TY - JOUR A1 - Zottnick, Sven H. A1 - Sprenger, Jan A. P. A1 - Finze, Maik A1 - Müller‐Buschbaum, Klaus T1 - Statistic Replacement of Lanthanide Ions in Bis‐salicylatoborate Coordination Polymers for the Deliberate Control of the Luminescence Chromaticity JF - ChemistryOpen N2 - Based on the strand‐like coordination polymer (CP) type \(^{1}\)\(_{∞}\)[Ln(BSB)\(_{3}\)(py)\(_{2}\)], [BSB]−=bis‐salicylatoborate anion, mixed Eu/Tb‐containing compounds of the constitution \(^{1}\)\(_{∞}\)[Eu\(_{x}\)Tb\(_{1-x}\)(BSB)\(_{3}\)(py)\(_{2}\)] were synthesised ionothermally for a phase width of (x=0.25–0.75) and characterized regarding structure and optical properties. Previously, known only for other lanthanides, the mixed 1D−Eu/Tb‐CPs show excellent options for statistic replacement of the Ln‐cations during synthesis yielding solid solutions. The products are highly luminescent, with the chromaticity being a direct function of the amount of the respective Ln‐ions. Corresponding to an overall addition of emission intensities, the green Tb\(^{3+}\) emission and the red Eu\(^{3+}\) emission allow for a chromaticity control that also includes yellow emission. Control of the luminescence colour renders them suitable examples of the versatility of statistic replacement of metal ions in coordination chemistry. In addition, crystallization of [EMIm]\(_{2}\)[YCl\(_{5}\)(py)] illuminates possible other products of the ionothermal reactions of [EMIm][BSB] with LnCl\(_{3}\) constituted by components not being part of the main CPs. KW - borates KW - coordination polymers KW - ionic liquids KW - lanthanides KW - luminescence Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-239953 VL - 10 IS - 2 SP - 164 EP - 170 ER - TY - JOUR A1 - Matthes, Philipp R. A1 - Schönfeld, Fabian A1 - Zottnick, Sven H. A1 - Müller-Buschbaum, Klaus T1 - Post-synthetic shaping of porosity and crystal structure of Ln-Bipy-MOFs by thermal treatment JF - Molecules N2 - The reaction of anhydrous lanthanide chlorides together with 4,4'-bipyridine yields the MOFs \(^{2}\)\(_{∞}\)[Ln\(_{2}\)Cl\(_{6}\)(bipy)\(_{3}\)]*2bipy, with Ln = Pr-Yb, bipy = 4,4'-bipyridine, and \(^{3}\)\(_{∞}\)[La\(_{2}\)Cl\(_{6}\)(bipy)\(_{5}\)]*4bipy. Post-synthetic thermal treatment in combination with different vacuum conditions was successfully used to shape the porosity of the MOFs. In addition to the MOFs microporosity, a tuneable mesoporosity can be implemented depending on the treatment conditions as a surface morphological modification. Furthermore, thermal treatment without vacuum results in several identifiable crystalline high-temperature phases. Instead of collapse of the frameworks upon heating, further aggregation under release of bipy is observed. \(^{3}\)\(_{∞}\)[LaCl\(_{3}\)(bipy)] and \(^{2}\)\(_{∞}\)[Ln\(_{3}\)Cl\(_{9}\)(bipy)\(_{3}\)], with Ln = La, Pr, Sm, and \(^{1}\)\(_{∞}\)[Ho\(_{2}\)Cl\(_{6}\)(bipy)\(_{2}\)] were identified and characterized, which can also exhibit luminescence. Besides being released upon heating, the linker 4,4'-bipyridine can undergo activation of C-C bonding in ortho-position leading to the in-situ formation of 4,4':2',2 '':4 '',4'''-quaterpyridine (qtpy). qtpy can thereby function as linker itself, as shown for the formation of the network \(^{2}\)\(_{∞}\)[Gd\(_{2}\)Cl\(_{6}\)(qtpy)\(_{2}\)(bipy)\(_{2}\)]*bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs. KW - energy transfer KW - ligand