the services for data harmonization and provision of project-related real-world data in both the FHIR MII Core dataset format (CDS) and the OMOP CDM format as well as utilization and a Service Platform Prototype to streamline data management and use.ConclusionOur development shows a possible approach to extend the MII concepts to non-university healthcare providers to enable cross-site research on real-world data. Our Service Platform Prototype can thus pave the way for intersectoral data sharing, federated analysis, and provision of SMART-on-FHIR applications to support clinical decision making.

Rate enhancements for the reduction of dioxygen by a MnII complex were observed in the presence of redox-inactive group 2 metal ions. The rate changes were correlated with an increase in the Lewis acidity of the group 2 metal ions. These studies led to the isolation of heterobimetallic complexes containing MnIII–(μ-OH)–MII cores (MII = CaII, BaII) in which the hydroxo oxygen atom is derived from O2. This type of core structure has relevance to the oxygen-evolving complex within photosystem II.

Heterobimetallic cores are important units within the active sites of metalloproteins but are often difficult to duplicate in synthetic systems. We have developed a synthetic approach for the preparation of a complex with a MnII–(μ-OH)–FeIII core, in which the metal centers have different coordination environments. Structural and physical data support the assignment of this complex as a heterobimetallic system. A comparison with analogous homobimetallic complexes, MnII–(μ-OH)–MnIII and FeII–(μ-OH)–FeIII cores, further supports this assignment.

A high-throughput methodology combined with X-ray powder diffraction measurements was used to investigate the reactivity of the TetraThiaFulvalene TetraCarboxylic acid ((TTF-TC)H4) with divalent metals (M = Ni, Co) under various reaction conditions (stoichiometry, pH, temperature). Two new crystalline phases were identified and then studied by single crystal X-ray diffraction. Whereas the first one appears to be a simple salt, the second one, formulated {[M(H2O)4]2(TTF-TC)}·4H2O, is built of 2:1 M:TTF-TC molecular complexes and labeled MIL-136(Ni, Co) (MIL stands for Materials Institute Lavoisier). The combination of thermogravimetric analysis and thermodiffraction studies reveals that MIL-136(Ni) exhibits a complex dehydration behavior. Indeed, a partial dehydration/rehydration process led to the single-crystal-to-single-crystal transformation of the molecular compound in a two-dimensional coordination polymer formulated {[Ni2(H2O)5(TTF-TC)]}·H2O (MIL-136′(Ni)). Magnetic and redox properties of MIL-136(Ni, Co) were investigated. Magnetic measurements indicate that all the magnetic coupling, intra- and intermolecular, are very weak; thus, the magnetic data of MIL-136(Ni, Co) have been interpreted in term of single-ion spin orbit coupling. Solid state cyclic voltammetry of MIL-136(Ni, Co) presents three reversible waves which were assigned to the redox activity of the TTF core and the metallic cations. In contrast to solids based on TTF linkers and alkaline ions, the MIL-136(Ni, Co) complexes do not act as excellent positive electrode materials for Li batteries, but present two reversible electron oxidation of the TTF core. These observations were tentatively related to the strength of the metal-carboxylate bond.

The reactions of [MII(TpmMe)(H2O)3]2+ (M = Ni, Co, Fe; TpmMe = tris(3,5-dimethyl-1-pyrazoyl)methane) with [Bu4N](Tp)FeIII(CN)3 in MeCN−Et2O afford three pentanuclear cyano-bridged clusters, [(Tp)3(TpmMe)2FeIII3MII2(CN)9]ClO4·15H2O (M = Ni, 1; M = Co, 2) and [(Tp)3(TpmMe)2FeIII3FeII2(CN)9]BF4·15H2O (3). Single-crystal X-ray analyses reveal that they show the same trigonal bipyramidal structure featuring a D3h-symmetry core, in which two opposing TpmMe-ligated MII ions situated in the two apical positions are linked through cyanide bridges to an equatorial triangle of three Tp-ligated FeIII (S = 1/2) centers. Magnetic studies for complex 1 show ferromagnetic coupling giving an S = 7/2 ground state and an appreciable magnetic anisotropy with a negative D7/2 value equal to −0.79 cm-1. Complex 2 shows zero-field splitting parameters deducted from the magnetization data with D = −1.33 cm-1 and g = 2.81. Antiferromagnetic interaction was observed in complex 3.

