Synthesis and Crystal Structure of [Cd10Se4(SePh)12(PPh3)4] and [Cd16(SePh)32(PPh3)2]

Behrens, Silke; Bettenhausen, Marco; Eichhöfer, Andreas; Fenske, Dieter

doi:10.1002/anie.199727971

Cited by 50 publications

(46 citation statements)

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“…We studied five cluster molecules in four compounds: [Cd 4 (SePh) 6 4 ] (Ph = phenyl, Pr = n-propyl). The compounds were prepared using an organo-metallic synthesis route, utilizing standard Schlenk techniques for inert atmosphere conditions, and were crystallized from solution.…”

Section: Methodsmentioning

confidence: 99%

“…Addition of 0.08 ml (0.36 mmol) of Se(SiMe 3 ) 2 leads to the formation of a pale yellow solution from which [Cd 10 Se 4 (SePh) 12 (PPr 3 ) 4 ] could be crystallized by overlayering with heptane. The structures of the cluster-molecule compounds were determined using single-crystal XRD [6,7]. CdSe cores of cluster molecules are composed of adamantane and/or berylene cages, which are the structural units of bulk CdSe.…”

Section: Methodsmentioning

confidence: 99%

“…The studies of semiconductor cluster molecules, however, have been mostly limited to single compounds, thus restricting the extraction of size dependent features. Recent progress in the synthesis of CdSe cluster molecules has allowed us to perform a comprehensive size dependent spectroscopic study of a homologous series of compounds with 4, 8, 10, 17 and 32 Cd atoms [3,6,7], with the largest cluster molecule in the series already overlapping in size with the smallest CdSe nanocrystals. Particular attention was given to the nature of the emission and here we present the results of continuous wave (CW) and time-resolved (TR) wavelength and temperature dependent measurements of CdSe cluster-molecule fluorescence.…”

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confidence: 99%

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Molecular Limit of a Bulk Semiconductor: Size Dependent Optical Spectroscopy Study of CdSe Cluster Molecules

Soloviev

Eichhöfer²,

Fenske³

et al. 2001

phys. stat. sol. (b)

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Steady state and time-resolved photoluminescence measurements of a homologous series of CdSe cluster molecules were performed over a broad temperature range (T = 5-200 K). The absorption and low temperature PLE onset of the clusters shifts systematically to the blue in smaller clusters, manifesting the quantum confinement effect. The emission in all cluster molecules is observed only at low temperatures and is red-shifted significantly from the absorption onset. It is assigned to optically forbidden transitions involving surface states, as substantiated by the ms range of lifetimes and by the involvement of low frequency vibrations of capping selenophenol ligands in the nonradiative relaxation of excited cluster molecules.1. Introduction Semiconductor clusters, composed of less than 100 atoms and still possessing the bonding type of the bulk semiconductor are interesting molecular models of the solid state [1-3]. Such compounds, usually referred to as cluster molecules, can be synthesized nowadays in preparative amounts and their structure and composition are determined precisely from single-crystal X-ray diffraction measurements (XRD) (Fig. 1a).We have investigated the optical properties of the cluster molecules, to determine if aside from serving as a structural model for the bulk semiconductor, they also display the zero-dimensional limit of its electronic properties.Size dependence of electronic structure and optical properties of larger semiconductor quantum dots revealing quantum confinement effects, have been studied extensively [4,5]. The studies of semiconductor cluster molecules, however, have been mostly limited to single compounds, thus restricting the extraction of size dependent features. Recent progress in the synthesis of CdSe cluster molecules has allowed us to perform a comprehensive size dependent spectroscopic study of a homologous series of compounds with 4, 8, 10, 17 and 32 Cd atoms [3,6,7], with the largest cluster molecule in the series already overlapping in size with the smallest CdSe nanocrystals. Particular attention was given to the nature of the emission and here we present the results of continuous wave (CW) and time-resolved (TR) wavelength and temperature dependent measurements of CdSe cluster-molecule fluorescence.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Molecular Limit of a Bulk Semiconductor: Size Dependent Optical Spectroscopy Study of CdSe Cluster Molecules

Soloviev

Eichhöfer²,

Fenske³

et al. 2001

phys. stat. sol. (b)