KW - Ln-MOFs KW - luminescence crystal structure KW - metal-organic frameworks KW - shaping of porosity KW - thermal treatment KW - luminescence KW - crystal scructure KW - coordination polymers KW - solid state Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-148404 VL - 20 ER - TY - THES A1 - Dannenbauer, Nicole T1 - Koordinationspolymere und -verbindungen mit intrinsischer Lumineszenz auf Basis von Selten-Erd-Chloriden, Thiazol, Thiolaten und Amin-Co-Liganden T1 - Coordination polymers and compounds with intrinsic luminescence based on rare earth chlorides, thiazole, thiolates and amine co-ligands N2 - In dieser Arbeit konnten 69 neue und neuartige Koordinationspolymere sowie Komplexe mit schwefelhaltigen Liganden auf Selten-Erd-Chlorid-Basis synthetisiert und strukturell charak-terisiert werden. Durch die Umsetzung der Chloride mit dem Liganden Thiazol konnten bei Raumtemperatur, abhängig vom Ionenradius und der eingesetzten Menge Thiazol, sowohl Koordinationspolymere wie 1∞[LnCl3(thz)6]·thz (Ln = La, Ce), dimere Komplexe [Ln2Cl6(thz)8]·3(thz) (Ln = La, Ce, Pr, Nd), [Pr2Cl6(thz)8] sowie monomere Komplexe [LnCl3(thz)4]2·thz (Ln = Sm , Eu , Tb, Ho) erhalten werden. Mittels temperaturabhängiger Pulverdiffraktometrie und in-situ Infra-rotspektroskopie sowie DTA/TG-Messungen konnte exemplarisch an 1∞[LaCl3(thz)6]·thz und [Pr2Cl6(thz)8] gezeigt werden, dass stufenweise thermisch bedingt Thiazolmoleküle aus den Strukturen abgegeben werden bis hin zur Rückbildung des eingesetzten LnCl3. Unter der Vo-raussetzung, dass die flüchtige Komponente Thiazol resorbiert wird, ist daher ein Kreispro-zess denkbar. Ferner konnten zusätzlich wasserhaltige Phasen wie der vierkernige Cluster [Pr4Cl10(OH)2(thz)8(H2O)2] erhalten werden. Durch die Zugabe eines geeigneten Linkermoleküls in das Reaktionssystem aus trivalenten Lanthanidchloriden und Thiazol konnten unter solvothermalen Bedingungen eine Vielzahl an Koordinationspolymeren und Komplexen erhalten werden. Als Linker oder als end-on Ligan-den eigneten sich sowohl eine Reihe an ditopischer Pyridylliganden 4,4'-Biypridin (bipy), 1,2-Di-(4-pyridyl)ethen (dpe), trans-1-(2-Pyridyl)-2-(4-pyridyl)ethylen (tppe), 1,2-Di-(4-pyridyl)ethan (dpa), sowie die Diazine Pyrazin (pyz) und Pyrimidin (pym) oder auch Azole wie 1,2,4-Triazol (tzH) und Pyrazol (pzH). Mittels Einkristallstrukturanalyse und pulverdiffrakto-metrischer Methoden konnten die dreidimensionalen Gerüstverbindungen 3∞[LnCl3(dpa)2]·thz (Ln = Ce - Sm, Gd - Lu), die Schichtstrukturen 2∞[Ln2Cl6(bipy)3(thz)2]·thz (Ln = La, Ce), 2∞[LnCl3(tzH)2(thz)]·thz (Ln = Pr, Sm - Gd) und die strangartigen Koordinationspolymere 1∞[LnCl3(bipy)(thz)2]·thz (Ln = Pr, Nd), 1∞[LnCl3(bipy)(thz)2]·thz (Ln = Sm, Eu - Er, Yb), 1∞[Ln2Cl6(dpe)2(thz)4]·dpe (Ln = Ce, Nd), 1∞[LnCl3(dpe)(thz)2]· 0.5 (dpe) 0.5 (thz) (Ln = Sm, Gd - Dy, Er, Yb), 1∞[HoCl3(dpe)(thz)2]·thz, 1∞[La2Cl6(dpa)(thz)6], 1∞[Pr2Cl6(pyz) (thz)6], 1∞[Ln2Cl6(tzH)4(thz)2] (Ln = Pr, Sm, Gd) sowie die Komplexe [LnCl3(tppe)2(thz)2] (Ln = Nd, Tb, Ho, Er), [Ln2Cl6(pyz)(thz)6]·2(thz) (Ln = Tb, Er), [Ln2Cl6(pym)2(thz)4] (Ln = Tb , Er), [LnCl3(pzH)3(thz)2] (Ln = Pr, Gd) charakterisiert werden.   