Redox Control of Light‐Induced Platinum‐Cluster‐to‐Iron Charge Transfer in a Bis(ferrocenylethynyl)‐Substituted Hexanuclear Platinum Derivative

Abstract

Placing equivalent redox-active groups as end-caps in molecular arrays is often used to evaluate whether intramolecular electronic communication occurs through organic [1] or metalcontaining fragments. [2][3][4][5][6][7][8][9] To this end, ferrocenyl (Fc = [(h-C 5 H 5 )Fe(h-C 5 H 4 )]) pendant groups (often as ferrocenylethynyl termini), [3][4][5] are commonly used because of their chemical robustness, synthetic versatility, and reversible redox properties. They have been attached to mono- [2,3,6,10] or dinuclear [4, 7] , (dppm = methylenebis-[(diphenyl)phosphine]) with two terminal (Fc-C C)À groups bridging the opposite sides of a triangular Cu[5b] and [Pt 2 Au(dppm) 2 X(h 1 -C CÀFc) 2 ].[4a] Electron transfer from, to, or across the cluster-containing spacer, triggered by external stimuli, would make these units promising candidates for the preparation of connector elements in nanoscale switchable molecular devices.[11] Indeed, the utilization of carbonyl

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“…The structures retain the main features that we have already observed in the structurally related 1 ‐Y 2 ,16 [{Pt 6 } (CCPh) 2 ],14b [{Pt 6 }(CCFc) 2 ] (Fc={(η 5 ‐C 5 H 5 )Fe(η 5 ‐C 5 H 4 )})14d and [(Pt 6 )(CCC 6 H 3 [CC{Pt 3 }] 2 ) 2 ] ({Pt 3 }={Pt 3 (P t Bu 2 ) 3 (CO) 2 }),14a that are otherwise exceedingly rare for hexanuclear complexes of the whole transition series. All these complexes contain a tetrahedral core of platinum atoms with two opposite edges bridged by a further two (“apical”) platinum centers.…”

Ferrocenylethynyl - a versatile platform for new molecules to novel materials

“…The example below from Albinati et al [80] shows a bis(ferrocenylethynyl) complex (79) where the Fc units are connected via a Pt 6 (μ-PtBu 2 ) 4 (CO) 4 metal cluster (Figure 8, top). No significant electronic communication was observed between the two terminal Fc units as shown by the unsplit redox wave at 0.3 V (Figure 8, bottom).…”