Growth format, electronic architecture, magnetic, and optical properties of aromatic cyclo‐Cu3Au3 homotops

Tsipis, Constantinos A.; Depastas, Ioannis G.; Kefalidis, Christos E.

doi:10.1002/jcc.20715

Cited by 7 publications

(7 citation statements)

References 66 publications

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“…For binary alloy trimers triangular structures are the most stable forms with angles of 63.7° (∠AuAgAu), 57.4° (∠AgAuAg), 53.8° (∠CuAuCu), and 70.3° (∠AuCuAu) for Au 2 Ag, AuAg 2 , AuCu 2 , and Au 2 Cu clusters, respectively, and these results confirm previous studies. , …”

Section: Resultssupporting

confidence: 90%

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

2010

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The interactions of pure (Au(k), Ag(k), and Cu(k); k = 1-3) and binary alloy (Au(n)Ag(m) and Au(n)Cu(m); m + n = k Cu > Ag. In binary alloy clusters, alloying Au(k) with copper and silver decreases the attraction of Au toward H(2)S, while alloying Ag(k) and Cu(k) by gold increases the attraction of Ag and Cu toward H(2)S, significantly. Dissociation energy values for isolated metal clusters specify the more favorable formation of binary alloy clusters (Au(n)Ag(m) and Au(n)Cu(m)) over pure ones. The nature of M-S bonds (M = Au, Ag, and Cu) is also interpreted by means of the quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). According to these theories, the M-S bonds are found to be partially electrostatic and partially covalent. EDA results identify that these bonds have less than 35% covalent character and more than 65% electrostatic, and the covalent character increases in different metals in the order Au > Cu > Ag.

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Section: Resultssupporting

confidence: 90%

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

2010

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“…In a recent work, we showed that NICS profiles can be used to characterize aromaticity in inorganic species and to classify inorganic clusters into aromatic, nonaromatic, and antiaromatic categories 23. More recently, Stanger41 has checked the performance of this method for organic species and Tsipis et al42 have applied it to study cyclo‐ Cu 3 Au 3 homotops. In this work, we use NICS profiles to classify the studied compounds and to analyze the [X 2 M 3 ] regions where the changes in aromaticity as a function of the distance from the alkali metal to the center of the Mg 3 ring are more important.…”

Section: Computational Detailsmentioning

confidence: 99%

Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts

et al. 2009

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In this work, we analyze the geometry and electronic structure of the [X(n)M(3)](n-2) species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo-[M(3)](2-) unit. The cyclo-[M(3)](2-) ring is held together through a three-center two-electron bond of sigma-character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo-[M(3)](2-) ring and leads to a change from sigma-aromaticity in the bound state of the cyclo-[M(3)](2-) to pi-aromaticity in the XM(3) (-) and X(2)M(3) metallic clusters. Our results also show that the aromaticity of the cyclo-[M(3)](2-) unit in the X(2)M(3) metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M(3) ring. The Na(2)Mg(3), Li(2)Mg(3), and X(2)Ca(3) clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M(3) ring, whereas X(2)Be(3) and K(2)Mg(3) keep its aromaticity relatively constant along this process.

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“…58 Recently, the NICS criterion has been successfully used to characterize aromaticity in inorganic species and to classify inorganic clusters into aromatic, nonaromatic, and antiaromatic categories. 59 Moreover, the performance of this method for organic species has been demonstrated 60 and Tsipis et al 61 have applied it to study cyclo-Cu 3 Au 3 bimetallic clusters. In addition, NICS profiles have been recently used to classify trigonal alkaline earth metal clusters and their alkali metal salts and to analyze the [X 2 M 3 ] regions where the changes in aromaticity are more important.…”

Section: Theoretical Dft Studymentioning

confidence: 99%

Relevant and unprecedented C–H/σ supramolecular interactions involving σ-aromatic M₂X₂cores

et al. 2014

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A novel type of C-H/σ supramolecular interaction involving σ-aromatic M2X2 (M = Cu, Hg; X = Cl, Br, I, S) cores is reported for the first time. Three new polymeric coordination copper complexes, {[Cu(μ-Cl)(Cl)(μ-L)]2}n (1), {[Cu(μ-I)(μ-L)]2}n (2) and [Cu(Br)2(μ-L)(CH3CN)2]2 (3), have been synthesized with the organic ligand α,ω-bis(benzotriazoloxy)propane system (L) and halides as counterions. A very interesting C-H/σ supramolecular interaction has been observed in the solid state structure of compound 2, similar to a C-Hπ interaction, which has been confirmed by Bader's "atoms-in-molecules" AIM analysis. The Nucleus Independent Chemical Shift (NICs) method was used to evaluate the aromatic character of the different cores in this study. The influence of the nature of the metal ions, bridging atoms, oxidation states, and coordination environments around the metal centers on the strength of the aromaticity of the M2X2 cores was theoretically analyzed and explained. The binding ability of the 1-alkoxy-1,2,3-benzotriazole ring to establish π-π and C-H/π interactions and how its coordination to Cu(I) and Cu(II) ions affects the strength of the aforementioned interactions have been discussed. The electron deficient triazole ring and its π-acidity increases upon coordination of the Cu ion, leading to the formation of a lone pair (lp)-π interaction involving the five-membered ring of the ligand, which has also been analyzed. We have also analyzed the C-H/σ interactions of previously reported X-ray crystal structures of different coordination polymers based on a binuclear copper(I) complex and 2,3-dimethylpyrazine, dithioethers, and benzotriazol-1-yl-based pyridyl units as ligands using I- as a counter-ion. Complex 1 shows antiferromagnetic behavior with a magnetic coupling constant of J = -7.9 cm(-1). Moreover, photoluminescence and TGA studies of the complexes were also carried out.

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Growth format, electronic architecture, magnetic, and optical properties of aromatic cyclo‐Cu₃Au₃ homotops

Cited by 7 publications

References 66 publications

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts

Relevant and unprecedented C–H/σ supramolecular interactions involving σ-aromatic M₂X₂cores

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Growth format, electronic architecture, magnetic, and optical properties of aromatic cyclo‐Cu3Au3 homotops

Cited by 7 publications

References 66 publications

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

Nature and Strength of M−S Bonds (M = Au, Ag, and Cu) in Binary Alloy Gold Clusters

Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts

Relevant and unprecedented C–H/σ supramolecular interactions involving σ-aromatic M2X2cores

Contact Info

Product

Resources

About

Growth format, electronic architecture, magnetic, and optical properties of aromatic cyclo‐Cu₃Au₃ homotops

Relevant and unprecedented C–H/σ supramolecular interactions involving σ-aromatic M₂X₂cores