Dendritic arrays of [Re63-Se)8] 2+ core-containing clusters: Exploratory synthesis and electrochemical studies

Bryan K. Roland, Ware H. Flora, Hugh D. Selby, Neal R Armstrong, Zhiping Zheng

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The reaction between the previously reported site-differentiated cluster solvate [Re63-Se)8-(PEt3) 5(MeCN)](SbF6)2 (1) with pyridyl-based ditopic ligands 4,4′-trimethylenedipyridine (2), 1,2-bis(4-pyridyl)-ethane (3), and (E)-1,2-bis(4-pyridyl)ethene (4) afforded cluster complexes of the general formula [Re63-Se)8(PEt3) 5(L)](SbF6)2 (5-7), where L represents one of the pyridyl-based ligands. Reacting these cluster complex-based ligands with the fully solvated cluster complex [Re63-Se) 8(MeCN)6](SbF6)2 (8) produced dendritic arrays of the general formula {Re63-Se) 8[Re63-Se)8(PEt 3)5(L)]6}(SbF6)14 (9-11), each featuring six circumjacent [Re63-Se) 8(PEt3)5]2- units bridged to a [Re63-Se)8]2-core cluster by the pyridyl-based ligands. Electrochemical studies using a thin-layer electrochemical cell revealed cluster-based redox events in these cluster arrays. For 9 (L = 2), one reversible oxidation event corresponding to the removal of 7 electrons was observed, indicating noninteraction or extremely weak interactions between the clusters. For 10 (L = 3), two poorly resolved oxidation waves were found. For 11 (L = 4), two reversible oxidation events, corresponding respectively to the removal of 1 and 6 electrons, were observed with the 1-electron oxidation event occurring at a potential 150 mV more positive than the 6-electron oxidation. These electrochemical studies suggest intercluster coupling in 11 via through-bond electronic delocalization, which is consistent with electronic spectroscopic studies of this same molecule.

Original languageEnglish (US)
Pages (from-to)6620-6625
Number of pages6
JournalJournal of the American Chemical Society
Volume128
Issue number20
DOIs
StatePublished - May 24 2006

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Electrons
Ligands
Oxidation
Ethane
Electrochemical cells
Oxidation-Reduction
Molecules
1,2-bis(4-pyridyl)ethene
4,4-trimethylenedipyridine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Dendritic arrays of [Re63-Se)8] 2+ core-containing clusters : Exploratory synthesis and electrochemical studies. / Roland, Bryan K.; Flora, Ware H.; Selby, Hugh D.; Armstrong, Neal R; Zheng, Zhiping.

In: Journal of the American Chemical Society, Vol. 128, No. 20, 24.05.2006, p. 6620-6625.

Research output: Contribution to journalArticle

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title = "Dendritic arrays of [Re6(μ3-Se)8] 2+ core-containing clusters: Exploratory synthesis and electrochemical studies",
abstract = "The reaction between the previously reported site-differentiated cluster solvate [Re6(μ3-Se)8-(PEt3) 5(MeCN)](SbF6)2 (1) with pyridyl-based ditopic ligands 4,4′-trimethylenedipyridine (2), 1,2-bis(4-pyridyl)-ethane (3), and (E)-1,2-bis(4-pyridyl)ethene (4) afforded cluster complexes of the general formula [Re6(μ3-Se)8(PEt3) 5(L)](SbF6)2 (5-7), where L represents one of the pyridyl-based ligands. Reacting these cluster complex-based ligands with the fully solvated cluster complex [Re6(μ3-Se) 8(MeCN)6](SbF6)2 (8) produced dendritic arrays of the general formula {Re6(μ3-Se) 8[Re6(μ3-Se)8(PEt 3)5(L)]6}(SbF6)14 (9-11), each featuring six circumjacent [Re6(μ3-Se) 8(PEt3)5]2- units bridged to a [Re6(μ3-Se)8]2-core cluster by the pyridyl-based ligands. Electrochemical studies using a thin-layer electrochemical cell revealed cluster-based redox events in these cluster arrays. For 9 (L = 2), one reversible oxidation event corresponding to the removal of 7 electrons was observed, indicating noninteraction or extremely weak interactions between the clusters. For 10 (L = 3), two poorly resolved oxidation waves were found. For 11 (L = 4), two reversible oxidation events, corresponding respectively to the removal of 1 and 6 electrons, were observed with the 1-electron oxidation event occurring at a potential 150 mV more positive than the 6-electron oxidation. These electrochemical studies suggest intercluster coupling in 11 via through-bond electronic delocalization, which is consistent with electronic spectroscopic studies of this same molecule.",
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AB - The reaction between the previously reported site-differentiated cluster solvate [Re6(μ3-Se)8-(PEt3) 5(MeCN)](SbF6)2 (1) with pyridyl-based ditopic ligands 4,4′-trimethylenedipyridine (2), 1,2-bis(4-pyridyl)-ethane (3), and (E)-1,2-bis(4-pyridyl)ethene (4) afforded cluster complexes of the general formula [Re6(μ3-Se)8(PEt3) 5(L)](SbF6)2 (5-7), where L represents one of the pyridyl-based ligands. Reacting these cluster complex-based ligands with the fully solvated cluster complex [Re6(μ3-Se) 8(MeCN)6](SbF6)2 (8) produced dendritic arrays of the general formula {Re6(μ3-Se) 8[Re6(μ3-Se)8(PEt 3)5(L)]6}(SbF6)14 (9-11), each featuring six circumjacent [Re6(μ3-Se) 8(PEt3)5]2- units bridged to a [Re6(μ3-Se)8]2-core cluster by the pyridyl-based ligands. Electrochemical studies using a thin-layer electrochemical cell revealed cluster-based redox events in these cluster arrays. For 9 (L = 2), one reversible oxidation event corresponding to the removal of 7 electrons was observed, indicating noninteraction or extremely weak interactions between the clusters. For 10 (L = 3), two poorly resolved oxidation waves were found. For 11 (L = 4), two reversible oxidation events, corresponding respectively to the removal of 1 and 6 electrons, were observed with the 1-electron oxidation event occurring at a potential 150 mV more positive than the 6-electron oxidation. These electrochemical studies suggest intercluster coupling in 11 via through-bond electronic delocalization, which is consistent with electronic spectroscopic studies of this same molecule.

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