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The unit cell of the title compound, [Ni(C16H10ClN6)2]·2CH3OH, consists of a neutral complex and two methanol mol­ecules. In the complex, the two tridentate 2-(3-(4-chloro­phen­yl)-1H-1,2,4-triazol-5-yl)-6-(1H-pyrazol-1-yl)pyridine ligands coordinate to the central NiII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo­octa­hedral coordination sphere. Neighbouring tapered mol­ecules are linked through weak C—H(pz)⋯π(ph) inter­actions into monoperiodic chains, which are further linked through weak C—H⋯N/C inter­actions into diperiodic layers. The inter­molecular contacts were qu­anti­fied using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H 32.8%, C⋯H/H⋯C 27.5%, N⋯H/H⋯N 15.1%, and Cl⋯H/H⋯Cl 14.0%. The average Ni—N bond distance is 2.095 Å. Energy framework analysis at the HF/3–21 G theory level was performed to qu­antify the inter­action energies in the crystal structure. [ABSTRACT FROM AUTHOR]

Lanthanide coordination compounds NMe4[LnL4], NEt4[LnL4] and PPh4[LnL4] (Ln3+ = Eu, Gd, Tb) with the carbacylamidophosphate (CAPh) ligand dimethyl-N-trichloroacetylamidophosphate (HL= Cl3CC(O)N(H)P(O)(OMe)2) were synthesized. These complexes are characterized using infrared, ultraviolet diffuse reflection, and luminescence spectroscopy as well as through elemental and X-ray analyses. The effect of changing the cation type on the structure and luminescence properties of the tetrakis-complex [LnL4]− was analyzed. TD-DFT calculations reveal cation-specific contributions to the excited states in tetrakis complexes, with [PPh4]+ playing a central role in both singlet and triplet states. This leads to longer donor–acceptor distances compared to NMe4[LnL4] and NEt4[LnL4]. Additionally, intramolecular energy transfer (IET) calculations for Eu3+ and Tb3+ tetrakis compounds reveal Tb3+ sensitization via S1 and Eu3+via the typical T1 state. [ABSTRACT FROM AUTHOR]

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-trichloroacetyl) phosphoramidate (HL) and tetraphenylphosphonium, of composition PPh4[LuL4] (L = CAPh = carbacylamidophosphate), or (C24H20)-[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL4]- with a coordination number of 8[O] for LuIII, while PPh4+ serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodecahedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four molecules in the unit cell. Weak hydrogen bonds O⋯HC(Ph), Cl⋯HC(Ph) and N⋯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed. [ABSTRACT FROM AUTHOR]

The tetra­kis complex of neodymium(III), tetra­kis­{μ-N-[bis­(pyrrolidin-1-yl)phos­phor­yl]acet­am­id­ato}bis(pro­pan-2-ol)neodymiumsodium pro­pan-2-ol monosol­vate, [NaNd(C10H16Cl3N3O2)4(C3H8O)2]·C3H8O or NaNdPyr4(i-PrOH)2·i-PrOH, with the amide type CAPh ligand bis(N,N-tetra­methylene)(tri­chloro­acetyl)phos­phoric acid tri­amide (HPyr), has been synthesized, crystallized and characterized by X-ray diffraction. The complex does not have the tetra­kis­(CAPh)lanthanide anion, which is typical for ester-type CAPh-based coordin­ation compounds. Instead, the NdO8 polyhedron is formed by one oxygen atom of a 2-propanol mol­ecule and seven oxygen atoms of CAPh ligands in the title compound. Three CAPh ligands are coordinated in a bidentate chelating manner to the NdIII ion and simultaneously binding the sodium cation by μ2-bridging PO and CO groups while the fourth CAPh ligand is coordinated to the sodium cation in a bidentate chelating manner and, due to the μ2-bridging function of the PO group, also binds the neodymium ion. [ABSTRACT FROM AUTHOR]

The caesium salt of dimethyl-N-benzoylamidophosphate, namely, aqua[dimethyl (N-enzoylamido-O)phosphonato-O]caesium, [Cs(C9H11NO4P)(H2O)] or CsL•H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoylamidophosphate anions towards the caesium cations. [ABSTRACT FROM AUTHOR]