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“…[32] The reaction chemistry of the silylated reagents E(SiMe 3 ) 2 and PhESiMe 3 is now a proven entry into 12-16 nanocluster materials, and can be used for the preparation of the heavier chalcogen and group 12 metal congeners including [Cd 10 Se 4 -(SePh) 12 (PPr 3 ) 4 ], [33] [Cd 32 Se 14 (SePh) 36 (PPh 3 ) 4 ], [34] [Hg 10 Te 4 (TePh) 12 (PR 3 ) 4 ], [35] [Hg 10 Se 4 (SePh) 12 4 ]. [36] Furthermore, these low temperature synthetic methods used to prepare the nanoclusters allow a systematic investigation of the change in photophysical properties as a function of group 12 metal or chalcogen.…”

Section: Silver Sulfide Nanoclustersmentioning

confidence: 99%

Metal Chalcogenide Clusters on the Border between Molecules and Materials

2009

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The preparative and materials chemistry of high nuclearity transition metal chalcogenide nanoclusters has been in the focus of our research for many years. These polynuclear metal compounds possess rich photophysical properties and can be understood as intermediates between mononuclear complexes and binary bulk phases. Based on our previous results we discuss herein recent advances in three different areas of cluster research. In the field of copper selenide clusters we present the synthesis of monodisperse, nanostructured α‐Cu2Se via the thermolysis of well‐defined cluster compounds as well as our approaches in the synthesis of functionalized clusters. In case of silver chalcogenides we established a strategy to synthesis cluster compounds containing several hundreds of silver atoms with the nanoclusters arranging in a closely packed crystal lattice. Finally the presented chalcogenide clusters of the group 12 metals (Zn, Cd, Hg) can be taken as model compounds for corresponding nanoparticles as even the smallest of frameworks display a clear structural relationship to the bulk materials.

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“…The Cd atoms Cd1 Ϫ Cd3 have all distorted tetrahedral environments, coordinated by the Te atoms of the µ 2 -TePh Ϫ (Te2, Te3, Te4)-and the µ 3 -Te 2Ϫ (Te1)-as well as the P atoms of the P n Pr 2 Ph (P1)-ligands (the bond angles are as follows: µ 2 TeϪCdϪµ 2 Te 96.04 degrees Ϫ 115.52(2); µ 2 TeϪCdϪTe1 93. 16 [26]. The value for the CdϪP1 bond length of the four outer Cd1 atoms coordinated by the P n Pr 2 Ph ligands is found to be 261.83 (15) pm.…”

Section: Synthesis and Structurementioning

confidence: 99%

Synthesis, Structure, and Optical Properties of New Cadmium Chalcogenide Clusters of the Type [Cd10E4(E'Ph)12(PR3)4], (E, E' = Te, Se, S)

Eichhöfer¹,

Aharoni²,

Banin³

2002

Z. anorg. allg. Chem.

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New cadmium chalcogenide cluster molecules [Cd 10 E 4 (E'Ph) 12 (P n Pr 3 ) 4 ], E ϭ Te, E' ϭ Te (1) and [Cd 10 E 4 (E'Ph) 12 -(P n Pr 2 Ph) 4 ] E ϭ Te, E' ϭ Se (2); E ϭ Te E' ϭ S (3); E ϭ Se, E' ϭ S (4) have been synthesized and structurally characterized by single crystal X-ray structure analysis. The influence of the variation of the chalcogen atom is investigated by structural means and by optical spectroscopy. All cluster-molecules have a broad emission in the blue-visible range at low temperature as indicated by photoluminescence (PL) measurements. A clear classification of the emis-

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Synthesis and Crystal Structure of [Cd₁₀Se₄(SePh)₁₂(PPh₃)₄] and [Cd₁₆(SePh)₃₂(PPh₃)₂]

Cited by 50 publications

References 10 publications

Molecular Limit of a Bulk Semiconductor: Size Dependent Optical Spectroscopy Study of CdSe Cluster Molecules

Molecular Limit of a Bulk Semiconductor: Size Dependent Optical Spectroscopy Study of CdSe Cluster Molecules

Metal Chalcogenide Clusters on the Border between Molecules and Materials

Synthesis, Structure, and Optical Properties of New Cadmium Chalcogenide Clusters of the Type [Cd10E4(E'Ph)12(PR3)4], (E, E' = Te, Se, S)

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