49669-14-9Relevant articles and documents
Tetradentate N^N°N^N-type luminophores for Pt(II) complexes: Synthesis, photophysical and quantum-chemical investigation
Cnudde, Marvin,Brünink, Dana,Doltsinis, Nikos L.,Strassert, Cristian A.
, (2021)
Herein we report on dianionic tetradentate, pyridin-azole-based ligands for luminescent Pt(II) complexes. To improve their solubility in common organic solvents, a hexyl-chain was inserted in the periphery of the luminophoric ligand and different substituents were introduced at the 1H-pyrazole moieties including 4-hexylphenyl- (L1), adamantyl- (L2) and 3,5-dimethoxyphenyl (L3) substituents. For the new ligand precursors L1 and L2, the corresponding Pt(II) complexes Pt1 and Pt2 were synthesized and characterized by exact mass spectrometry as well as by 1H NMR. L3 was also successfully synthesized and isolated, but due to the limited solubility of the resulting coordination compound, the purification and structural characterization of the corresponding Pt(II) complex Pt3 was not achieved. The absorption and steady-state as well as time-resolved photoluminescence spectra of Pt1 and Pt2 were investigated and interpreted employing TD–DFT. We found that the S1 states for Pt1 and Pt2 can be described mainly as single electron HOMO→LUMO excitations with a 1MP-ILCT character comprising the diazole units and the pyridine rings. At room temperature, Pt1 and Pt2 show phosphorescence in the green region of the electromagnetic spectrum peaking at 506 nm and 497 nm with photoluminescence quantum yields reaching 17% and 25%, respectively. DFT calculations show that the T1 states of Pt1 and Pt2 can be mainly described as monoelectronic HOMO→LUMO excitations with predominant 3MP-ILCT character.
Bis(pyrazolato) Bridged Diiron Complexes: Ferromagnetic Coupling in a Mixed-Valent HS-FeII/LS-FeIII Dinuclear Complex
Dechert, Sebastian,Demeshko, Serhiy,Hua, Shao-An,Meyer, Franc,Wong, Joanne W. L.,Ye, Shengfa
, p. 4137 - 4145 (2020/11/23)
Using a new bis(tridentate) compartmental pyrazolate-centered ligand HL, the bis(pyrazolato)-bridged diiron complex [L2FeII2][OTf]2 (1) and its singly oxidized mixed-valent congener [L2FeIIFeIII][OTf]3 (2) have been synthesized and structurally characterized. While 1 features two HS-FeII ions coordinated to two cis-axial pyridine moieties in a highly distorted octahedral environment, the metal ions in 2 are coordinated by the ligand strand in a trans-axial configuration. Very different Fe–N bond lengths and distinctly different coordination polyhedra are associated with pronounced valence localization in the case of 2. The electronic structures and magnetic properties of 1 and 2 have been further investigated by M?ssbauer spectroscopy and variable temperature magnetic susceptibility measurements. In the case of 1, weak antiferromagnetic coupling is observed between the two HS-FeII ions (J = –0.6 cm–1), while the HS-FeII and LS-FeIII ions in 2 are ferromagnetically coupled (J = +5.2 cm–1) to give an ST = 5/2 ground state with significant zero-field splitting (DFe(II) = 2.3 cm–1). The findings are rationalized with the help of DFT computations.
Mono- And Dinuclear Coinage Metal Complexes Supported by an Imino-Pyridine-NHC Ligand: Structural and Photophysical Studies
Simler, Thomas,M?bius, Karen,Müller, Kerstin,Feuerstein, Thomas J.,Gamer, Michael T.,Lebedkin, Sergei,Kappes, Manfred M.,Roesky, Peter W.
, p. 3649 - 3661 (2019/11/13)
A new imino-pyridine-NHC (NHC = N-heterocyclic carbene) hybrid ligand was accessed through a multistep synthesis, and its coordination chemistry was examined among coinage metals. Mononuclear copper, silver, and gold complexes as well as dinuclear homo- and heterometallic complexes were isolated and fully characterized by spectroscopic methods as well as X-ray crystallography. A comparative study of the structural and photophysical properties of the complexes was performed to get more insight into structure-property relationships. The photoluminescence (PL) properties were investigated in the solid state at temperatures between 20 and 295 K, and systematically compared with those of related complexes bearing a bipyridine-NHC ligand and previously reported by our group. The PL properties can be finely "tuned" depending on the coordinated metals, and the weak emission of the complexes can be traced back to the structural flexibility of the imino-pyridine-NHC framework.