by He, Xiaoming, Herranz, Fernando, Cheng, Eddie Chung-Chin, Vilar, Ramon and Yam, Vivian Wing-Wah
Abstract:
A series of bis(dicyclohexylphosphino)methane (dcpm)-containing gold(I) thiolate complexes with urea receptors, 1-3, has been successfully designed and synthesized, and their photophysical and anion-binding properties have been studied. The linker between the thiolate and the urea group, and the electronic environment of the urea moiety, have been found to exert a great influence on the photophysical and anion-binding properties of the complexes. Complex 3 displays an intense long-lived orange-red luminescence at around 620 nm in the solid state and in the glass state at 77 K, which is considerably red shifted from the band seen in a solution of dichloromethane at room temperature, suggesting the presence of AuAu interactions. Upon introducing an electron-withdrawing NO(2) group, complex 1 was found to show high selectivity and sensitivity for F(-) through a drastic color change from yellow to red. The anion-binding constants of the complexes have been determined from electronic absorption and (1)H NMR spectroscopy titration studies and the data were found to fit well to a 1:1 binding model for the interactions between the complexes and the anions. Complexes 1 and 2 show the same anion selectivity trend of F(-) > AcO(-) > H(2)PO(4)(-) > Cl(-) approximately Br(-) approximately I(-), which is consistent with the trend in anion basicity. In addition, complex 1 has been shown to exhibit higher binding affinity for anions compared with those of complexes 2 and 3, probably due to the higher acidity of the urea moiety as a result of the introduction of the NO(2) group.
Reference:
Design, synthesis, photophysics, and anion-binding studies of bis(dicyclohexylphosphino)methane-containing dinuclear gold(I) thiolate complexes with urea receptors. (He, Xiaoming, Herranz, Fernando, Cheng, Eddie Chung-Chin, Vilar, Ramon and Yam, Vivian Wing-Wah), In Chemistry (Weinheim an der Bergstrasse, Germany), volume 16, 2010.
Bibtex Entry:
@article{He:2010ky,
author = {He, Xiaoming and Herranz, Fernando and Cheng, Eddie Chung-Chin and Vilar, Ramon and Yam, Vivian Wing-Wah},
title = {{Design, synthesis, photophysics, and anion-binding studies of bis(dicyclohexylphosphino)methane-containing dinuclear gold(I) thiolate complexes with urea receptors.}},
journal = {Chemistry (Weinheim an der Bergstrasse, Germany)},
year = {2010},
volume = {16},
number = {30},
pages = {9123--9131},
month = aug,
affiliation = {Centre for Carbon-Rich Molecular and Nano-Scale, Metal-Based Materials Research, Department of Chemistry and HKU-CAS Joint Laboratory on New Materials, The University of Hong Kong, Pokfulam Road, Hong Kong, P.R. China.},
doi = {10.1002/chem.201000647},
pmid = {20602366},
language = {English},
rating = {0},
date-added = {2013-11-24T10:31:48GMT},
date-modified = {2020-07-09T13:27:51GMT},
abstract = {A series of bis(dicyclohexylphosphino)methane (dcpm)-containing gold(I) thiolate complexes with urea receptors, 1-3, has been successfully designed and synthesized, and their photophysical and anion-binding properties have been studied. The linker between the thiolate and the urea group, and the electronic environment of the urea moiety, have been found to exert a great influence on the photophysical and anion-binding properties of the complexes. Complex 3 displays an intense long-lived orange-red luminescence at around 620 nm in the solid state and in the glass state at 77 K, which is considerably red shifted from the band seen in a solution of dichloromethane at room temperature, suggesting the presence of AuAu interactions. Upon introducing an electron-withdrawing NO(2) group, complex 1 was found to show high selectivity and sensitivity for F(-) through a drastic color change from yellow to red. The anion-binding constants of the complexes have been determined from electronic absorption and (1)H NMR spectroscopy titration studies and the data were found to fit well to a 1:1 binding model for the interactions between the complexes and the anions. Complexes 1 and 2 show the same anion selectivity trend of F(-) > AcO(-) > H(2)PO(4)(-) > Cl(-) approximately Br(-) approximately I(-), which is consistent with the trend in anion basicity. In addition, complex 1 has been shown to exhibit higher binding affinity for anions compared with those of complexes 2 and 3, probably due to the higher acidity of the urea moiety as a result of the introduction of the NO(2) group.},
url = {http://eutils.ncbi.nlm.nih.gov/entrez/eutils/elink.fcgi?dbfrom=pubmed&id=20602366&retmode=ref&cmd=prlinks},
uri = {url{papers3://publication/doi/10.1002/chem.201000647}}
}