Luminescent heterobimetallic complexes. Electronic structure and spectroscopy of [MPt(dppm)2(C![[triple bond, length half m-dash]](https://www.rsc.org/images/entities/char_e007.gif)
CPh)2]PF6(M = Au or Ag) and crystal structure of [AuPt(dppm)2(CCPh)2]PF6(dppm = Ph2PCH2PPh2)
Abstract
The crystal structure of [AuPt(dppm)2(C![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
CPh)2]PF6·H2O (dppm = Ph2PCH2PPh2) has been determined: triclinic, space group P![[1 with combining macron]](https://www.rsc.org/images/entities/char_0031_0304.gif)
, Z= 2, a= 11.146(4), b= 14.512(2), c= 20.322(3)Å, α= 81.55(1), β= 101.27(2), γ= 109.35(2)°. The complex cation consists of a square-planar P–Pt(CCPh)2–P and a linear P–Au–P moiety and the measured intramolecular Pt–Au separation is 2.910(1)Å. The absorption and emission spectra of the complex and of [AgPt(dppm)2(CCPh)2]PF6 and trans-[Pt(dppm)2(CCPh)2] have been measured. Both dinuclear complexes possess low-energy intense electronic absorption bands {[AuPt(dppm)2(CCPh)2]PF6, λmax= 387 nm, εmax= 1.11 × 104 dm3 mol–1 cm–1; [AgPt(dppm)2(CCPh)2]PF6, λmax= 368, εmax= 1.63 × 104 dm3 mol–1 cm–1} which are red-shifted from that of trans-[Pt(dppm)2(CCPh)2]. In solid form, all three complexes exhibit photoluminescence at room temperature. Extended-Hückel molecular orbital calculations have been performed on the model complexes [AuPt(dmpm)2(CCPh)2]+ and trans-[Pt(dmpm)2(CCPh)2](dmpm = Me2PCH2PMe2).
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![[triple bond, length half m-dash]](https://www.rsc.org/images/entities/h2_char_e007.gif)
CPh)2]PF6(M = Au or Ag) and crystal structure of [AuPt(dppm)2(C