Family of Carboxylate- and Nitrate-diphenoxo Triply Bridged Dinuclear Ni^IILn^III Complexes (Ln = Eu, Gd, Tb, Ho, Er, Y): Synthesis, Experimental and Theoretical Magneto-Structural Studies, and Single-Molecule Magnet Behavior

Seven acetate-diphenoxo triply bridged M^II-Ln^III complexes (M^II = Ni^II and Ln^III = Gd, Tb, Ho, Er, and Y; M^II = Zn^II and Ln^III = Ho^III and Er^III) of formula [M­(μ-L)­(μ-OAc)­Ln­(NO₃)₂], one nitrate-diphenoxo triply bridged Ni^II–Tb^III complex, [Ni­(μ-L)­(μ-NO₃)­Tb­(NO₃)₂]·2CH₃OH, and two diphenoxo doubly bridged Ni^II-Ln^III complexes (Ln^III = Eu, Gd) of formula [Ni­(H₂O)­(μ-L)­Ln­(NO₃)₃]·2CH₃OH have been prepared in one pot reaction from the compartmental ligand <i>N</i>,<i>N</i>′,<i>N</i>″-trimethyl-<i>N</i>,<i>N</i>″-bis­(2-hydroxy-3-methoxy-5-methylbenzyl)­diethylenetriamine (H₂L). Moreover, Ni^II-Ln^III complexes bearing benzoate or 9-anthracenecarboxylate bridging groups of formula [Ni­(μ-L)­(μ-BzO)­Dy­(NO₃)₂] and [Ni­(μ-L)­(μ-9-An)­Dy­(9-An)­(NO₃)₂]·3CH₃CN have also been successfully synthesized. In acetate-diphenoxo triply bridged complexes, the acetate bridging group forces the structure to be folded with an average hinge angle in the M­(μ-O₂)­Ln bridging fragment of ∼22°, whereas nitrate-diphenoxo doubly bridged complexes and diphenoxo-doubly bridged complexes exhibit more planar structures with hinge angles of ∼13° and ∼2°, respectively. All Ni^II-Ln^III complexes exhibit ferromagnetic interactions between Ni^II and Ln^III ions and, in the case of the Gd^III complexes, the <i>J</i>_NiGd coupling increases weakly but significantly with the planarity of the M–(O)₂–Gd bridging fragment and with the increase of the Ni–O–Gd angle. Density functional theory (DFT) theoretical calculations on the Ni^IIGd^III complexes and model compounds support these magneto-structural correlations as well as the experimental <i>J</i>_NiGd values, which were found to be ∼1.38 and ∼2.1 cm^–1 for the folded [Ni­(μ-L)­(μ-OAc)­Gd­(NO₃)₂] and planar [Ni­(H₂O)­(μ-L)­Gd­(NO₃)₃]·2CH₃OH complexes, respectively. The Ni^IIDy^III complexes exhibit slow relaxation of the magnetization with Δ/<i>k</i>_B energy barriers under 1000 Oe applied magnetic fields of 9.2 and 10.1 K for [Ni­(μ-L)­(μ-BzO)­Dy­(NO₃)₂] and [Ni­(μ-L)­(μ-9-An)­Dy­(9-An)­(NO₃)₂]·3CH₃CN, respectively

Family of Carboxylate- and Nitrate-diphenoxo Triply Bridged Dinuclear Ni^IILn^III Complexes (Ln = Eu, Gd, Tb, Ho, Er, Y): Synthesis, Experimental and Theoretical Magneto-Structural Studies, and Single-Molecule Magnet Behavior

