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Synthesis, Crystal Structure and Fluorescent Properties of Dinuclear Zinc Complex
摘要： A dinuclear zinc complex [Zn2(qnal)2(CH3COO)2] (Hqnal: N-(8'-quinolyl)-2-hydroxy-1-naphthaldimine) was synthesized and characterized by X-ray crystallography. The complex crystallizes in monoclinic system, space group C2/c with a = 40.00(3), b = 7.690(5), c = 27.492(16) ?, β = 120.446(11)°, V = 17290(8) ?3, Z = 8. Dc = 1.537 g/cm3, Mr = 843.48, F(000) = 3456, μ(MoKα) = 1.374 mm-1, S = 1.033, R = 0.0403 and wR = 0.1049 for 4454 observed reflections (I > 2σ(I)). It exhibits a 3D supramolecular architecture constructing by π-π stacking interactions between quinolyl and naphthyl rings and shows luminescent property in the yellow region.
关键词： Zinc complex,Dinuclear,Fluorescence,Crystal structure
更新于2025-09-23 15:22:29
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Magnetic and Luminescence Properties of Two Dinuclear Lanthanide Complexes with Butterfly-like Arrangement
摘要： Two dinuclear lanthanide complexes with pentadentate ligand 3-[bis(pyridine-2-ylmethyl)amino]propane-1,2-diol (H2L), formulated as [Ln2(HL)2(NO3)2(H2O)2]·1.5NO3·0.5I [Ln = Tb (ZTU-1) and Eu (ZTU-2); ZTU = Zhaotong University] were synthesized and structurally characterized. ZTU-1 and ZTU-2 are isomorphous and feature a butterfly-like arrangement. The fluorescence properties of ZTU-1 and ZTU-2 are investigated and slow magnetic relaxation behavior is observed in ZTU-1.
关键词： Lanthanides,Slow magnetic relaxation,Luminescence,Dinuclear lanthanide complex
更新于2025-09-23 15:21:01
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Partially Solvated Dinuclear Ruthenium Compounds Bridged by Quinoxaline-Functionalized Ligands as Ru(II) Photocage Architectures for Low-Energy Light Absorption
摘要： Ruthenium compounds with coordinated photo-labile molecules that can be selectively released by irradiation with a visible light source are finding increasing applications in photoactivated chemotherapy (PCT) as photocages. Earlier photocages based on mononuclear Ru(II) compounds lack absorption in the therapeutic window (λ > 600 nm). In previous work, we synthesized the first partially solvated tppz bridged (tppz= 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine) dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers. To further explore the effect of the bridging ligand on Ru(II) photocage design, we used quinoxaline-functionalized bridging ligand platforms to prepare [{RuII(NCCH3)4}2(μ-BL)](PF6)4[BL = dpq, 2,3-di(pyridin-2-yl)quinoxaline (1); BL = dpb, 2,3-di(pyridin-2-yl)benzo[g]quinoxaline (2)]. The compounds are capable of absorbing green light with tails extending beyond 650 nm which can be exploited for applications as PCT agents. Experimental results were additionally verified by DFT calculations. The use of two Ru(II) centers equipped with quinoxaline-based bridging ligands is a promising design strategy for the synthesis of a new family of dinuclear Ru(II) photocage prototypes with the ability to absorb low-energy visible light.
关键词： photoactivated chemotherapy,Ruthenium compounds,photocages,low-energy light absorption,dinuclear Ru(II) complexes
更新于2025-09-23 15:19:57
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Modulation of the properties of dinuclear lanthanide complexes through utilizing different ?2-diketonate co-ligands: near-infrared luminescence and magnetization dynamics
摘要： A family of new dinuclear lanthanide complexes as the simplest entities showing intramolecular magnetic interactions, [Ln2(dbm)2(L)2(CH3OH)2] (Ln = Tb (1), Dy (2), Ho (3), Er (4), Yb (5), Lu (6)), [Ln2(acac)2(L)2(EtOH)2] (Ln = Dy (7), Er (8)), [Dy2(TTA)2(L)2(CH3OH)2]·2CH2Cl2 (9) and [Dy2(tfa)2(L)2(CH3OH)2] (10) (H2L = N’-(2-hydroxy-5-methylphenyl)-pyrazine-2-carbohydrazide, Hdbm = 1,3-diphenyl-1,3-propanedione, Hacac = acetylacetone, HTTA = 2-thenoyltrifluoroacetone, Htfa = trifluoroacetylacetone), were constructed successfully by the reaction of a Schiff base ligand H2L and four different β-diketonate salts. As for complexes 4, 5 and 8, all exhibit the characteristic emission peaks of the corresponding Er3+, Yb3+ and Er3+ ions, respectively. Meanwhile, the excitation wavelength (510 nm) of 5 is located in the visible region, confirming its significant potential application value. Magnetic studies indicate that complexes 9 and 10 exhibit characteristic slow relaxation of magnetization with the energy barriers (Ueff) of 102 K for 9 and 140 K for 10 under a zero dc field. Under the optimized dc fields, slow magnetic relaxations are present in 2 and 7, and the Ueff values of 9 and 10 have been improved. This proves that the β-diketonate co-ligands deserve an important role in regulating Dy-SMMs influenced by the diverse perturbations of the axial crystal field originating from minor changes in the coordination environment.
