| 1. |
- Adranno, Brando, et al.
(författare)
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Broadband white-light-emitting electrochemical cells
- 2023
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Ingår i: Advanced Photonics Research. - : John Wiley & Sons. - 2699-9293. ; 4:5
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Tidskriftsartikel (refereegranskat)abstract
- Emerging organic light-emitting devices, such as light-emitting electrochemical cells (LECs), offer a multitude of advantages but currently suffer from that most efficient phosphorescent emitters are based on expensive and rare metals. Herein, it is demonstrated that a rare metal-free salt, bis(benzyltriphenylphosphonium)tetrabromidomanganate(II) ([Ph3PBn]2[MnBr4]), can function as the phosphorescent emitter in an LEC, and that a careful device design results in the fact that such a rare metal-free phosphorescent LEC delivers broadband white emission with a high color rendering index (CRI) of 89. It is further shown that broadband emission is effectuated by an electric-field-driven structural transformation of the original green-light emitter structure into a red-emitting structure.
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| 2. |
- Adranno, Brando, et al.
(författare)
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Enhanced stability and complex phase behaviour of organic-inorganic green-emitting ionic manganese halides
- 2023
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 52:19, s. 6515-6526
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Tidskriftsartikel (refereegranskat)abstract
- Light-emitting materials based on earth-abundant metals, such as manganese hold great promise as emitters for organic lighting devices. In order to apply such emitter materials and, in particular, to overcome the problem of self-quenching due to cross-relaxation, we investigated a series of tetrabromidomanganate ([MnBr4]2−) salts with bulky tetraalkylphosphonium counter cations [Pnnn]+, namely [Pnnnn]2[MnBr4] (n = 4 (1), 6 (2) and 8 (3)), which can be obtained by a straightforward reaction of the respective phosphonium bromide and MnBr2. Variation of the cation size allows control of the properties of the resulting ionic materials. 1 and 3 qualify as ionic liquids (ILs), where 1 features a melting point of 68 °C, and 3 is liquid at room temperature and even at very low temperatures. Furthermore, 1 and 2 show the formation of higher-ordered thermotropic mesophases. For 1 a transition to a thermodynamically metastable smectic liquid crystalline phase can be observed at room temperature upon reheating from the metastable glassy state; 2 appears to form a plastic crystalline phase at ∼63 °C, which persists up to the melting point of 235 °C. The photoemission is greatly affected by phase behaviour and ion dynamics. A photoluminescence quantum yield of 61% could be achieved, by balancing the increase in Mn2+-Mn2+ separation and reducing self-quenching through increasingly large organic cations which leads to adverse increased vibrational quenching. Compared to analogous ammonium compounds, which have been promoted as @#x0308;inorganic hybrid perovskite, the phosphonium salts show superior performance, with respect to photoluminescent quantum yield and thermal and air/humidity stability. As the presented compounds are not sensitive to the atmosphere, in particular moisture, and show strong visible electroluminescence in the green region of light, they are important emitter materials for use in organic light-emitting devices.
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| 3. |
- Adranno, Brando, et al.
(författare)
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The 8-hydroxyquinolinium cation as a lead structure for efficient color-tunable ionic small molecule emitting materials
- 2023
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Ingår i: Advanced Photonics Research. - : John Wiley & Sons. - 2699-9293. ; 4:3
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Tidskriftsartikel (refereegranskat)abstract
- Albeit tris(8-hydroxyquinolinato) aluminum (Alq3) and its derivatives are prominent emitter materials for organic lighting devices, and the optical transitions occur among ligand-centered states, the use of metal-free 8-hydroxyquinoline is impractical as it suffers from strong nonradiative quenching, mainly through fast proton transfer. Herein, it is shown that the problem of rapid proton exchange and vibration quenching of light emission can be overcome not only by complexation, but also by organization of the 8-hydroxyquinolinium cations into a solid rigid network with appropriate counter-anions (here bis(trifluoromethanesulfonyl)imide). The resulting structure is stiffened by secondary bonding interactions such as pi-stacking and hydrogen bonds, which efficiently block rapid proton transfer quenching and reduce vibrational deactivation. Additionally, the optical properties are tuned through methyl substitution from deep blue (455 nm) to blue-green (488 nm). Time-dependent density functional theory (TDFT) calculations reveal the emission to occur from which an unexpectedly long-lived S-1 level, unusual for organic fluorophores. All compounds show comparable, even superior photoluminescence compared to Alq3 and related materials, both as solids and thin films with quantum yields (QYs) up to 40-50%. In addition, all compounds show appreciable thermal stability with decomposition temperatures above 310 °C.
