Reactions of niobium and tantalum hexanuclear halide clusters with cadmium(II) halides, diamagnetic and paramagnetic clusters with semiconducting properties

Vojnović, Marija; Brničević, Nevenka; Bašic, Ivan; Trojko, Rudolf; Miljak, M.; Desnica-Frankovic, I.D.

doi:10.1016/s0025-5408(01)00510-4

Cited by 16 publications

(12 citation statements)

References 28 publications

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“…(2)]: The c dia Pascal term represents general atomic (ionic) diamagnetic contributions tabulated in the literature, [12,20] whereas the c dia deloc term represents the diamagnetic contribution from fifteen electrons delocalised over the cluster. [12,21,22] The term c tip is the temperature-independent paramagnetic term [23] for the cluster. The temperature-dependent part c spin in Equation (1) is discussed below.…”

Section: Resultsmentioning

confidence: 99%

“…The analysis presented in this work can be compared with the previous magnetic-susceptibility analysis of related com- [21] Indeed, the structure of the latter exhibits the same structural arrangement of the paramagnetic [(Ta 6 Cl 12 …”

Section: Dft Computationsmentioning

confidence: 88%

“…[21] Although one chlorine anion and five water molecules randomly occupy six terminal ligand sites of the [(Ta 6 Cl 12 …”

Section: Dft Computationsmentioning

confidence: 99%

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High‐Temperature Experimental and Theoretical Study of Magnetic Interactions in Diamond and Pseudo‐Diamond Frameworks Built up from Hexanuclear Tantalum Clusters

Perić

Cordier

Cuny

et al. 2011

Chemistry A European J

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Magnetic interactions in solid-state tantalum cluster compounds have been evidenced by using magnetic susceptibility measurements and corroborated by broken-symmetry DFT calculations. The three selected compounds are based on [Ta(6)X(12)(H(2)O)(6)](3+) (X=Cl or/and Br) units with edge-bridged Ta(6) octahedral clusters. Although two of them crystallise in the tetragonal space group I4(1)/a, all compounds exhibit a similar arrangement of paramagnetic clusters related to the diamond structural framework (Fd ̅3m space group). Magnetic parameters were fitted by using the [5,4] Padé approximant of high-temperature series expansion of susceptibility for the Heisenberg model (S=1/2) in the diamond framework, assuming only nearest-neighbouring interactions. Such a model appropriately describes magnetic-susceptibility measurements at temperatures T>0.7|J|/k. The magnetic interaction parameter J between two [Ta(6)Cl(12)(H(2)O)(6)](3+) clusters is estimated to be -64.28(7) cm(-1) ; it has been enhanced by replacing several chlorine inner ligands with bromine ones (J=-123(3) cm(-1) for two [Ta(6)Br(7.7(1))Cl(4.3(1))(H(2)O)(6)](3+) clusters) and is strongest between two bromine [Ta(6)Br(12)(H(2)O)(6)](3+) clusters with a value of -155(1) cm(-1) . Broken-symmetry DFT calculations within spin-dimer analysis confirmed this trend. Those interactions can be explained on the basis of the overlap between singly occupied a(2u) orbitals localised on neighbouring clusters.

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Section: Resultsmentioning

confidence: 99%

Section: Dft Computationsmentioning

confidence: 88%

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High‐Temperature Experimental and Theoretical Study of Magnetic Interactions in Diamond and Pseudo‐Diamond Frameworks Built up from Hexanuclear Tantalum Clusters

Perić

Cordier

Cuny

et al. 2011

Chemistry A European J

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“…The existence of several different oxidation states of the ½M 6 X i 12 nþ cluster unit (n ¼ 2, 3, 4) is the main specificity of these compounds. The clusters with n ¼ 2 or 4 are diamagnetic, whereas those with n ¼ 3 are paramagnetic [1][2][3][4][5]. The molecular orbital model wherein the highest occupied molecular orbital (HOMO) of the ½M 6 X i 12 nþ cluster core is an orbital singlet, doubly occupied when n ¼ 2, singly occupied when n ¼ 3 and empty (LUMO) when n ¼ 4 makes clear the above mentioned behaviour [6].…”

