[AuHg(o-C6H4PPh2)2I]: A Dinuclear Heterometallic  Blue Emitter

López‐de‐Luzuriaga, José M.; Monge, Miguel; Olmos, M. Elena; Pascual, David

doi:10.3390/inorganics3010027

Cited by 9 publications

(9 citation statements)

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“…In the case of 1 ·2C 2 H 4 Cl 2 , the Au I –Hg II distance of 2.9194(7) Å is one of the shortest described until date, being longer only than that of 2.866(2) Å recently described for [6-(Ph 2 P)-5-Ace] 2 Hg·AuCl . The rest of the Au I –Hg II lengths reported range from 2.934(1) to 3.361(1) Å in complexes containing bridging ligands between the metal atoms − ,,,,− and from 3.1860(2) to 3.4983(3) Å in the case of unsupported intermetallic contacts. , …”

Section: Resultsmentioning

confidence: 82%

“…In addition, in the MS-ESI spectrum, besides the peak due to the bromide anion ( m / z = 80.91), the signal that corresponds to the cation [CuHg( o -C 6 H 4 PPh 2 ) 2 ] + also appears at m / z = 787.07. Finally, the molar conductivity of [CuHg( o -C 6 H 4 PPh 2 ) 2 Br] ( 4 ) in CH 2 Cl 2 solution indicates that, as in the case of complexes [AuHg( o -C 6 H 4 PPh 2 ) 2 I] and 3 , the anion, instead of dissociating in solution, is bonded to a metal center.…”

Section: Resultsmentioning

confidence: 97%

“…Nevertheless, the number of examples described in the literature is very limited, especially with 11-group elements. Thus, there are a few examples of complexes displaying interactions between mercury and gold(I) or gold(III), such as, for instance, [HgAuCl 2 (μ-2-C 6 H 4 PPh 2 ) 2 ], [HgAu(CH 2 P(S)Ph 2 ) 2 ][PF 6 ], {[Au(μ-C 3 ,N 3 -bzim)] 3 } 2 [Hg( o -C 6 F 4 )] 3 , [Hg(C 6 F 5 ) 2 {Au(C 6 F 5 )(PMe 3 )} 2 ], , [Hg{Au(C 6 F 5 )(μ-2-C 6 H 4 PPh 2 )} 2 ], and [Hg{Au(C 6 F 5 )Cl 2 (μ-2-C 6 H 4 PPh 2 )} 2 ], [6-(Ph 2 P)-5-Ace] 2 Hg·AuCl, and {[6-(Ph 2 P)-5-Ace] 2 Hg · Au}[O 3 SCF 3 ] ([6-(Ph 2 P)-5-Ace] = 6-diphenylphosphinoacenaphth-5-yl); or a very few examples of the interaction between mercury and silver or copper, as the hexanuclear complex [Ag 2 Hg(mes) 2 (SO 3 CF 3 ) 2 ] 2 (mes = mesityl) or [6-(Ph 2 P)-5-Ace] 2 Hg·AgCl and [6-(Ph 2 P)-5-Ace] 2 Hg·Ag(O 3 SCF 3 ), which are the only examples that present short Ag(I)···Hg(II) interactions, or [Hg{Fe[Si(OMe) 3 ](CO) 3 (μ-dppm)} 2 Cu]PF 6 (dppm = PPh 2 CH 2 PPh 2 ) and [Cu{Hg(Ph–CHN–CH 2 –CH 2 –NCH-Ph)} 2 }], which are the only two examples reported with Hg(II)···Cu(I) contacts. Interestingly, a recent study by Hupf et al also reports about the low number of complexes bearing Hg(II)···M (M = Hg(II), Au(I), and Ag(I)) interactions.…”

Section: Introductionmentioning

confidence: 99%

“…Its analytical and spectroscopic data agree with the proposed stoichiometry. For instance, its 31 33 and 3, the anion, instead of dissociating in solution, is bonded to a metal center.…”

Section: ■ Introductionmentioning

confidence: 99%

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Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