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| 4. |
- Babizhetskyy, Volodymyr, et al.
(författare)
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Crystal and electronic structures of the new ternary gallide Zr12Pd40−xGa31+y (x = 0–1.5, y = 0–0.5)
- 2023
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Ingår i: Journal of Solid State Chemistry. - 0022-4596 .- 1095-726X. ; 327
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Tidskriftsartikel (refereegranskat)abstract
- Zr12Pd40Ga31 was prepared from the elements by arc melting under argon and subsequent annealing at 870 K for 720 h. Single-crystal X-ray diffraction reveals that Zr12Pd40Ga31 crystallizes in a new hexagonal structure type: Pearson symbol (PS) hP166, space group P6/mmm, a = 18.7670(6) Ǻ, c = 8.6634(6) Ǻ). The crystal structure consists of three types of atomic layers – two flat sheets at z = 0 (layer A) and z = 0.5 (C) and one corrugated at z = 0.25 and z = 0.75 (B), which stack in the sequence … ABCB … along the [001] direction. The structure shows close vicinity to a series of hexagonal structures with PS hP164–hP171. These compounds show peculiar structural variability expressed in the different atomic occupations of the Wyckoff positions along and around the 3-fold and 6-fold axes. Homogeneity range and lattice parameters of new ternary compound Zr12Pd40−xGa31+y (x = 0–1.5, y = 0–0.5) have been refined from EDX and powder XRD data. Electronic structure calculations and bonding analysis have been performed for an idealized model revealing domination of the Pd–Ga and Ga–Ga interactions.
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| 5. |
- Celania, Chris, et al.
(författare)
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The Prolific Ternary System Pt/Sn/Nd : Insertion of Pt into the Structures of Sn/Nd Intermetallics Yields Structural Complexity and Wealth
- 2023
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 62:24, s. 9369-9378
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Tidskriftsartikel (refereegranskat)abstract
- The understanding of structure and bonding in intermetallic phases still lags behind that of molecular compounds. For that reason, exploring intermetallic phases and identifying structural patterns and relationships are particularly important for closing this knowledge gap. In particular, here we report on the addition of increasing amounts of platinum to ∼2:1 mixtures of tin and neodymium, which yields eight ternary Pt/Sn/Nd compounds, four of which have not been reported before. Interestingly, except for PtSnNd (1), all observed ternary phases of the system can be derived from the binary compounds Sn2Nd and Sn5Nd2 by adding Pt to the composition(s), as they lie on or close to two lines: Sn2Nd-Pt (Pt0.21(1)Sn2Nd (2), PtSn2Nd (3), Pt1.33Sn2Nd (4), Pt2-xSn2+xNd (x = 0.27(3), 5), and Pt3Sn2Nd (6)) or Sn5Nd2-Pt (Pt1.5Sn5-xNd2 (x = 0.16(2), 7) and Pt3Sn5Nd2-x (x = 0.161(8), 8)). While the introduction of increasing amounts of Pt to the binaries Sn2Nd and Sn5Nd2 leads to stepwise changes in the coordination environment of Nd, Pt preserves its coordination over the entire system in the form of interpenetrating bipyramidal {PtSn5Nd5} clusters.
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| 6. |
- Grilli, Davide, et al.