Section: Introductionmentioning

confidence: 99%

“…Heretofore, single crystal X-ray diffraction data have been accessible for a number of paramagnetic tantalum and niobium hexanuclear clusters [3][4][5]7], but their magnetic susceptibility data are rather scarce in the literature. Magnetic exchange interactions between paramagnetic cluster units (intercluster interactions) were detected for [(Ta 6 Cl 12 )Cl(H 2 O) 5 ]CdBr 4 Á 6H 2 O [3], [(Ta 6 Br 12 )Br 3 ] [4] and Lu[(Nb 6 Cl 12 )Cl 6 ] [8]. A temperature dependent measurement of the inverse intensity of an EMR line of the [Nb 6 F 12 ] 3+ cluster unit also confirmed intercluster interactions [5].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structure, spectroscopic and thermal properties of [Et4N][Ta6Br12(H2O)6]Br4·4H2O (Et=ethyl)—A new compound with the paramagnetic [Ta6Br12]3+ cluster core

Perić¹,

Jozić²,

Planinić³

et al. 2009

Journal of Solid State Chemistry

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The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans-[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl, Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

Vojnović

Brničević

Bašic

et al. 2002

Z. anorg. allg. Chem.

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Cubic [Ta 6 Br 12 (H 2 O) 6 ][CuBr 2 X 2 ]·10H 2 O and triclinic [Ta 6 Br 12 (H 2 O) 6 ]X 2 ·trans-[Ta 6 Br 12 (OH) 4 (H 2 O) 2 ]·18H 2 O (X ϭ Cl, Br, NO 3 ) cocrystallize in aqueous solutions of [Ta 6 Br 12 ] 2ϩ in the presence of Cu 2ϩ ions. The crystal structures of [Ta 6 Br 12 (H 2 O) 6 ]Cl 2 ·trans-[Ta 6 Br 12 (OH) 4 (H 2 O) 2 ]·18H 2 O (1) and [Ta 6 Br 12 (H 2 O) 6 ]Br 2 ·trans-[Ta 6 Br 12 (OH) 4 (H 2 O) 2 ]·18H 2 O (3) have been solved in the triclinic space group P 1 (No. 2). Crystal data: 1, a ϭ 9.3264(2) Å , b ϭ 9.8272(2) Å , c ϭ 19.0158(4) Å , Ͱ ϭ 80.931(1)°, β ϭ 81.772(2)°, γ ϭ 80.691(1)°; 3, a ϭ 9.3399(2) Å , b ϭ 9.8796(2) Å , c ϭ 19.0494(4) Å ; Ͱ ϭ 81.037(1)°, β ϭ 81.808(1)°, γ ϭ 80.736 (1)°. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta 6 Br 12 ] 2ϩ in the [Ta 6 Br 12 (H 2 O) 6 ] 2ϩ cation and [Ta 6 Br 12 ] 4ϩ in trans-[Ta 6 Br 12 (OH) 4 (H 2 O) 2 ]. Average bond distances

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Reactions of niobium and tantalum hexanuclear halide clusters with cadmium(II) halides, diamagnetic and paramagnetic clusters with semiconducting properties

Cited by 16 publications

References 28 publications

High‐Temperature Experimental and Theoretical Study of Magnetic Interactions in Diamond and Pseudo‐Diamond Frameworks Built up from Hexanuclear Tantalum Clusters

High‐Temperature Experimental and Theoretical Study of Magnetic Interactions in Diamond and Pseudo‐Diamond Frameworks Built up from Hexanuclear Tantalum Clusters

Synthesis, crystal structure, spectroscopic and thermal properties of [Et4N][Ta6Br12(H2O)6]Br4·4H2O (Et=ethyl)—A new compound with the paramagnetic [Ta6Br12]3+ cluster core

The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans-[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl, Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

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