“…Several CN stretching bands appear for each complex because the three cyanido ligands are in two different environments, as discussed in the Single-Crystal X-ray Structures section. Similar observations have been reported for the isostructural bpy-coordinated manganese complex [MnN(CN) 3 bpy] − . The 1 H NMR spectra of the complexes exhibit two sets of signals for the pyridyl rings in the bpy derivatives and one set of PPh 4 + signals.…”
Section: Results
and Discussionsupporting
confidence: 84%
“…Further, X-ray structural analysis confirmed that the bpy derivatives chelated at the ax and eq sites. It was reported that two sets of pyridyl signals were observed in the 1 H NMR spectrum of [MnN(CN) 3 bpy] − . Therefore, the inequivalent 1 H NMR signals of the bpy derivatives in the rhenium complexes could be attributed to ax–eq coordination of the ligands to the nitridorhenium(V) ions.…”
Tricyanidonitridorhenium(V) complexes
with 2,2′-bipyridine
(bpy) derivatives in which the 4 and 4′ positions were substituted
by X, [ReN(CN)3(X2bpy)]− (X
= NMe2, NH2, OMe, Me, Cl, and Br), were newly
synthesized and characterized. The structures of the new complexes
were determined by single-crystal X-ray analysis. UV–vis spectra
of the complexes in dimethyl sulfoxide (DMSO) showed that the peak
maximum wavelengths of rhenium-to-π* bpy-type-ligand charge
transfer were in the range of 474–542 nm. Cyclic voltammograms
in n-(C4H9)4NPF6–DMSO showed one-electron oxidation and reduction waves
corresponding to the Re(VI/V) and X2bpy0/– processes, respectively. The new complexes and [ReN(CN)3bpy]− showed photoluminescence in the crystalline
phase at 295 and 80 K and in DMSO at 295 K. The origin of the emission
in DMSO was attributed to the triplet nature of the rhenium-to-π*
bpy-type-ligand charge-transfer transition. Density functional theory
calculations showed that the highest occupied and lowest unoccupied
molecular orbitals were primarily localized on the d
xy
orbital of the rhenium and π* orbitals of the bpy-type
ligand, respectively.
“…Several CN stretching bands appear for each complex because the three cyanido ligands are in two different environments, as discussed in the Single-Crystal X-ray Structures section. Similar observations have been reported for the isostructural bpy-coordinated manganese complex [MnN(CN) 3 bpy] − . The 1 H NMR spectra of the complexes exhibit two sets of signals for the pyridyl rings in the bpy derivatives and one set of PPh 4 + signals.…”
Section: Results
and Discussionsupporting
confidence: 84%
“…Further, X-ray structural analysis confirmed that the bpy derivatives chelated at the ax and eq sites. It was reported that two sets of pyridyl signals were observed in the 1 H NMR spectrum of [MnN(CN) 3 bpy] − . Therefore, the inequivalent 1 H NMR signals of the bpy derivatives in the rhenium complexes could be attributed to ax–eq coordination of the ligands to the nitridorhenium(V) ions.…”
Tricyanidonitridorhenium(V) complexes
with 2,2′-bipyridine
(bpy) derivatives in which the 4 and 4′ positions were substituted
by X, [ReN(CN)3(X2bpy)]− (X
= NMe2, NH2, OMe, Me, Cl, and Br), were newly
synthesized and characterized. The structures of the new complexes
were determined by single-crystal X-ray analysis. UV–vis spectra
of the complexes in dimethyl sulfoxide (DMSO) showed that the peak
maximum wavelengths of rhenium-to-π* bpy-type-ligand charge
transfer were in the range of 474–542 nm. Cyclic voltammograms
in n-(C4H9)4NPF6–DMSO showed one-electron oxidation and reduction waves
corresponding to the Re(VI/V) and X2bpy0/– processes, respectively. The new complexes and [ReN(CN)3bpy]− showed photoluminescence in the crystalline
phase at 295 and 80 K and in DMSO at 295 K. The origin of the emission
in DMSO was attributed to the triplet nature of the rhenium-to-π*
bpy-type-ligand charge-transfer transition. Density functional theory
calculations showed that the highest occupied and lowest unoccupied
molecular orbitals were primarily localized on the d
xy
orbital of the rhenium and π* orbitals of the bpy-type
ligand, respectively.
“… Carol Hua (Northwestern University) is the recipient of the Cornforth Medal. Hua studied at the UNSW and worked with Deanna D'Alessandro at The University of Sydney for her PhD (completed in 2015), and was co‐author of reports in the European Journal of Inorganic Chemistry on [MnN(CN) 3 (diimine)] − complexes, and in Angewandte Chemie on switchable spin‐crossover iron(II) metal–organic frameworks . After postdoctoral research with D'Alessandro (2016) and Michael Zaworotko at the University of Limerick (2016–2017), she moved to Northwestern University, where she is carrying out research on 2D and 3D porous redox‐active materials in the group of David Harris.…”
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