(författare)
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Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)–z : A Symmetric Mirror Homologous Series in the La–Ni–Si System
- 2023
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 62:27, s. 10736-10742
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Tidskriftsartikel (refereegranskat)abstract
- A series of four homologous silicides have been discovered during systematic explorations in the central part of the La–Ni–Si system at 1000 °C. All compounds La12.5Ni28.0Si18.3 (n = 3; a = 28.8686(8), c = 4.0737(2) Å, Z = 3), La22.1Ni39.0Si27.8 (n = 4; a = 20.9340(6), c = 4.1245(2) Å, Z = 1), La32.9Ni49.8Si39.3 (n = 5; a = 24.946(1), c = 4.1471(5) Å, Z = 1), and La44.8Ni66.1Si53.4 (n = 6; a = 28.995(5), c = 4.158(1) Å, Z = 1) crystallize in the hexagonal space group P63/m and can be generalized according to Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)–z with n = 3–6. Their crystal structures are based on AlB2-type building blocks, fused La-centered Ni6Si6 hexagonal prisms, yielding larger oligomeric equilateral domains with the edge size equal to n. The domains extend along the c axis and show checkered ordering of the cationic and anionic parts, while all their atoms are located on mirror planes. Lan(n+1)+xNin(n+5)+ySi(n+1)(n+2)–z can be considered as a mirror series to the La-rich La(n+1)(n+2)Nin(n–1)+2Sin(n+1), where an exchange of the formal cationic and anionic sites, i.e., La and Si, occurs. The La–Ni–Si system is the first system where two such analogous series have been observed.
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| 7. |
- Hammond, Oliver S., et al.
(författare)
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Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids
- 2023
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Ingår i: Small. - : John Wiley and Sons Inc. - 1613-6810 .- 1613-6829. ; 29
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Tidskriftsartikel (refereegranskat)abstract
- A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]−, bis(mandelato)borate, [BMB]− and bis(salicylato)borate, [BScB]−, are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]− by [BMB]−, or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems. © 2023 The Authors.
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| 8. |
- Hiti, Ethan A., et al.
(författare)
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Isolation of anhydrous tetrabutylphosphonium lanthanide hexa- and penta-nitrates from ionic liquids
- 2023
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Ingår i: Polyhedron. - : Elsevier BV. - 0277-5387 .- 1873-3719. ; 232
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Tidskriftsartikel (refereegranskat)abstract
- Our attempts to use an ionic liquid strategy to force f-element coordination of soft donor adenine and 4,5-dicyanoimidazole using 1-pot reactions in water using hydrated lanthanide salts failed, instead resulting in the isolation of anhydrous lanthanide nitrate salts. Reactions of previously ground mixtures of 40 % aq. [P4444][OH] and adenine with Nd(NO3)3·6H2O or Sm(NO3)3·6H2O followed by hand grinding and heating to 90 °C for 10 h led to hot crystallization of anhydrous [P4444]2[Nd(NO3)5] and [P4444]2[Sm(NO3)5]. The same reaction with 4,5-dicyanoimidazole and Nd(NO3)3·6H2O but without heating (10 h, room temperature) to prevent ligand decomposition, led to crystallization of anhydrous [P4444]3[Nd(NO3)6]. [P4444]3[Nd(NO3)6] could also be isolated by conducting the first reaction without using adenine. The single crystal X-ray diffraction structures of the three new anhydrous salts were examined to provide clues to the observed behavior. The [P4444]+ cations allow charge balance while forming box-type encapsulations around the anionic counterpart which has been previously reported in similar structures. The fact that these anhydrous salts were prepared from water with hydrated starting materials and no precautions taken to keep the crystal growing process anhydrous, suggests synthetic strategies that can potentially be beneficial for more advanced separations procedures.
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| 9. |
- Pawłów, J., et al.