et al. 2015

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Heteronuclear complexes PPh 2 ) 2 ]X (M = Au, X = ClO 4 (1); M = Ag, X = BF 4 (2); M = Ag, X = CF 3 CO 2 (3); M = Cu, X = Br (4)) were prepared by the treatment of [Hg(o-C 6 H 4 PPh 2 ) 2 ] with one equivalent of the corresponding coinage metal salt. Their crystal structures, determined by X-ray diffraction methods, display Hg II ··· M I (M = Au, Ag, Cu) contacts. Ab initio calculations show similar interaction energies (ca. 40 kJ·mol −1 ) and similar origin (dispersive forces) for these Hg···Au, Hg···Ag, and Hg···Cu interactions. ■ INTRODUCTIONNowadays, relativistic effects have shown an enormous importance to understand the chemical and physical properties of the heaviest 6s transition and post-transition metallic elements. From them, the element whose physical and chemical properties are more influenced by these effects is gold. 1−3 Probably, the most important structural consequence of the relativistic effects in gold is the high tendency to form closedshell interactions between gold(I) centers. This type of interactions were first described by Schmidbaur in 1988, 4 and subsequently, theoretical studies quantified the strength of these interactions up to −57 kJ·mol −1 , a surprisingly strong value, from which a non-negligible 26% is due to relativistic effects. 5 These strong interactions made possible a high number of structural motifs, 2,6 and in addition, parallel to this, the complexes often displayed interesting optical properties. 7−9 In the case of other heavy atoms, although the contraction of the radius due to the relativistic effects is not so important as in gold, these effects also play an important role in their properties. 10−14 Also, more recent studies on the relativity of the lead−acid or mercury batteries attribute a non-negligible 80% or 30%, respectively, of the electromotoric forces to the relativistic effects. 15,16 On the other hand, a logical next step in these studies was the study of the relativity in heteronuclear systems in which different metals maintain noncovalent interactions between them and in which at least one of them is a heavy 6s element, preferably gold. The synthesis of these complexes has been possible, making use of different synthetic strategies (acid− base, transmetalation, etc.). In such a way, a good number of heterometallic gold(I) compounds were described in which gold maintains an interaction with different closed shell ions such as Ag I , Bi III , Tl I , or Cu I , among others. 17−23 Thus, for instance, with the, in principle, more favorable coinage congeners, the energy of Au I ···Ag I and Au I ···Cu I contacts has been theoretically estimated to be 22 and 17 kJ·mol −1 , respectively. Besides, both of them have in common a high electronic correlation contribution probably induced by the relativistic effects present in gold. 24 In addition, the importance of the dispersive-type forces is evident in the intermetallic acid−base interactions that take place between gold(I) and thallium(I) or bismuth(III), which are, in both cases, around 20% of the total inter...

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

“…Its analytical and spectroscopic data agree with the proposed stoichiometry. For instance, its 31 33 and 3, the anion, instead of dissociating in solution, is bonded to a metal center.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

et al. 2015

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“…The solicited manuscript by José M. López-de-Luzuriaga and his collaborators describes direct applications in blue emitters [18]. Homonuclear and heteronuclear complexes which exhibit metallophilicity are widely studied as vapochromic sensors for volatile organic compounds (VOCs).…”

Section: The Present Issuementioning

confidence: 99%

Frontiers in Gold Chemistry

Mohamed

2015

Inorganics

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Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of gold.

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Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions

Olaru

Kögel

Aoki

et al. 2019

Chemistry A European J

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The reaction of 2,6‐F2C6H3SiMe3 with Ph2PLi provided 2,6‐(Ph2P)2C6H3SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6‐(Ph2P)2C6H3]− (PCP)−. The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6‐(Ph2PAuCl)2C6H3SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3SiF and yielded the neutral tetranuclear complex linear‐[Au4Cl2(PCP)2] (3) comprising a string‐like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF4 (ArF=3,5‐(CF3)2C6H3) in the presence of tht, the formation of the dicationic tetranuclear complex linear‐[Au4(PCP)2(tht)2](BArF4)2 (4) was observed, in which the string‐like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo‐[Au4(PCP)2(tht)2](BArF4) (5), which comprises a rhomboidal motif of four Au atoms. In 3–5, the Au atoms are associated by a number of significant aurophilic interactions. The atom‐economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2Cl3(PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6‐(Ph2PAuCl)2C6H3]− (AuCAu)− containing a central carbanionic binding site and two “gold‐arms” contributing pincer‐type chelation trough metallophilic interactions. Compounds 1–6 were characterized experimentally by multinuclear NMR spectroscopy and X‐ray crystallography and computationally using a set of real‐space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI‐D) as well as the Non‐Covalent Interaction (NCI) Index.

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[AuHg(o-C6H4PPh2)2I]: A Dinuclear Heterometallic Blue Emitter

Cited by 9 publications

References 43 publications

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Frontiers in Gold Chemistry

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions

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[AuHg(o-C6H4PPh2)2I]: A Dinuclear Heterometallic Blue Emitter

Cited by 9 publications

References 43 publications

Study of the Nature of Closed-Shell HgII···MI (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell HgII···MI (M = Cu, Ag, Au) Interactions

Frontiers in Gold Chemistry

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d10–d10 Interactions

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Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Study of the Nature of Closed-Shell Hg^II···M^I (M = Cu, Ag, Au) Interactions

Tri‐ and Tetranuclear Metal‐String Complexes with Metallophilic d¹⁰–d¹⁰ Interactions