First metal-organic coordination polymer based on the[{Mo_(6)I_(8)}(CN)_(6)]^(2-)cluster anion was obtained using the salts Cs_(1.3)Na_(0.7)[{Mo_(6)I_(8)}(CN)_(6)]·2H_(2)O(1)and K[Ag(CN)_(2)],as well as bis(diphe...First metal-organic coordination polymer based on the[{Mo_(6)I_(8)}(CN)_(6)]^(2-)cluster anion was obtained using the salts Cs_(1.3)Na_(0.7)[{Mo_(6)I_(8)}(CN)_(6)]·2H_(2)O(1)and K[Ag(CN)_(2)],as well as bis(diphenylphosphino)methane(dppm),as precursors.In contrast to the previously reported coordination polymers based on octahedral cyanide cluster complexes,the 1D polymer[{Ag_(2)(dppm)_(2)}{Mo_(6)I_(8)}(CN)_(6)](2)demonstrated an order of magnitude increase in the cluster-centred photoluminescence quantum yield(Φem)in the solid state at 300 K in comparison with the ionic salt 1.Moreover,2 exhibits bright X-ray-induced emission,which is two orders of magnitude more intense than that of 1 and is characterized by a light yield of 10800 photons per MeV.Therefore,2 represents the first effective scintillating compound based on octahedral molybdenum clusters.The polymer has exceptional thermal,photo-and hydrolytic stability and exhibits minimal degradation upon X-ray irradiation,retaining its emission intensity following exposure to the dose of 2.2×10^(5) rad.It should be noted that this level of radiation resistance is superb even for inorganic scintillation materials.The high light yield and exceptional stability of the compound enabled us to use it to manufacture scintillation screens for X-ray visualisation.These screens provide a spatial resolution of up to 9 line pairs per mm,representing the first example of a scintillation device based on molybdenum clusters.展开更多
Obtaining nanosized,solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices.In this work,two seven-nuclear rhenium cluster complexes Cs_(7)[{Re_(3)S_(...Obtaining nanosized,solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices.In this work,two seven-nuclear rhenium cluster complexes Cs_(7)[{Re_(3)S_(4)(CN)_(9)}{Re_(4)S_(4)}(CN)_(9)]·10H_(2)O(1)and K_(7)[{Re_(3)Se_(4)(CN)_(9)}{Re_(4)Se_(4)}(CN)_(9)]·15H_(2)O(2)were prepared and comprehensively characterized.The obtained clusters with an even number of cluster valence electrons(CVE)are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type.Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet(MS=0)and magnetic doublet(MS=±1)states with a temperature-dependent population.These states,according to DFT calculations,may originate from the zero-field splitted S=1 ground state,which is quite surprising given that clusters with an even number of CVE usually possess low-spin states(S=0)due to the delocalized nature of the frontier molecular orbitals(MOs)and the effective removal of MO degeneracy by Jahn-Teller spatial distortion of the clusters.We have also succeeded in controlling one-electron oxidation of the clusters,which results in an odd number of CVE and drives the compound into a conventional paramagnetic S=1/2 state.展开更多
基金supported by the Russian Science Foundation(project 19-73-20196-P)Measurements were performed at the“Center for Optical and Laser Materials Research”(St Petersburg State University,St Petersburg,Russian Federation)the Russian Science Foundation(project 22-73-10226)for the financial support of X-ray-induced emission light output measurements and the preparation and characterization of scintillation screens for X-ray visualization.
文摘First metal-organic coordination polymer based on the[{Mo_(6)I_(8)}(CN)_(6)]^(2-)cluster anion was obtained using the salts Cs_(1.3)Na_(0.7)[{Mo_(6)I_(8)}(CN)_(6)]·2H_(2)O(1)and K[Ag(CN)_(2)],as well as bis(diphenylphosphino)methane(dppm),as precursors.In contrast to the previously reported coordination polymers based on octahedral cyanide cluster complexes,the 1D polymer[{Ag_(2)(dppm)_(2)}{Mo_(6)I_(8)}(CN)_(6)](2)demonstrated an order of magnitude increase in the cluster-centred photoluminescence quantum yield(Φem)in the solid state at 300 K in comparison with the ionic salt 1.Moreover,2 exhibits bright X-ray-induced emission,which is two orders of magnitude more intense than that of 1 and is characterized by a light yield of 10800 photons per MeV.Therefore,2 represents the first effective scintillating compound based on octahedral molybdenum clusters.The polymer has exceptional thermal,photo-and hydrolytic stability and exhibits minimal degradation upon X-ray irradiation,retaining its emission intensity following exposure to the dose of 2.2×10^(5) rad.It should be noted that this level of radiation resistance is superb even for inorganic scintillation materials.The high light yield and exceptional stability of the compound enabled us to use it to manufacture scintillation screens for X-ray visualisation.These screens provide a spatial resolution of up to 9 line pairs per mm,representing the first example of a scintillation device based on molybdenum clusters.
基金funded by the Russian Science Foundation(project no.23-13-00081).
文摘Obtaining nanosized,solution-processable molecules and ions with switchable magnetic moments is crucial for the development of storage devices.In this work,two seven-nuclear rhenium cluster complexes Cs_(7)[{Re_(3)S_(4)(CN)_(9)}{Re_(4)S_(4)}(CN)_(9)]·10H_(2)O(1)and K_(7)[{Re_(3)Se_(4)(CN)_(9)}{Re_(4)Se_(4)}(CN)_(9)]·15H_(2)O(2)were prepared and comprehensively characterized.The obtained clusters with an even number of cluster valence electrons(CVE)are found to consist of triangular and tetrahedral fragments strongly bonded together by bridging inner ligands and constitute a new structural type.Magnetochemical analysis of complexes has revealed the presence of non-magnetic singlet(MS=0)and magnetic doublet(MS=±1)states with a temperature-dependent population.These states,according to DFT calculations,may originate from the zero-field splitted S=1 ground state,which is quite surprising given that clusters with an even number of CVE usually possess low-spin states(S=0)due to the delocalized nature of the frontier molecular orbitals(MOs)and the effective removal of MO degeneracy by Jahn-Teller spatial distortion of the clusters.We have also succeeded in controlling one-electron oxidation of the clusters,which results in an odd number of CVE and drives the compound into a conventional paramagnetic S=1/2 state.
