2,1,3-Benzoselenadiazole as Mono- and Bidentate N-Donor for Heteroleptic Cu(I) Complexes: Synthesis, Characterization and Photophysical Properties

IF 3.1 4区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
V. Ferraro, Fabian Hoffmann, Olaf Fuhr, Burkhard Luy, Stefan Bräse
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引用次数: 0

Abstract

Mono- and binuclear Cu(I) complexes were isolated employing 2,1,3-benzoselenadiazole (BSeD) as the N-donor ligand, and triphenylphosphine or bis[(2-diphenylphosphino)phenyl] ether (DPEphos) as P-donors. Then, 77Se NMR was measured for the free ligand and the corresponding Cu(I) derivatives, and the related signal was downshifted by 12.86 ppm in the case of [Cu(BSeD)(PPh3)2(ClO4)], and around 15 ppm for the binuclear species. The structure of [Cu(BSeD)(PPh3)2(ClO4)] and [Cu2(μ2-BSeD)(DPEphos)2(ClO4)2] was confirmed by single-crystal X-ray diffraction. The geometry of the Cu(I) complexes was optimized through DFT calculations, and the nature of the Cu···O interaction was investigated through AIM analysis. The three Cu(I) complexes were characterized by intense absorption under 400 nm and, after being excited with blue irradiation, [Cu(BSeD)(PPh3)2(ClO4)] and [Cu2(μ2-BSeD)(PPh3)4(ClO4)2] exhibited weak red emissions centered at 700 nm. The lifetimes comprised between 121 and 159 μs support the involvement of triplet excited states in the emission process. The photoluminescent properties of [Cu(BSeD)(PPh3)2(ClO4)] were supported by TDDFT computations, and the emission was predicted at 710 nm and ascribed to a metal-to-ligand charge transfer (3MLCT) process, in agreement with the experimental data.
2,1,3-苯并硒二唑作为异色 Cu(I) 配合物的单齿和双齿 N-载体:合成、表征和光物理性质
以 2,1,3-苯并硒二唑 (BSeD) 为 N-供体配体,三苯基膦或双[(2-二苯基膦)苯基]醚 (DPEphos) 为 P-供体,分离出单核和双核 Cu(I) 配合物。然后,对游离配体和相应的 Cu(I) 衍生物进行了 77Se NMR 测量,发现[Cu(BSeD)(PPh3)2(ClO4)]的相关信号下移了 12.86 ppm,而双核物种的相关信号下移了约 15 ppm。单晶 X 射线衍射证实了[Cu(BSeD)(PPh3)2(ClO4)]和[Cu2(μ2-BSeD)(DPEphos)2(ClO4)2]的结构。通过 DFT 计算优化了 Cu(I)配合物的几何形状,并通过 AIM 分析研究了 Cu-O 相互作用的性质。这三种 Cu(I) 复合物在 400 纳米波长下具有强烈的吸收特性,而[Cu(BSeD)(PPh3)2(ClO4)]和[Cu2(μ2-BSeD)(PPh3)4(ClO4)2]经蓝色照射激发后,在 700 纳米波长处显示出微弱的红色发射。它们的寿命介于 121 和 159 μs 之间,证明三重激发态参与了发射过程。TDDFT 计算支持[Cu(BSeD)(PPh3)2(ClO4)]的光致发光特性,预测其在 710 纳米波长处发射,并将其归因于金属到配体的电荷转移(3MLCT)过程,这与实验数据一致。
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来源期刊
Inorganics
Inorganics Chemistry-Inorganic Chemistry
CiteScore
2.80
自引率
10.30%
发文量
193
审稿时长
6 weeks
期刊介绍: Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD
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