The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2${\rm{Au}_{2}^{+}} {\rm{N}_{2}} $ and Au2+N2O${\rm{Au}_{2}^{+}} {\rm{N}_{2}{\rm{O}}} $
The impact of optical excitation on the binding in complexes of the cationic gold dimer: Au2+N2${\rm{Au}_{2}^{+}} {\rm{N}_{2}} $ and Au2+N2O${\rm{Au}_{2}^{+}} {\rm{N}_{2}{\rm{O}}} $
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DOI：
10.1002/ntls.20220023
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发表时间：
2022-08
期刊：
影响因子：
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通讯作者：
M. Förstel;Nima‐Noah Nahvi;Kai Pollow;T. Studemund;Alice E. Green;A. Fielicke;S. Mackenzie;O. Dopfer
中科院分区：
文献类型：
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作者：
M. Förstel;Nima‐Noah Nahvi;Kai Pollow;T. Studemund;Alice E. Green;A. Fielicke;S. Mackenzie;O. Dopfer
The vibrationally resolved Ã2Σ+← X∼2${\tilde{\rm{X}}}^{2} $Σ+transitions of Au2+N2${\rm{Au}_{2}^{+}} {\rm{N}_{2}} $ and Au2+N2O${\rm{Au}_{2}^{+}} {\rm{N}_{2}{\rm{O}}} $ are reported together with a detailed characterization of important geometric and electronic properties, enabling a deep understanding of the bonding mechanism at the molecular level. Comparison with time‐dependent density functional theory calculations reveals that the ligand stabilizes the Au2+${\mathrm{Au}}_{2}^{+}$ entity in the X∼2${\tilde{\rm{X}}}^{2} $Σ+state by donating electron density into the half‐filled bonding orbital leading to the strengthening of the Au-Au$\text{Au-Au}$, N-N$\text{N-N}$, and N-O$\text{N-O}$ bonds. This effect is reversed in the Ã2Σ+state, where the Au-Au$\text{Au-Au}$ bonding orbital is already filled and the ligand destabilizes the Au-Au$\text{Au-Au}$ bond by donating into the antibonding orbitals of Au2+${\mathrm{Au}}_{2}^{+}$. The spectral detail obtained provides a deep understanding of the interplay of multiple electronic states in gas‐phase metal‐complex cations, opening the door for a systematic approach in the study of excited state reactivity in organometallic chemistry.Key pointsHigh‐resolution spectroscopic characterization of Au2+L${\mathrm{Au}}_{2}^{+}\text{L}$ complexes by photodissociation of mass‐selected ions in the optical range and determination of fundamental molecular constants and ligand binding energiesDetailed insight into geometric and electronic structure of ground and excited state of catalytically relevant gold cluster cationsEffect of ligands on chemical bonding and reactivity of Au2+${\mathrm{Au}}_{2}^{+}$ in ground and excited electronic state
The vibrationally resolved Ã2Σ+← X∼2${\tilde{\rm{X}}}^{2} $Σ+transitions of Au2+N2${\rm{Au}_{2}^{+}} {\rm{N}_{2}} $ and Au2+N2O${\rm{Au}_{2}^{+}} {\rm{N}_{2}{\rm{O}}} $ are reported together with a detailed characterization of important geometric and electronic properties, enabling a deep understanding of the bonding mechanism at the molecular level. Comparison with time‐dependent density functional theory calculations reveals that the ligand stabilizes the Au2+${\mathrm{Au}}_{2}^{+}$ entity in the X∼2${\tilde{\rm{X}}}^{2} $Σ+state by donating electron density into the half‐filled bonding orbital leading to the strengthening of the Au-Au$\text{Au-Au}$, N-N$\text{N-N}$, and N-O$\text{N-O}$ bonds. This effect is reversed in the Ã2Σ+state, where the Au-Au$\text{Au-Au}$ bonding orbital is already filled and the ligand destabilizes the Au-Au$\text{Au-Au}$ bond by donating into the antibonding orbitals of Au2+${\mathrm{Au}}_{2}^{+}$. The spectral detail obtained provides a deep understanding of the interplay of multiple electronic states in gas‐phase metal‐complex cations, opening the door for a systematic approach in the study of excited state reactivity in organometallic chemistry.Key pointsHigh‐resolution spectroscopic characterization of Au2+L${\mathrm{Au}}_{2}^{+}\text{L}$ complexes by photodissociation of mass‐selected ions in the optical range and determination of fundamental molecular constants and ligand binding energiesDetailed insight into geometric and electronic structure of ground and excited state of catalytically relevant gold cluster cationsEffect of ligands on chemical bonding and reactivity of Au2+${\mathrm{Au}}_{2}^{+}$ in ground and excited electronic state