[SeCl_(3)][GaCl_(4)](1)and[TeCl_(3)][GaCl_(4)](_(2))are prepared via Lewis-acid-base reaction of SeCl_(4)or TeCl_(4)with GaCl_(3)at 50℃(1)and 1_(4)0℃(_(2))in quantitative yield.The ionic compounds contain pseudo-tet...[SeCl_(3)][GaCl_(4)](1)and[TeCl_(3)][GaCl_(4)](_(2))are prepared via Lewis-acid-base reaction of SeCl_(4)or TeCl_(4)with GaCl_(3)at 50℃(1)and 1_(4)0℃(_(2))in quantitative yield.The ionic compounds contain pseudo-tetrahedral[SeCl_(3)]^(+)/[TeCl_(3)]^(+)cations with a prominent stereochemically active electron lone pair at Se(IV)/Te(IV)as well as tetrahedral[GaCl_(4)]^(-)anions.Both compounds crystallize in the polar chiral space group P1 with an unidirectional alignment of all tetrahedral building units.展开更多
The highly luminescent MOFs_(∞)^(3)[Ce(Im)_(3)ImH]·ImH,_(∞)^(3)[Tb(Im)_(3)],and the dense framework_(∞)^(3)[Sr_(0.95)Eu_(0.05)(Im)_(2)](Im−=imidazolate-anion,C_(3)N_(2)H_(3)^(−))were grown on nanostructured ma...The highly luminescent MOFs_(∞)^(3)[Ce(Im)_(3)ImH]·ImH,_(∞)^(3)[Tb(Im)_(3)],and the dense framework_(∞)^(3)[Sr_(0.95)Eu_(0.05)(Im)_(2)](Im−=imidazolate-anion,C_(3)N_(2)H_(3)^(−))were grown on nanostructured macroporous aluminium oxide(AAO)membranes.Thereby,luminescent coatings on the membranes were achieved.Three different growth processes unusual for MOFs were investigated and compared:a film growth process in situ to MOF formation from the linker melt,electride induction with solvated electrons,and chemical vapour deposition(CVD)to additionally utilize the gas phase.Deposition from the organic melt has proved to be a fast approach to achieve various film thicknesses of the luminescent frameworks.The electride-based approach offers excellent homogenization at an atomic level for the highest quantum yields of QY>90%for_(∞)^(3)[Sr_(0.95)Eu_(0.05)(Im)_(2)]including the formation of barite rose analogous crystals prior to growth of a complete film on AAO membranes.For_(∞)^(3)[Tb(Im)_(3)]and_(∞)^(3)[Ce(Im)_(3)ImH]·ImH,deposition of bundles of crystals by CVD on AAO is possible while also maintaining the luminescence of the original MOFs but without complete layers.In order to elaborate the divalent character of europium,being the basis of the high efficiency of the luminescence,EPR studies were carried out on_(∞)^(3)[Sr_(1−x)Eu_(x)(Im)_(2)],x=0.01,0.05 and 1.展开更多
基金the Deutsche Forschungsgemeinschaft(DFG)for funding within the project“Crown-Ether-Coordination-Compounds with Unusual Structural and Optical Properties/Crown I(FE 911/14-1)”B.W.is grateful for support through the BIOVIA Science Ambassador program.L.B.gratefully acknowledge funding from the DFG(project Ba4020).
文摘[SeCl_(3)][GaCl_(4)](1)and[TeCl_(3)][GaCl_(4)](_(2))are prepared via Lewis-acid-base reaction of SeCl_(4)or TeCl_(4)with GaCl_(3)at 50℃(1)and 1_(4)0℃(_(2))in quantitative yield.The ionic compounds contain pseudo-tetrahedral[SeCl_(3)]^(+)/[TeCl_(3)]^(+)cations with a prominent stereochemically active electron lone pair at Se(IV)/Te(IV)as well as tetrahedral[GaCl_(4)]^(-)anions.Both compounds crystallize in the polar chiral space group P1 with an unidirectional alignment of all tetrahedral building units.
基金support of the Deutsche Forschungsgemeinschaft within the priority program SPP-1362“MOFs”.
文摘The highly luminescent MOFs_(∞)^(3)[Ce(Im)_(3)ImH]·ImH,_(∞)^(3)[Tb(Im)_(3)],and the dense framework_(∞)^(3)[Sr_(0.95)Eu_(0.05)(Im)_(2)](Im−=imidazolate-anion,C_(3)N_(2)H_(3)^(−))were grown on nanostructured macroporous aluminium oxide(AAO)membranes.Thereby,luminescent coatings on the membranes were achieved.Three different growth processes unusual for MOFs were investigated and compared:a film growth process in situ to MOF formation from the linker melt,electride induction with solvated electrons,and chemical vapour deposition(CVD)to additionally utilize the gas phase.Deposition from the organic melt has proved to be a fast approach to achieve various film thicknesses of the luminescent frameworks.The electride-based approach offers excellent homogenization at an atomic level for the highest quantum yields of QY>90%for_(∞)^(3)[Sr_(0.95)Eu_(0.05)(Im)_(2)]including the formation of barite rose analogous crystals prior to growth of a complete film on AAO membranes.For_(∞)^(3)[Tb(Im)_(3)]and_(∞)^(3)[Ce(Im)_(3)ImH]·ImH,deposition of bundles of crystals by CVD on AAO is possible while also maintaining the luminescence of the original MOFs but without complete layers.In order to elaborate the divalent character of europium,being the basis of the high efficiency of the luminescence,EPR studies were carried out on_(∞)^(3)[Sr_(1−x)Eu_(x)(Im)_(2)],x=0.01,0.05 and 1.
