Control of aurophilic interaction: conformations and electronic structures of one-dimensional supramolecular architectures

Imoto, Hiroaki; Nishiyama, Shintaro; Yumura, Takashi; Watase, Seiji; Matsukawa, Kimihiro; Naka, Kensuke

doi:10.1039/c7dt01383c

Cited by 11 publications

(10 citation statements)

References 32 publications

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“…Dimerization of the E ‐form vinyl radical species produces cyclic diarsenic compounds, cis ‐DHDAs ( 32 ). Platinum, palladium, gold, and copper complexes with cis ‐DHDA ligands ( 33 – 37 ) were synthesized (Scheme ) . Notably, the two arsenic atoms are fixed at a short distance (ca.…”

Section: Conjugated Polymersmentioning

confidence: 99%

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The Dawn of Functional Organoarsenic Chemistry

Imoto

Naka

2018

Chemistry A European J

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Organoarsenic chemistry was actively studied until the middle of 20th century. Although various properties of organoarsenic compounds have been computationally predicted, for example, frontier orbital levels, aromaticity, and inversion energies, serious concern to the danger of their synthetic processes has restricted experimental studies. Conventional synthetic routes require volatile and toxic arsenic precursors. Recently, nonvolatile intermediate transformation (NIT) methods have been developed to safely access functional organoarsenic compounds. Important intermediates in the NIT methods are cyclooligoarsines, which are prepared from nonvolatile inorganic precursors. In particular, the new approach has realized experimental studies on conjugated arsenic compounds: arsole derivatives. The elucidation of their intrinsic properties has triggered studies on functional organoarsenic chemistry. As a result, various kinds of arsenic-containing π-conjugated molecules and polymers have been reported for the last few years. In this minireview, progress of this recently invigorated field is overviewed.

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Section: Conjugated Polymersmentioning

confidence: 99%

“…Platinum,p alladium,g old, and copperc omplexes with cis-DHDA ligands (33)(34)(35)(36)(37)w ere synthesized (Scheme 18). [85][86][87][88][89][90][91][92] Notably,t he two arsenic atoms are fixed at as hort distance (ca. 3 ).…”

Section: Poly(vinylenearsine)smentioning

confidence: 99%

The Dawn of Functional Organoarsenic Chemistry

Imoto

Naka

2018

Chemistry A European J

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“…Since bidentate ligand structure is suitable for construction of intra‐ and/or intermolecular aurophilic interactions, some bidentate arsenic ligands have been applied for aurophilic architectures. [ 3a,3e,3f,4c,7 ] Gold(I) halide (AuX, X = Cl, Br, I) complexes with 1,2‐bis(diphenylarsanyl)ethane (dpae) varies luminescent properties depending on crystal polymorphs. [ 3a ] We also previously reported that one‐dimensional aurophilic chains of AuCl complexes are supported by 1,4‐dihydro‐1,4‐diarsinines, and the substituents of the ligands highly affect the electron transition energies via conformational change.…”

Section: Introductionmentioning

confidence: 99%

“…[ 3a ] We also previously reported that one‐dimensional aurophilic chains of AuCl complexes are supported by 1,4‐dihydro‐1,4‐diarsinines, and the substituents of the ligands highly affect the electron transition energies via conformational change. [ 4c,7 ]…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands

et al. 2020

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Recently, we have developed synthetic methods for preparing diarsenic ligands. Herein, dinuclear gold(I) chloride complexes with various kinds of diarsenic ligands [Au 2 Cl 2 (diars)] were synthesized (diars = dpae, dpap, dpab, cis-dpav, transdpav, dpapz, and dpaq). X-ray crystallography revealed that they can form intra-or intermolecular aurophilic interactions depending on the ligand structure except for dpab. Crystal polymorphs of Au 2 Cl 2 (dpae) and Au 2 Cl 2 (dpap) were observed [a

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“…Furthermore, the photoluminescent characters might be modulated as metallophilic interaction changed by the functional guest molecules/ions introduced into the M···M interaction systems. Some groups [ 4 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 ] have made significant progress in this area. For example, Catalano et al introduced BF 4 − and CH 3 OH through anion-cation/anion–π interaction to the hetero-metallic coordinated [AuCu-(PPh 2 py) 3 ](BF 4 ) 2 Au(I)···Cu(I) complex [ 4 ].…”

Section: Introductionmentioning

confidence: 99%

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation

Yang

et al. 2018

Nanomaterials

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MP2 (Second order approximation of Møller–Plesset perturbation theory) and DFT/TD-DFT (Density functional theory/Time-dependent_density_functional_theory) investigations have been performed on metallophilic nanomaterials of host clusters [Au(NHC)2]+⋅⋅⋅[M(CN)2]−⋅⋅⋅[Au(NHC)2]+ (NHC = N-heterocyclic carbene, M = Au, Ag) with high phosphorescence. The phosphorescence quantum yield order of clusters in the experiments was evidenced by their order of μS1/ΔES1−T1 values (μnormalS1: S0 → S1 transition dipole, ∆EnormalS1−normalT1: splitting energy between the lowest-lying singlet S1 and the triplet excited state T1 states). The systematic variation of the guest solvents (S1: CH3OH, S2: CH3CH2OH, S3: H2O) are employed not only to illuminate their effect on the metallophilic interaction and phosphorescence but also as the probes to investigate the recognized capacity of the hosts. The simulations revealed that the metallophilic interactions are mainly electrostatic and the guests can subtly modulate the geometries, especially metallophilic Au⋅⋅⋅M distances of the hosts through mutual hydrogen bond interactions. The phosphorescence spectra of hosts are predicted to be blue-shifted under polar solvent and the excitation from HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) was found to be responsible for the 3MLCT (triplet metal-to-ligand charge transfer) characters in the hosts and host-guest complexes. The results of investigation can be introduced as the clues for the design of promising blue-emitting phosphorescent and functional materials.

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Control of aurophilic interaction: conformations and electronic structures of one-dimensional supramolecular architectures

Cited by 11 publications

References 32 publications

The Dawn of Functional Organoarsenic Chemistry

The Dawn of Functional Organoarsenic Chemistry

Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands

Phosphorescent Modulation of Metallophilic Clusters and Recognition of Solvents through a Flexible Host-Guest Assembly: A Theoretical Investigation

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