Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

Abstract

OH functionalized triarylphosphines were used to assemble zirconocene-based metalloligands with phosphine donor sites in varying positions. These complexes were subsequently treated with different gold precursors to obtain early-late heterometallic compounds in which the metal atoms exhibit different intermetallic distances. All compounds were fully investigated by spectroscopic techniques, photoluminescence measurements and single crystal X-ray diffraction. Quantum chemical calculations were also performed. Some compounds show bright emission even at room temperature with quantum yields of up to 19 % (excitation at 350 nm). Furthermore, the reactivity of dimethyl zirconocene derivatives towards gold complexes was investigated, revealing simultaneous ligand exchange and transmetallation reactions.

Phosphine-substituted 1,2,3-triazoles as P,C- and P,N-ligands for photoluminescent coinage metal complexes

“…Note that a downfield shift in the range of 30-40 ppm is characteristic upon coordination of arylphosphines to AuCl. 64,65 Complex 6 crystallizes in the trigonal space group P3 1 21 with additional solvent molecules (CH 2 Cl 2 and tetrahydrothiophene, for details refer to ESI, Fig. S1 ‡) in the asymmetric unit (Fig.…”

Bis(6‐methylene‐2,2′‐bipyridine)phenylphosphine—A Flexible Ligand for the Construction of Trinuclear Coinage‐Metal Complexes

“…These compounds exhibit aurophilic contacts and their photophysical properties have been investigated. In other contributions, we reported heterobimetallic compounds of gold and zirconium or iron and gold . Braunstein et al.…”

“…In other contributions,w e reportedh eterobimetallic compounds of gold and zirconium or iron and gold. [24,25] Braunstein et al also preparedr elated carbene/phosphine ligands in whicht he phosphorusa toms are directly attached to the N-heterocyclic carbene (NHC) scaffold, resulting in complexes with very short intermetallic distances. [26] Although the design of these complexes can be rationalized very well, their photophysical properties are not fully understood.…”

(μ-Di-tert-butylsilanediolato)bis[bis(η5-cyclopentadienyl)methylzirconium]

“…Cp 2 Zr(CH 3 )(OR)]. If the comparison is restricted to just the latter structures, the Zr-C bond length range is somewhat narrower from 2.26-2.33 Å with a median of 2.29 Å (Bestgen et al, 2016;Black et al, 2008;Breen & Stephan, 1996;Chapman et al, 2012;Frö mel et al, 2013;Gambarotta et al, 1985;Jian et al, 2018;Koch et al, 2000;Mariott & Chen, 2005;Matchett et al, 1988;Normand et al, 2016;Stuhldreier et al, 2000). There are 15 structures containing siloxide ligands bonded to a zirconocene unit in a pseudo-tetrahedral environment used to compare Zr-O and O-Si distances in 1.…”

“…AQESIZ (Mukherjee et al, 2011); AXIBOA (Boulho et al2016); BESGOW (Bolig & Chen, 2004); BODMIR (Helmstedt et al, 2008); BUHVAD (Xu et al, 2015); BUYSOD10 (Longato et al, 1985); CADRUU (Hunter et al, 1983); COHTEY (Waymouth et al, 1984); COPRII (Ho et al, 1984); DAGKAX and DAGKIF (Gambarotta et al, 1985); DITHAP (Martin et al, 1985); EHEFUT (Neu et al, 2011); EKEVEX, EKEVIB, EKEVOH, EKEVUN, EKEWAU and EKEWEY (Normand et al, 2016); ESISAA (Zuccaccia et al, 2004); GIPYUZ (Matchett et al, 1988); HEMCOR (Askham et al, 1994); HIKHUF and HIKJAN (Gurubasavaraj et al, 2007); HUVLAL (Fujdala et al, 2003); IGUDOD (Hü erlä nder et al, 2002); JITVAK and JITVEO (Mandal et al, 2007); JUGCIZ (Boulho et al, 2015); KEXYER (Erker et al, 1990); KODQAV (Koch et al, 2000); KUPQAP (Mariott & Chen, 2005); LEDBEB (Askham et al, 1993); LEPXAH (Mukherjee et al, 2013); MOJHEZ (Black et al, 2008); NAHYOL (Bai et al, 2005); NAPXUY (Pineda et al, 2005); NIMNOM (Johnson et al, 1997); ODOBIU, ODOBOA and ODOBUG (Frö mel et al, 2013); OKUFUX (Bestgen et al, 2016); OZUCAO (Kelsen et al, 2011); PEDFUA (Singh et al, 2006); QIZCEI ; REDTUQ (Cummings et al, 2006); TIWKUG (Yang, Schulz et al, 2008); TOWMUN (Breen & Stephan, 1996); VIBSOO (Waymouth et al, 1990); WAJLO...…”