Synthese und Struktur der Nanocluster [Hg₃₂Se₁₄(SePh)₃₆], [Cd₃₂Se₁₄(SePh)₃₆(PPh₃)₄], [Et₂P(Ph)C₄H₈OSiMe₃]₅[Cd₁₈I₁₇(PSiMe₃)₁₂] und [Et₃NC₄H₈OSiMe₃]₅[Cd₁₈I₁₇(PSiMe₃)₁₂]

Abstract

Rote Kristalle von 1 wurden durch Umsetzung von HgII‐Salzen mit PhSeSiMe3 in organischen Lösungsmitteln erhalten. Je nach eingesetzter HgII‐Quelle und Bedingungen kristallisiert 1 in der kubischen Raumgruppe P23 oder in der trigonalen P32. Der Durchmesser des kubisch kristallisierenden Clusters beträgt ca. 2400 pm (Bild des Hg32Se50‐Clustergerüstes siehe rechts). Weiterhin wurden die anderen Titelverbindungen hergestellt und in Form farbloser Kristalle isoliert.magnified image

Nanopartikuläre Funktionsmaterialien

“…So zeigen Metallchalkogenidcluster ebenfalls Lumineszenz, wobei die Wellenlänge der Emission jedoch nicht über den Durchmesser des Clusterkerns, sondern durch die jeweilige Ligandenhülle bestimmt wird. [289] 34 ] zeigen. [290] Allerdings tritt eine gewisse Reifung der ursprünglich 1-3 nm großen Clusterkerne ein, sodass nach der Thermolyse monodisperse a-Cu 2 Se-NPs mit einem Durchmesser von 15 4À -Clustern überraschend Supraleitung mit einer Sprungtemperatur von etwa 7 K beobachtet werden.…”

Thermal Properties of [M10Se4(SePh)12(PR3)4] (M = Zn, Cd, Hg)Cluster Molecules – Synthesis and Structure of[Cd32Se14(SePh)36(L)4]; L = OPPh3, OC4H8

“…[16] The 'Hg 34 Te 16 Se 36 ' cluster core is completely formed by 20 adamantane cages and can be considered as an idealized fragment of the cubic sphalerite lattice, but with a mercury vacancy in the centre. Although the cluster cores of 5 and 6 are also formed by adamantane cages, except the barrelane cages at the four [7] (below) with the differing part highlighted in black. 4 ], there is a mercury vacancy on what should be a formal atomposition, the centre of 5 and 6 lies within the centre of theinner adamantane cage and thus on a tetrahedral hole.…”

“…This cluster framework is built up of 13-fused CdSe adamantane cages with four barrelene CdSe cages at each of the corners. Adamantane cages are the building blocks of the cubic zincblende structure of CdSe, while barrelene [5] [Cd 32 S 14 (SCH 2 CH(OH)CH 3 ) 36 (H 2 O) 4 ] [6] and [Hg 32 Se 14 (SePh) 36 ], [7] but slightly different to the closely related cluster [Cd 32 Se 14 (SePh) 36 (PPh 3 ) 4 ] [7] and distinctly dif-ferent to a recently characterized cluster of composition [Hg 34 Te 16 (SePh) 36 (PPhnPr 2 ) 4 ]. [16] The difference in structure in relative to that found in 5 and 6 ( Figure 6) lies with the build up of the CdSe framework.…”

“…Up to now the largest CdSe cluster compound that has been synthesized and characterized by single-crystal X-ray analysis contains thirty two cadmium atoms with the common formula [Cd 32 E 14 (EЈR) 36 (L) 4 ] (E = Se, S; EЈ = Se, S; L = neutral ligand). [5][6][7] Weller and coworkers found evidence from extended X-ray absorption fine structure (EXAFS) and UV/ Vis [8] that the next stable cluster molecule in size is [Cd 54 Se 32 (SeR) 52 ] 8-, but no crystal structure from singlecrystal XRD has been reported to date. It is therefore, a major goal to find new synthetic routes to enlarge the number of species in this class of materials.…”

Characterization and Catalytic Activity of New Metal‐organic Frameworks Resulted from Self‐assembly of Ph3SnCl, K[Cu(CN)2] and Nitrogen Donor Ligands

“…The first step, in the temperature range of 140-290 ℃, involves the loss of triphenyltin cyanide that seems to be good volatile leaving group similar to trimethylsilyl halogenide groups, which are used as leaving groups in cluster synthesis in solutions. [37][38][39] The second step, in the temperature range 300-380 ℃, is the loss of the aromatic ligand. The behavior of this class of compounds is contrary to the behavior of the early reported copper(I) cyanide of the type [(Ph 3 Sn) 3 2 O, where x＝0-2, y＝0 or 2 and L is bipodal ligand; 27 wherein the bipodal ligands were found to be lost before triphenyltin cyanide.…”