The linear-type heterometallic tetramers, MnIII2(5-MeOsaltmen)2MII2(L)22·2H2O (MII = Cu, 1a; Ni, 2a), where 5-MeOsaltmen2- = N,N‘-(1,1,2,2-tetramethylethylene) bis(5-methoxysalicylideneiminate), and H2L = 3-{2-[(2-hydroxy-benzylidene)-amino]-2-methyl-propylimino}-butan-2-one oxime, have been synthesized and characterized from structural and magnetic points of view. These two compounds are isostructural and crystallize in the same monoclinic P21/n space group. The structure has a [MII−NO−MnIII−(O)2−MnIII−ON−MII] skeleton, where −NO− is a linking oximato group derived from the non-symmetrical Schiff-base complex [MII(L)] and −(O)2− is a biphenolato bridge in the out-of-plane [Mn2(5-MeOsaltmen)2]2+ dimer. The solvent-free compounds, 1b and 2b, have also been prepared by drying of the parent compounds, 1a and 2a, respectively, at 100 °C under dried nitrogen. After this treatment, the crystallinity is preserved, and 1b and 2b crystallize in a monoclinic P21/c space group without significant changes in their structures in comparison to 1a and 2a. Magnetic measurements on 1a and 1b revealed antiferromagnetic MnIII···CuII interactions via the oximato group and weak ferromagnetic MnIII···MnIII interactions via the biphenolato bridge leading to an ST = 3 ground state. On the other hand, the diamagnetic nature of the square planar NiII center generates an ST = 4 ground state for 2a and 2b. At low temperature, these solvated (a) and desolvated (b) compounds display single-molecule magnet behavior modulated by their spin ground state.

Synthesis of an analogue of the C-cluster of C. hydrogenoformans carbon monoxide dehydrogenase requires formation of a planar NiII site and attachment of an exo iron atom in the core unit NiFe4S5. The first objective has been achieved by two reactions:  (i) displacement of Ph3P or ButNC at tetrahedral NiII sites of cubane-type [NiFe3S4]+ clusters with chelating diphosphines, and (ii) metal atom incorporation into a cuboidal [Fe3S4]0 cluster with a M0 reactant in the presence of bis(1,2-dimethylphosphino)ethane (dmpe). The isolated product clusters [(dmpe)MFe3S4(LS3)]2- (M = NiII (9), PdII (12), PtII (13); LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3−)) contain the cores [MFe3(μ2-S*)(μ3-S)3]+ having planar MIIP2S2 sites and variable nonbonding M···S* distances of 2.6−3.4 Å. Reaction (i) involves a tetrahedral → planar NiII structural change between isomeric cubane and cubanoid [NiFe3S4]+ cores. Based on the magnetic properties of 12 and earlier considerations, the S = 5/2 ground state of the cubanoid cluster arises from the [Fe3S4]- fragment, whereas the S = 3/2 ground state of the cubane cluster is a consequence of antiferromagnetic coupling between the spins of Ni2+ (S = 1) and [Fe3S4]-. Other substitution reactions of [NiFe3S4]+ clusters and 1:3 site-differentiated [Fe4S4]2+ clusters are described, as are the structures of 12, 13, [(Me3P)NiFe3S4(LS3)]2-, and [Fe4S4(LS3)L‘]2- (L‘ = Me2NC2H4S-, Ph2P(O)C2H4S-). This work significantly expands our initial report of cluster 9 (Panda et al. J. Am. Chem. Soc. 2004, 126, 6448−6459) and further demonstrates that a planar MII site can be stabilized within a cubanoid [NiFe3S4]+ core.