Coordination compounds of lanthanides NEt4[NaLn2L4(H2O)], Na[NaLn2L4(H2O)]·2H2O (Ln = La3+, Nd3+) with the bis-chelating carbacylamidophosphate ligand tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (H2L) were obtained for the first time via reactions of Na2L with lanthanide nitrates. The complexes were characterized by IR and NMR spectroscopy and laser desorption/ionization mass spectrometry. From X-ray diffraction analysis, it was established that the complex anions in the obtained compounds have a structure of a quadruple-stranded helicate, which encapsulates a sodium cation and a molecule of water into the negatively charged environment of the ligand fluorine and carbonyl oxygen atoms. Upon excitation by the 266 nm harmonic line of the Nd:YAG pulsed laser, the NEt4[NaNd2L4(H2O)] complex exhibits IR-emission at 300 and 77 K with the 4F3/2 emission lifetime of 2 μs. [ABSTRACT FROM AUTHOR]

The anionic tetra­kis-complex of lanthanum(III) NMe4LaL4 with the CAPh-ligand dimethyl (2,2,2-tri­chloro­acet­yl)phospho­ramidate (HL), namely, tetra­methyl­ammonium tetra­kis­{2,2,2-tri­chloro-1-[(di­meth­oxy­phosphor­yl)imino]­ethano­lato}lanthanum(III), (C4H12N)[La(C4H6Cl3NO4P)4], has been synthesized, crystallized and structurally characterized by X-ray diffraction. The lanthanide ion is surrounded by four anionic, bis-chelating CAPh ligands forming the complex anion with a coordination number of eight for La3+ and NMe4+ as the counter-ion. The coordination polyhedron of the La3+ ion was inter­preted as a triangular dodeca­hedron. [ABSTRACT FROM AUTHOR]

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-trichloroacetyl) phosphoramidate (HL) and tetraphenylphosphonium, of composition PPh4[LuL4] (L = CAPh = carbacylamidophosphate), or (C24H20)-[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL4]- with a coordination number of 8[O] for LuIII, while PPh4+ serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodecahedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four molecules in the unit cell. Weak hydrogen bonds O⋯HC(Ph), Cl⋯HC(Ph) and N⋯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed. [ABSTRACT FROM AUTHOR]

Searching for prospective luminescent materials, the series of new lanthanide coordination compounds CsLnL4(Ln = La, Pr, Nd, Sm – Er, and Yb; L− = {C6H5CONPO(OCH3)2}-) was synthesized. X-ray diffraction studies of CsNdL4and CsYbL4have been performed establishing polymeric structures of thetetrakis-complexes built from [LnL4]−anions and cesium cations functioning as linkers. The IR, absorption, emission, excitation spectra, and decay time measurements at 298 and 77 K, as well as thermal gravimetric analyses, were used to characterize the complexes. [ABSTRACT FROM PUBLISHER]

Materials based on Eu 3+ and Tb 3+ coordination compounds are of great interest due to their strong red and green luminescence. Appropriate selection of ligands plays a huge role in optimizing their photophysical properties. Another very helpful instrument for such optimization is theoretical modelling, which permits the prediction of the emissive properties of materials through intramolecular energy transfer analysis. The ligands that allow for achieving high efficiency of Eu 3+ and Tb 3+ emissions include carbacylamidophosphates (CAPh, HL). In this brief review, we summarize recent research for lanthanides CAPh-based coordination compounds of general formulas Cat[LnL] 4 , [LnL 3 Q] and [Ln(HL) 3 (NO 3 ) 3 ], where Cat + = Cs + , NEt4 + , PPh 4 + and Q = 1,10-phenanthroline, 2,2-bipyridine or triphenylphosphine oxide, involving the use of thermal gravimetric analysis, X-ray analysis, and absorption and luminescence spectroscopy. We carried out a comparison with selected Ln 3+ β-diketonates. Possibilities and developments of theoretical calculations on energy transfer rates are also presented., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Kariaka, Lipa, Carneiro Neto, Malta, Gawryszewska and Amirkhanov.)

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt 4 [LnL 4 ] (Ln 3+ =La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt 4 + on the structure and properties of the tetrakis-complex [LnL4] - is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5 D 0 → 7 F 4 transition, observed in the luminescence spectrum of NEt 4 [EuL 4 ], is discussed based on theoretical calculations., (© 2022 Wiley-VCH GmbH.)

In both independent mol-ecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the Nd(III) atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodeca-hedral geometry. In the phosphoryl ligands, the benzene rings are twisted with respect to the planes of the sp(2)-hybridized C atoms of the chelate rings by 12.1 (1)-24.7 (1)°.