关键词： single-molecule magnets,dinuclear lanthanide complexes,β-diketonate co-ligands,near-infrared luminescence,magnetization dynamics
更新于2025-09-23 15:19:57
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Structural, Photophysical and Magnetic Studies of {Ln2} Assembled about Oxime
摘要： A series of bifunctional [Hpy]2[Ln2(NO3)2(ampy)4(H2shi)2] ({Ln2}; Ln = Eu(1), Gd(2) and Dy(3); H3shi = salicylhydroxamic acid; Hampy = 5-aminopyridine-2-carboxylic acid) have been synthesized and characterized. Single-crystal X-ray diffraction analyses reveal that complexes 1 and 3 are isostructural. The complexes {Ln2} exhibit either photophysical or magnetic properties in respect to the central lanthanide ion. It is rarely observed that 1 gives bright and red emission with high quantum yield (16%) and a long luminescence lifetime (547 μs). Magnetic measurement reveals that 3 exhibits significant single molecule magnet behavior with an effective energy barrier of 31 K.
关键词： single-molecule magnet,fluorescence,dinuclear,lanthanide
更新于2025-09-23 15:19:57
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Molecular isomeric engineering of naphthyl-quinoline-containing dinuclear platinum complexes to tune emission from deep red to near infrared
摘要： Four isomeric dinuclear platinum complexes of (C^N)2Pt2(m-OXT)2 are synthesized and characterized with different C^N cyclometalating ligands and the same ancillary ligand of 5-(4-octylphenyl)-1,3,4-oxadiazole-2-thiol (m-OXT). These isomeric C^N ligands are 1-naphthyl-1-isoquinoline (niq), 2-naphthyl-1-isoquinoline (2niq), 1-naphthyl-2-quinoline (nq) and 2-naphthyl-2-quinoline (2nq). The isomeric effect on the photophysical, electrochemical and electroluminescence properties of (C^N)2Pt2(m-OXT)2 was systematically studied. It is found that the emissions were easy to tune from deep red to near infrared for (C^N)2Pt2(m-OXT)2 by changing the C^N isomers. Furthermore, the complexes with 2-naphthyl in these presented better electroluminescence (EL) properties than the complexes with 1-naphthyl. In contrast to the (2nq)2Pt2(l-OXT)2-doped devices displaying a deep-red emission peaked at 686 nm with an external quantum efficiency (EQE) of 3.21%, the (2niq)2Pt2(l-OXT)2-doped devices exhibited a near-infrared emission peaked at 704 nm with a significantly increased EQE of 8.86% and a radiant emittance of 986 mW cm?2. Our research provides an efficient strategy to tune emission from deep red to near infrared by a simple isomeric engineering of dinuclear platinum(II) complexes.
关键词： deep red emission,isomeric engineering,near infrared emission,dinuclear platinum complexes,electroluminescence
更新于2025-09-19 17:15:36
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Photophysical, electrochemical, and DFT studies of the novel azacrown-bridged dinuclear ruthenium dye sensitizers for solar cells
摘要： A dinuclear ruthenium bipyridyl complex with 1,10-diaza-18-crown-6 bridging ligand was synthesized and characterized. Its photophysical and electrochemical properties were also studied. DFT computations were performed to complement the experimental investigations. Analysis of the results indicates that the path in which charges move from one metal center to the other is significant for effective electronic coupling. However, electron transfer between the two ruthenium centers is hindered by the azacrown bridging ligand, compared to the smooth electronic transfer reported for a related dye involving an azo bridging ligand.
关键词： Bridging ligands,Dinuclear ruthenium complex,DFT,Charge transfer,Electronic coupling
更新于2025-09-12 10:27:22
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A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties
摘要： The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6 ?. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50–298 K and 10–200 K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb3+ to Eu3+ is thermally activated, with the most important pathway involving the 7F1 Eu3+ J-multiplet at room temperature. The energy transfer from the antenna to Eu3+ was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu3+ upper states rather than direct ligand–metal transfer to 5D1 or 5D0. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions.
关键词： temperature sensing,hetero-dinuclear complexes,lanthanide,energy transfer,optical thermometer
更新于2025-09-09 09:28:46