2021-03-29Zeitschriftenartikel DOI: 10.18452/24071
Binding of a TlCl Entity by a Tetragold Tetramercaptothiacalixarene Metalloligand via Metallophilic Interactions
p-tert-Butyltetramercaptotetrathiacalixarene was used as a coordination platform to synthesize and investigate gold(I) complexes with varying nuclearity. Aiming at the corresponding tetranuclear complex through salt metathesis it was found capable of binding a neutral, molecular TlCl entity by metallophilic interactions, as shown by structural and theoretical investigations. These Interactions lead to photoluminescence at low temperatures (see figure). The successive auration of p-tert-butyltetramercaptotetrathiacalixarene, H4(MTC), with gold(I) phosphine units was investigated. Through deprotonation with NaOMe, followed by salt metathesis reactions with (PR3)AuCl (R=Me, Ph) complexes with two and three [(PR3)Au]+ moieties could be prepared and isolated, namely [(Ph3PAu)2H2(MTC)] and [(Me3PAu)3H(MTC)]. In [(Me3PAu)3H(MTC)] two gold atoms already come close enough to undergo aurophilic interactions. To introduce a fourth [(PR3)Au]+ entity TlOEt had to be used for the deprotonation, which led to the finding that four gold atoms organised by the (MTC)4− coordination platform are able to bind and stabilize a TlCl entity, yielding [(Me3PAu)4TlCl(MTC)]. As evidenced by structural and theoretical investigations the binding occurs through strong metallophilic interactions, which lead to photoluminescence at low temperatures.
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