(författare)
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Influence of ionic liquid and oleic acid assisted methods on the spectroscopic properties of Nd3+-doped GdPO4 nano-particles
- 2023
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Ingår i: Journal of Materials Chemistry C. - 2050-7526 .- 2050-7534. ; 11:22, s. 7227-7242
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Tidskriftsartikel (refereegranskat)abstract
- We report a detailed analysis of both the structural and spectroscopic properties of Nd3+-doped GdPO4 nano-powders obtained via various wet synthesis methods. This type of material may be useful in optoelectronics, bioimaging and biomedicine. Three series of Nd3+-doped nano-materials with different concentrations of the optical activator (1–10 mol%) were obtained via ionic liquid assisted classical hydrothermal (IL HT) and microwave (IL MW) methods as well as via an oleic acid assisted hydrothermal (OA HT) method. A powder X-ray diffraction (PXRD) technique confirmed that the obtained GdPO4 nano-powders crystallize in a monoclinic system (P21/n) with the average grain size ranging from 40 to 100 nm; the smallest grains are obtained via the ionic liquid assisted microwave method, and no other phase has been detected for any of the materials obtained. Electron microscopy techniques i.e. SEM and TEM were used to demonstrate the differences in the morphology and grain size, which resulted in the spectroscopic properties of nano-materials. The nine-fold coordinated Gd3+ ion in GdPO4 is easily substituted by the Nd3+ one with the C1 symmetry due to their similar ionic radii, so that high-resolution low-temperature absorption and emission spectra do not show any structural distortion. The 4F3/2 excited state dynamics studied at 77 K showed abnormal behavior, similar to that already observed for Nd3+ ions embedded in the YPO4 and LuPO4 tetragonal orthophosphates crystallizing in a xenotime-type crystal system.
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| 10. |
- Ponou, Siméon, et al.
(författare)
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Optimization of Chemical Bonding through Defect Formation and Ordering-The Case of Mg7Pt4Ge4
- 2023
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Ingår i: Inorganic Chemistry. - 0020-1669 .- 1520-510X. ; 62:22, s. 8519-8529
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Tidskriftsartikel (refereegranskat)abstract
- The new phase Mg7Pt4Ge4 (Mg8□1Pt4Ge4; □ = vacancy) was prepared by reacting a mixture of the corresponding elements at high temperatures. According to single crystal X-ray diffraction data, it adopts a defect variant of the lighter analogue Mg2PtSi (Mg8Pt4Si4), reported in the Li2CuAs structure. An ordering of the Mg vacancies results in a stoichiometric phase, Mg7Pt4Ge4. However, the high content of Mg vacancies results in a violation of the 18-valence electron rule, which appears to hold for Mg2PtSi. First principle density functional theory calculations on a hypothetical, vacancy-free "Mg2PtGe"reveal potential electronic instabilities at EF in the band structure and significant occupancy of states with an antibonding character resulting from unfavorable Pt-Ge interactions. These antibonding interactions can be eliminated through introduction of Mg defects, which reduce the valence electron count, leaving the antibonding states empty. Mg itself does not participate in these interactions. Instead, the Mg contribution to the overall bonding comes from electron back-donation from the (Pt, Ge) anionic network to Mg cations. These findings may help to understand how the interplay of structural and electronic factors leads to the "hydrogen pump effect"observed in the closely related Mg3Pt, for which the electronic band structure shows a significant amount of unoccupied bonding states, indicating an electron deficient system.
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| 11. |
- Provino, Alessia, et al.
