CYCLIC TRINUCLEAR GOLD(I) COMPOUNDS: SYNTHESIS, STRUCTURES AND SUPRAMOLECULAR ACID-BASE Π-Stacks

Burini, Alfredo; Mohamed, Ahmed A.; Fackler, John P.

doi:10.1080/02603590390464225

Cited by 109 publications

(96 citation statements)

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“…Although the former compound was studied for decades (22,23), the crystal structure of [Au(μ-C 2 ,N 3 -BzIm)] 3 was only recently published; it exhibited a semiprismatic conformation with one long (3.558 Å) and two short (3.346 Å) intertrimer distances to manifest its strong aurophilic interactions (11). The copper precursor for 1-4 has been studied by Dias et al (24) 3 ] that nonetheless represented weaker aurophilic interaction vs. its hexagonal polymorph (27).…”

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confidence: 99%

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Galassi

Ghimire

Otten

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Outer-shell s 0 /p 0 orbital mixing with d 10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au 4 Cu 2 {[Au 4 (μ-C 2 ,N 3 -EtIm) 4 Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4a)}, Au 2 Cu {[Au 2 (μ-C 2 ,N 3 -BzIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (1) and [Au 2 (μ-C 2 , N 3 -MeIm) 2 Cu(μ-3,5-(CF 3 ) 2 Pz)], (3a)}, AuCu 2 {[Au(μ-C 2 ,N 3 -MeIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (3b) and [Au(μ-C 2 ,N 3 -EtIm)Cu 2 (μ-3,5-(CF 3 ) 2 Pz) 2 ], (4b)} and stacked Au 3 /Cu 3 {[Au(μ-C 2 ,N 3 -BzIm)] 3 [Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 , (2)} form upon reacting Au 3 {[Au(μ-C 2 ,N 3 -(N-R)Im)] 3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu 3 {[Cu(μ-3,5-(CF 3 ) 2 Pz)] 3 (3,5-(CF 3 ) 2 Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d 10 -d 10 polar-covalent bond with ligandunassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d 10 centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm −1 , assignable to v Cu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (Φ PL = 0.90-0.97 vs. 0-0.83 for Au 3 and Cu 3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications. Here, we show that outer 4s/p (Cu I ) and 6s/p (Au I ) orbitals can admix with the respective valence 3d and 5d orbitals to sensitize a bona fide polar-covalent metal-metal bond between two d 10 centers manifest by two rather short, 2.8750(8) Å, Cu(I)-Au(I) bonds without any ligand-bite-size assistance. The reduced symmetry in this family of complexes is also shown to impart higher extinction coefficients and phosphorescence quantum yields than those attained by the parent homometallic precursor complexes.Heterometallic complexes are remarkable molecules owing to their unique catalytic and optoelectronic properties (2, 3). Heterometallic species involving coinage metals have received immense attention owing to their fascinating structural a...

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confidence: 99%

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Galassi

Ghimire

Otten

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…[11,12] In general, these adducts form structures in which the trinuclear metal complex [M 3 oarene acceptors such as hexafluorobenzene and octafluoronaphthalene. [13] Similar to the gold(I) adducts described above, the trinuclear pyrazolate complexes of Cu I , Ag…”

Section: H V Rasika Dias* and Chammi S Palehepitiya Gamagementioning

confidence: 87%

Arene‐Sandwiched Silver(I) Pyrazolates

Dias

Gamage

2007

Angew Chem Int Ed

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Vaughan and coworkers 17 synthesized the first gold(I) cyclic trinuclear complex (CTC) [Au(I) 3 (μ-1,2-piridyl) 3 ], which presents a planar 9-membered ring structure, exhibiting roughly a D 3h symmetry.…”

Section: Introductionmentioning

confidence: 99%

Cyclic trinuclear copper(i), silver(i), and gold(i) complexes: a theoretical insight

et al. 2015

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The metal-ligand, M-L, bonding situation in cyclic trinuclear complexes, CTCs, of copper(I), silver(I), and gold(I) was investigated in terms of the energy decomposition analysis (EDA-NOCV) and natural bond orbitals (NBOs). The anisotropy of the induced current density (ACID) and magnetic response were employed to evaluate the effect of electronic conjugation and metal-metal interactions in CTCs. The EDA-NOCV results show that the M-L bonding is stronger in gold(I) than in copper(I) or silver(I) complexes. Au(+)-L bonds present an elevated covalent character when compared with Cu(+)-L and Ag(+)-L bonds. The NBO analysis confirms the elevated covalent character observed for Au(+)-L bonds, indicating that the ligand-metal donation, L → M, and the metal-ligand back-donation, M → L, are more stabilizing in gold(I) than in copper(I) or silver(I) complexes. Both ACID and the magnetic response calculations reveal that there are cyclic conjugations in the ligands and a strong diatropic ring current indicating the presence of aromaticity. However, there is no through-bond M-L conjugation between the ligands and the metallic centers, as indicated by the absence of a continuous anisotropy boundary surface involving M-L bonds.

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CYCLIC TRINUCLEAR GOLD(I) COMPOUNDS: SYNTHESIS, STRUCTURES AND SUPRAMOLECULAR ACID-BASE Π-Stacks

Cited by 109 publications

References 1 publication

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Arene‐Sandwiched Silver(I) Pyrazolates

Cyclic trinuclear copper(i), silver(i), and gold(i) complexes: a theoretical insight

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CYCLIC TRINUCLEAR GOLD(I) COMPOUNDS: SYNTHESIS, STRUCTURES AND SUPRAMOLECULAR ACID-BASE Π-Stacks

Cited by 109 publications

References 1 publication

Cupriphication of gold to sensitize d 10 –d 10 metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d 10 –d 10 metal–metal bonds and near-unity phosphorescence quantum yields

Arene‐Sandwiched Silver(I) Pyrazolates

Cyclic trinuclear copper(i), silver(i), and gold(i) complexes: a theoretical insight

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Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields

Cupriphication of gold to sensitize d ¹⁰ –d ¹⁰ metal–metal bonds and near-unity phosphorescence quantum yields