Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2

Barbara Ballarin; Luigi Busetto; Maria Cristina Cassani; Cristina Femoni; Anna Maria Ferrari; Ivana Miletto; Giuseppe Caputo

doi:10.1039/c1dt11425e

Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂

Barbara Ballarin, Luigi Busetto, Maria Cristina Cassani, Cristina Femoni, Anna Maria Ferrari, Ivana Miletto, Giuseppe Caputo

Risultato della ricerca: Contributo su rivista › Articolo in rivista › peer review

Abstract

The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3- methylimidazolium nitrate, [NH ₂(CH ₂) ₂imMe)] NO ₃ ([3][NO ₃]) reacted with Ag ₂CO ₃ in dimethyl sulfoxide readily yielding a Ag(i)-(NHC-NH ₂) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(i) complex [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂ ([5][NO ₃] ₂) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO ₃] ₂ have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(i)-carbene compound contains dinuclear (AuL) ₂ cations in which pairs of gold(i) centres are linked by a pair of bridging ligands, with a Au⋯Au aurophilic contact of 3.2332(17) Å that is maintained in solution as documented by the DFT calculations. Complex [5][NO ₃] ₂ is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.

Lingua originale	Inglese
pagine (da-a)	2445-2455
Numero di pagine	11
Rivista	Dalton Transactions
Volume	41
Numero di pubblicazione	8
DOI	https://doi.org/10.1039/c1dt11425e
Stato di pubblicazione	Pubblicato - 28 feb 2012
Pubblicato esternamente	Sì

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10.1039/c1dt11425e

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Ballarin, B., Busetto, L., Cassani, M. C., Femoni, C., Ferrari, A. M., Miletto, I., & Caputo, G. (2012). Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂. Dalton Transactions, 41(8), 2445-2455. https://doi.org/10.1039/c1dt11425e

@article{5bb1aa8f69fa4311a83e13cdbb0eaa1d,

title = "Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2",

abstract = "The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3- methylimidazolium nitrate, [NH 2(CH 2) 2imMe)] NO 3 ([3][NO 3]) reacted with Ag 2CO 3 in dimethyl sulfoxide readily yielding a Ag(i)-(NHC-NH 2) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(i) complex [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2 ([5][NO 3] 2) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO 3] 2 have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(i)-carbene compound contains dinuclear (AuL) 2 cations in which pairs of gold(i) centres are linked by a pair of bridging ligands, with a Au⋯Au aurophilic contact of 3.2332(17) {\AA} that is maintained in solution as documented by the DFT calculations. Complex [5][NO 3] 2 is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.",

author = "Barbara Ballarin and Luigi Busetto and Cassani, {Maria Cristina} and Cristina Femoni and Ferrari, {Anna Maria} and Ivana Miletto and Giuseppe Caputo",

year = "2012",

month = feb,

day = "28",

doi = "10.1039/c1dt11425e",

language = "English",

volume = "41",

pages = "2445--2455",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

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Ballarin, B, Busetto, L, Cassani, MC, Femoni, C, Ferrari, AM, Miletto, I & Caputo, G 2012, 'Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂', Dalton Transactions, vol. 41, n. 8, pagg. 2445-2455. https://doi.org/10.1039/c1dt11425e

Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂. / Ballarin, Barbara; Busetto, Luigi; Cassani, Maria Cristina et al.
In: Dalton Transactions, Vol. 41, N. 8, 28.02.2012, pag. 2445-2455.

Risultato della ricerca: Contributo su rivista › Articolo in rivista › peer review

TY - JOUR

T1 - Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions

T2 - Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2

AU - Ballarin, Barbara

AU - Busetto, Luigi

AU - Cassani, Maria Cristina

AU - Femoni, Cristina

AU - Ferrari, Anna Maria

AU - Miletto, Ivana

AU - Caputo, Giuseppe

PY - 2012/2/28

Y1 - 2012/2/28

N2 - The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3- methylimidazolium nitrate, [NH 2(CH 2) 2imMe)] NO 3 ([3][NO 3]) reacted with Ag 2CO 3 in dimethyl sulfoxide readily yielding a Ag(i)-(NHC-NH 2) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(i) complex [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2 ([5][NO 3] 2) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO 3] 2 have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(i)-carbene compound contains dinuclear (AuL) 2 cations in which pairs of gold(i) centres are linked by a pair of bridging ligands, with a Au⋯Au aurophilic contact of 3.2332(17) Å that is maintained in solution as documented by the DFT calculations. Complex [5][NO 3] 2 is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.

AB - The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3- methylimidazolium nitrate, [NH 2(CH 2) 2imMe)] NO 3 ([3][NO 3]) reacted with Ag 2CO 3 in dimethyl sulfoxide readily yielding a Ag(i)-(NHC-NH 2) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(i) complex [Au 2(NH 2(CH 2) 2imMe) 2][NO 3] 2 ([5][NO 3] 2) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO 3] 2 have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(i)-carbene compound contains dinuclear (AuL) 2 cations in which pairs of gold(i) centres are linked by a pair of bridging ligands, with a Au⋯Au aurophilic contact of 3.2332(17) Å that is maintained in solution as documented by the DFT calculations. Complex [5][NO 3] 2 is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.

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Ballarin B, Busetto L, Cassani MC, Femoni C, Ferrari AM, Miletto I et al. Primary amino-functionalized N-heterocyclic carbene ligands as support for Au(i)⋯Au(i) interactions: Structural, electrochemical, spectroscopic and computational studies of the dinuclear [Au ₂(NH ₂(CH ₂) ₂imMe) ₂][NO ₃] ₂. Dalton Transactions. 2012 feb 28;41(8):2445-2455. doi: 10.1039/c1dt11425e