(författare)
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Solubility limits, magnetic and magnetocaloric properties of MoB-type GdCoxNi1−x (0.47 ≤ x ≤ 0.72)
- 2023
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Ingår i: Journal of Alloys and Compounds. - : Elsevier BV. - 0925-8388 .- 1873-4669. ; 948
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Tidskriftsartikel (refereegranskat)abstract
- The binary GdNi adopting the orthorhombic CrB-type (oS8, Cmcm) dissolves up to 21 at% Co (GdCo0.42Ni0.58), but when the Co content reaches 23.7 at% the crystal structure of the GdCoxNi1−x phase changes from the orthorhombic CrB-type to the tetragonal MoB-type (tI16, I41/amd). The latter remains stable between 23.7 and 36.0 at% Co (0.47 ≤ xCo ≤ 0.72), and there is a two-phase region compositional gap of ≈ 2.5 at% Co between the two structures. One of the two 8e sites available in the MoB-type structure is filled by Gd atoms, while Co and Ni atoms are randomly occupying the other 8e site. The lattice parameter a increases from 3.9485(1) Å to 3.9591(1) Å, while c decreases from 21.3286(1) Å to 21.2404(1) Å as xCo increases, both following a quadratic trend. As a result, the unit cell volume increases from 332.53(2) Å3 to 332.93(2) Å3 for, respectively, the Co-poor (GdCo0.47Ni0.53) and the Co-rich (GdCo0.72Ni0.28) sides of the solid solution, also following a quadratic trend with a negative deviation of the Zen’s law. The title compound becomes ferromagnetic with TC increasing linearly from 150 K for GdCo0.50Ni0.50 to 171 K for GdCo0.70Ni0.30; linear interpolation leads to TC = 127 K and 174 K for the two ends of the solid solution with xCo = 0.47 and 0.72, respectively. The magnetic susceptibility follows the Curie-Weiss law, indicating a trivalent state of Gd ions, with an effective magnetic moment slightly increasing with the Co content. The magnetocaloric effect, calculated in terms of the isothermal magnetic entropy change, decreases slightly as xCo increases, remaining large in the range 127–174 K.
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| 12. |
- Renier, Olivier, et al.
(författare)
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Investigation of the role of hydrogen bonding in ionic liquid-like salts with both N- and S-soft donors
- 2023
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Ingår i: CrystEngComm. - : Royal Society of Chemistry (RSC). - 1466-8033. ; 25:4, s. 530-540
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Tidskriftsartikel (refereegranskat)abstract
- In search of ionic liquids (ILs) with multiple types of soft donor atoms capable of preferentially complexing a range of soft metal ions over harder ions, we investigated structural clues to the role of hydrogen bonding in IL behavior through a series of salts with anions containing both N- and S-donor atoms based on azole thiolates. Reaction of equimolar amounts of triethylamine (Et3N) or diisobutylamine (DBA) with 1-phenyl-1H-tetrazole-5-thiol (PhTzSH), 1-methyl-1H-tetrazole-5-thiol (MeTzSH), or 5-methyl-1,3,4-dithiazole-2-thiol (MeDiTSH) yielded [Et3NH][MeTzS] (1), a yellow liquid, and the low melting yellow solids [DBAH][MeTzS] (2), [Et3NH][PhTzS] (3), [DBAH][PhTzS] (4), [Et3NH][MeDiTS] (5), and [DBAH][MeDiTS] (6). Thermal analysis revealed that all of them qualify as ILs with melting points below 100 °C. Single crystal X-ray structure analysis of 2–6 revealed the presence of an extensive H-bonding network that includes the rare N–H⋯S hydrogen bonds in 3, 4, and 6. These weaker interactions appear to significantly influence thermal behavior, where strong bonding leads to higher melting temperatures and lower decomposition points.
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| 13. |
- Shtender, Vitalii, et al.