Ferner konnten die erhaltenen Verbindungen weitestgehend auf ihre photolumineszenz-spektroskopischen sowie thermischen Eigenschaften hin untersucht werden. Außerdem konn-ten auch durch direkte Schwefelkoordination an die Ln3+-Zentren eindimensionale Koordina-tionspolymere 1∞[PrCl2(amt)(py)3] (amt- = 3-Amino-5-mercapto-1,2,4-triazolat), [HNEt3]1∞[LnCl2(amt)2] (Ln = Ho, Er) und Komplexe [LnCl2(Mbim)(py)3]·py (Ln = Y, Er; Mbim = 2-Mercaptobenzimdiazolat) generiert werden N2 - This thesis deals with the structural characterization of 69 novel coordination polymers and complexes synthesized with sulfur containing heterocyclic ligands and trivalent rare earth chlorides. Depending on the ionic radii of the used lanthanide chloride and the amount of the ligand thiazole coordination polymers as 1∞[LnCl3(thz)6]·thz (Ln = La, Ce), dimeric compounds [Ln2Cl6(thz)8]·3(thz) (Ln = La, Ce, Pr, Nd), [Pr2Cl6(thz)8] and monomeric complexes [LnCl3(thz)4]2·thz (Ln = Sm, Eu , Tb, Ho) were derived at room temperature. Using tempera-ture-dependent powder diffraction methods, in-situ IR-spectroscopy and DTA/TG measure-ments it was demonstrated that there is a stepwise, thermal induced release of thiazole molecules out of the structures to back-formation of crystalline lanthanide chloride in the cases of the coordination polymer 1∞[LaCl3(thz)6]·thz and the dimer [Pr2Cl6(thz)8]. This could be a cyclic process requiring the elusive ligand thiazole to be reabsorbed. Furthermore, hy-drous phases were also obtained like the tetranuclear cluster [Pr4Cl10(OH)2(thz)8(H2O)2]. It was possible to generate a series of various coordination polymers and complexes under solvothermal conditions adding suitable linker molecules into the reaction system of lantha-nide chloride and thiazole. Suitable linkers or end-on ligands are a range of ditopic pyridyl ligands like 4,4'-biypridine (bipy), 1,2-di-(4-pyridyl)ethene (dpe), trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (tppe), 1,2-di-(4-pyridyl)ethane (dpa), diazine as pyrazine (pyz) and pyrimi-dine (pym) as well as azole like 1,2,4-triazole (tzH) and pyrazole (pzH). By single-X-ray struc-ture determination and powder diffraction it was possible to characterize three dimensional networks 3∞[LnCl3(dpa)2]·thz (Ln = Ce - Sm, Gd - Lu), layer structures 2∞[Ln2Cl6(bipy)3(thz)2]·thz (Ln = La, Ce), 2∞[LnCl3(tzH)2(thz)]·thz (Ln = Pr, Sm - Gd) and strand like coordination polymers 1∞[LnCl3(bipy)(thz)2]·thz (Ln = Pr, Nd), 1∞[LnCl3(bipy)(thz)2]·thz (Ln = Sm, Eu - Er, Yb), 1∞[Ln2Cl6(dpe)2(thz)4]·dpe (Ln = Ce, Nd), 1∞[LnCl3(dpe)(thz)2]·0.5 (dpe) 0.5 (thz) (Ln = Sm, Gd - Dy, Er, Yb), 1∞[HoCl3(dpe)(thz)2]·thz, 1∞[La2Cl6(dpa)(thz)6], 1∞[Pr2Cl6(pyz) (thz)6], 1∞[Ln2Cl6(tzH)4(thz)2] (Ln = Pr, Sm, Gd) as well as the complexes [LnCl3(tppe)2(thz)2] (Ln = Nd, Tb, Ho, Er), [Ln2Cl6(pyz)(thz)6]·2(thz) (Ln = Tb, Er), [Ln2Cl6(pym)2(thz)4] (Ln = Tb , Er), [LnCl3(pyr)3(thz)2] (Ln = Pr, Gd). Furthermore, nearly all of the generated structures were investigated with regards to their photoluminescent and thermal properties.   Moreover, one dimensional coordination polymers 1∞[PrCl2(amt)(py)3] (amt- = 3-amino-5-mercapto-1,2,4-triazolate), [HNEt3]1∞[LnCl2(amt)2] (Ln = Ho, Er) and complexes [LnCl2(Mbim)(py)3]·py (Ln = Y, Er; Mbim = 2-mercaptobenzimdiazolate) were obtained by direct coordination of sulfur at Ln3+-centers. KW - Lanthanoide KW - Polymerkomplexe KW - Photolumineszenz KW - Thiolate KW - Thiazole KW - Selten-Erd-Chloride KW - Koordinationspolymere KW - Lumineszenz KW - Thiazol KW - rare earth chlorides KW - coordination polymers KW - luminescence KW - thiazole Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-136218 ER -