Seven acetate-diphenoxo triply bridged M^II-Ln^III complexes (M^II = Ni^II and Ln^III = Gd, Tb, Ho, Er, and Y; M^II = Zn^II and Ln^III = Ho^III and Er^III) of formula [M­(μ-L)­(μ-OAc)­Ln­(NO₃)₂], one nitrate-diphenoxo triply bridged Ni^II–Tb^III complex, [Ni­(μ-L)­(μ-NO₃)­Tb­(NO₃)₂]·2CH₃OH, and two diphenoxo doubly bridged Ni^II-Ln^III complexes (Ln^III = Eu, Gd) of formula [Ni­(H₂O)­(μ-L)­Ln­(NO₃)₃]·2CH₃OH have been prepared in one pot reaction from the compartmental ligand <i>N</i>,<i>N</i>′,<i>N</i>″-trimethyl-<i>N</i>,<i>N</i>″-bis­(2-hydroxy-3-methoxy-5-methylbenzyl)­diethylenetriamine (H₂L). Moreover, Ni^II-Ln^III complexes bearing benzoate or 9-anthracenecarboxylate bridging groups of formula [Ni­(μ-L)­(μ-BzO)­Dy­(NO₃)₂] and [Ni­(μ-L)­(μ-9-An)­Dy­(9-An)­(NO₃)₂]·3CH₃CN have also been successfully synthesized. In acetate-diphenoxo triply bridged complexes, the acetate bridging group forces the structure to be folded with an average hinge angle in the M­(μ-O₂)­Ln bridging fragment of ∼22°, whereas nitrate-diphenoxo doubly bridged complexes and diphenoxo-doubly bridged complexes exhibit more planar structures with hinge angles of ∼13° and ∼2°, respectively. All Ni^II-Ln^III complexes exhibit ferromagnetic interactions between Ni^II and Ln^III ions and, in the case of the Gd^III complexes, the <i>J</i>_NiGd coupling increases weakly but significantly with the planarity of the M–(O)₂–Gd bridging fragment and with the increase of the Ni–O–Gd angle. Density functional theory (DFT) theoretical calculations on the Ni^IIGd^III complexes and model compounds support these magneto-structural correlations as well as the experimental <i>J</i>_NiGd values, which were found to be ∼1.38 and ∼2.1 cm^–1 for the folded [Ni­(μ-L)­(μ-OAc)­Gd­(NO₃)₂] and planar [Ni­(H₂O)­(μ-L)­Gd­(NO₃)₃]·2CH₃OH complexes, respectively. The Ni^IIDy^III complexes exhibit slow relaxation of the magnetization with Δ/<i>k</i>_B energy barriers under 1000 Oe applied magnetic fields of 9.2 and 10.1 K for [Ni­(μ-L)­(μ-BzO)­Dy­(NO₃)₂] and [Ni­(μ-L)­(μ-9-An)­Dy­(9-An)­(NO₃)₂]·3CH₃CN, respectively

Thermally Activated Delayed Fluorescence (TADF) and Enhancing Photoluminescence Quantum Yields of [Cu^I(diimine)(diphosphine)]⁺ ComplexesPhotophysical, Structural, and Computational Studies

The complexes [Cu­(I)­(POP)­(dmbpy)]­[BF₄] (<b>1</b>) and [Cu­(I)­(POP)­(tmbpy)]­[BF₄] (<b>2</b>) (dmbpy = 4,4′-dimethyl-2,2′-bipyridyl; tmbpy = 4,4′,6,6′-tetramethyl-2,2′-bipyridyl; POP = bis­[2-(diphenylphosphino)-phenyl]­ether) have been studied in a wide temperature range by steady-state and time-resolved emission spectroscopy in fluid solution, frozen solution, and as solid powders. Emission quantum yields of up to 74% were observed for <b>2</b> in a rigid matrix (powder), substantially higher than for <b>1</b> of around 9% under the same conditions. Importantly, it was found that the emission of <b>2</b> at ambient temperature represents a thermally activated delayed fluorescence (TADF) which renders the compound to be a good candidate for singlet harvesting in OLEDs. The role of steric constraints within the complexes, in particular their influences on the emission quantum yields, were investigated by hybrid-DFT calculations for the excited triplet state of <b>1</b> and <b>2</b> while manipulating the torsion angle between the bipyridyl and POP ligands. Both complexes showed similar flexibility within a ±10° range of the torsion angle; however, <b>2</b> appeared limited to this range, whereas <b>1</b> could be further twisted with little energy demand. It is concluded that a restricted flexibility leads to a reduction of nonradiative deactivation and thus an increase of emission quantum yield