(författare)
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Honeycomb Constructs in the La-Ni Intermetallics : Controlling Dimensionality via p-Element Substitution
- 2023
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 62:37, s. 14843-14851
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Tidskriftsartikel (refereegranskat)abstract
- The new ternary compounds La15Ni13Bi5 and La9Ni8Sn5 were obtained by arc melting under argon from appropriate amounts of the elements and subsequent annealing at 800 °C for 2 weeks. Single-crystal X-ray diffraction reveals that they represent two new structure types: La15Ni13Bi5 crystallizes in the hexagonal space group P62m [hP33, a = 14.995(3), c = 4.3421(10) Å, V = 845.5(4) Å3, Z = 1] and La9Ni8Sn5 in P63/m [hP88, a = 23.870(15), c = 4.433(3) Å, V = 2187(3) Å3, Z = 4]. The crystal structures of both compounds are characterized by hexagonal honeycomb-based motifs formed by Ni and Sn that extend along the c axis. The building motif with its three-blade wind turbine shape is reminiscent of the organic molecule triptycene and is unprecedented in extended solids. First-principles calculations have been performed in order to analyze the electronic structure and provide insight into chemical bonding. They reveal significant electron transfer from La to Ni and the respective p-element, which supports the formation of the polyanionic Ni-p-element network. DFT calculations suggest paramagnetic-like behavior for both compounds, which was confirmed by magnetic measurements.
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| 14. |
- Tang, Shi, et al.
(författare)
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Fluorescent carbon dots from birch leaves for sustainable electroluminescent devices
- 2023
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Ingår i: Green Chemistry. - : Royal Society of Chemistry. - 1463-9262 .- 1463-9270. ; 25:23, s. 9884-9895
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Tidskriftsartikel (refereegranskat)abstract
- The shift from depleting petroleum compounds to regenerating biomass as the raw material for organic semiconductors is a prerequisite if organic electronics is to become truly sustainable. Here, we report on a one-pot solvothermal synthesis of a biomass-based carbon dot (bio-CD) fluorescent semiconductor, using birch leaves as the sole raw material. These bio-CDs are highly soluble in ethanol (45 g L-1), and deliver deep-red and narrowband emission (peak wavelength = 675 nm, full width at half maximum, FWHM = 28 nm) at a high photoluminescence quantum yield of 26% in ethanol solution. Systematic structural characterization shows that molecular pheophytin a is the single fluorophore, and that this fluorophore is localized in the bulk of the bio-CD away from its polar surface. The functionality of the birch-leaf-derived bio-CDs in sustainable organic electronics is demonstrated by its employment as the printable emitter in a light-emitting electrochemical cell, which delivers narrowband deep-red luminance of 110 cd m-2, with a FWHM of 29 nm, at an external quantum efficiency of 0.29%. This study thus reveals a promising avenue for the functional benign synthesis and the practical solution-based implementation of narrowband bio-CDs in sustainable optoelectronic technologies.
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| 15. |
- Wineinger, Hannah, et al.
(författare)
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Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4-Amino-1,2,4-triazole
- 2023
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Ingår i: European Journal of Inorganic Chemistry. - : WILEY-V C H VERLAG GMBH. - 1434-1948 .- 1099-1948. ; 26:31
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Tidskriftsartikel (refereegranskat)abstract
- Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH2-1,2,4-Triaz), 5-amino-tetrazole (5-NH2-HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1:1 and 1:3 ratios with CeCl3 center dot 7H(2)O, [C(2)mim](3)[CeCl6] ([C(2)mim](+) = 1-ethyl-2-methylimidazolium), and Ce(NO3)(3)center dot 6H(2)O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH2-1,2,4-Triaz is structure directing via eta(2)mu(2)kappa(2) bridging, with the formation of the dinuclear complexes [Ce2Cl2(mu(2)-4-NH2-1,2,4-Triaz)(4)(H2O)(8)]Cl-4 center dot 4H(2)O, [Ce-2(mu(2)-4-NH2-1,2,4-Triaz)(4)(4-NH2-1,2,4-Triaz)(2)(Cl)(6)], and [4-NH2-1,2,4-HTriaz][Ce-2(mu(2)-4-NH2-1,2,4-Triaz)(2)(mu(2)-NO3)(NO3)(6)(H2O)(2)]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce-6(mu(3)-O)(4)(mu(3)-OH)(2)(mu(3)-Cl)(2)(Cl)(6)(mu(2)-4-NH2-1,2,4-Triaz)(12)]center dot 7H(2)O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M6X8 core, and the first reported Ce(III) hexanuclear complex of this type.
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