Using the tricyano precursor, (Bu4N)(Tp)Fe(CN)3 (1), four new tetranuclear clusters, [(Tp)Fe(CN)3Cu(Tp)]2·2H2O (2), [(Tp)Fe(CN)3Cu(bpca)]2·4H2O (3) (bpca = bis(2-pyridylcarbonyl)amidate anion), [(Tp)Fe(CN)3Ni(tren)]2(ClO4)2·2H2O (4) (tren = tris(2-amino)ethylamine), and [(Tp)Fe(CN)3Ni(bipy)2]2[(Tp)Fe(CN)3]2·6H2O (5) (bipy = 2,2‘-bipyridine), have been synthesized and structurally characterized. The four clusters possess similar square structures, where FeIII and MII (M = CuII or NiII) ions alternate at the rectangle corners. There exist intermolecular π−π stacking interactions through pyrazolyl groups of Tp- ligands in complexes 2 and 4, which lead to 1D chain structures. Complex 5 shows a 3D network structure through the coexistence of π−π stacking effects and hydrogen-bonding interactions. Magnetic studies show intramolecular ferromagnetic interactions in all four clusters. The exchange parameters are +11.91 and +1.38 cm-1 for clusters 2 and 3, respectively, while uniaxial molecular anisotropy can be detected in complex 3 due to the distorted core in its molecular structure. Complex 4 has a ground state of S = 3 and shows SMM behavior with an effective energy barrier of U = 18.9 cm-1. Unusual spin-glass-like dynamic relaxations are observed for complex 5.

The phenol-based macrocyclic ligands (L2,3)2- and (L2,4)2-, derived from the [2:1:1] condensation of 2,6-diformyl-4-methylphenol, ethylenediamine, and 1,3-trimethylenediamine or 1,4-tetramethylenediamine, have a salen-like metal-binding site (salen = N,N‘-ethylenedisalicylideneaminate) and a saltn- or salbn-like metal-binding site (saltn = N,N‘-trimethylenedisalicylideneaminate, salbn = N,N‘-tetramethylenedisalicylideneaminate) sharing the phenolic moieties. They form the (μ-phenoxo)2CoIIMII complexes [CoMn(L2,3)(AcO)]ClO4·DMF (1), [CoMn(L2,4)(AcO)]ClO4 (2), [CoCo(L2,3)(AcO)]ClO4 (3), [CoCo(L2,4)(AcO)]ClO4 (4), [CoZn(L2,3)(AcO)]ClO4 (5), and [CoZn(L2,4)(AcO)]ClO4 (6). Complex 1 crystallizes in the monoclinic space group P21/c, with a = 10.027(3) Å, b = 11.713(3) Å, c = 26.821(9) Å, β = 93.85(2)°, V = 3142(1) Å3, and Z = 4. The Co and Mn ions are bridged by the two phenolic oxygens of the macrocycle and an acetate group in the syn-syn mode. The CoII in the salen site is of low-spin and assumes a square-pyramidal geometry with an acetate oxygen at the axial site. The MnII has a cis six-coordinate geometry with respect to the acetate oxygen and the DMF oxygen. The Mn is displaced 0.955 Å from the basal N2O2 least-squares plane. [CoMn(L2,4)(AcO)]ClO4·DMF (2‘) crystallizes in the monoclinic space group P21/c, with a = 10.166(5) Å, b = 11.934(4) Å, c = 27.380(8) Å, β = 93.97(3)°, V = 3313(1) Å3, and Z = 4. It has a dinuclear core similar to that of 1, with square-pyramidal CoII in the salen site and cis six-coordinate MnII in the salbn site. Complex 3 crystallizes in the triclinic space group P1̄, a = 12.118(3) Å, b = 12.156(2) Å, c = 9.977(1) Å, α = 112.49(1)°, β = 99.22(2)°, γ = 77.63(2)°, V = 1321.1(5) Å3, and Z = 2. Both CoII ions in the salen and saltn sites assume a square-pyramidal geometry with a bridging acetate group in the syn-syn mode. The displacement of the Co in the saltn site, from the basal N2O2 least-squares plane toward the apical acetate oxygen, is 0.53 Å. Complex 5 is found to be isostructural with 3. The complexes 1, 2, 4, 5, and 6 are reversibly oxygenated in DMF at 0 °C to afford a μ-peroxo dimer complex [{CoIIIMII(L)(AcO)}2(O22-)]2+. Complex 3 also forms such a μ-peroxo dimer complex but is irreversibly oxidized through an intramolecular-type μ-peroxo complex [CoIIICoIII(L2,3)(AcO)(O22-)]+.