The paper focuses
on exploiting aurophilic bonding to produce white
light emitting materials. Inorganic Click (iClick) is employed to
link two or four Au(I) metal ions through a triazolate bridge. Depending
on the choice of phosphine ligand (PEt3 or PPh3), dinuclear Au2-FO or tetranuclear Au4-FO
complexes can be controllably synthesized (FO = 2-(9,9-dioctylfluoreneyl-)).
The iClick products Au2-FO and Au4-FO are characterized
by combustion analysis and multinuclear NMR, TOCSY 1D, 1H–13C gHMBC, and 1H–13C gHSQC. In addition, the photophysical properties of Au2-FO and Au4-FO were examined in THF solution. Transient
absorption spectroscopy was employed to elucidate the excited state
features of the gold compounds. Solution processed OLEDs were fabricated
and characterized, which gave white light electroluminescence with
CIE coordinates (0.34, 0.36), as seen referenced to CIE standard illuminant
D65 (0.31, 0.32). TDDFT computational analysis of Au2-FO
and Au4-FO reveals the origin of light emission. In the
case of Au4-FO, direct excitation leads to increased aurophilic
bonding in the excited state, and as a result the emission profile
is broadened to cover a larger region of the visible spectrum, thus
giving white light emission. Designing molecules that can access or
increase aurophilic bonding in the excited state provides another
tool for fine-tuning the emission profiles of gold complexes.
This report describes the iClick synthesis and characterization of a metallopolymer that contains contiguous conjugation across the polymer repeat units and Pt(II) ions. A bifunctional A−Pt-B monomer, where A = azido and B = acetylide, was synthesized. Using a Cu(I) source, the A−Pt-B monomer was polymerized via azide−alkyne cycloaddition to give a low-molecular-weight metallopolymer. Photophysical interrogation and computation modeling of the metallopolymer indicates limited conjugation and the spectra are dominated by ligand-centered transitions and emission.
a b s t r a c tThe iClick (inorganic click) reactions between gold-acetylides and group 9 transition metal-azide complexes are presented. Complexes [Rh(CO)(PPh 3 ) 2 ][PPh 3 Au](3 (5). Complexes 3, 4, and 6 have been characterized by a combination of NMR spectroscopies, crystallography and combustion analysis.Published by Elsevier Ltd.
The first example of an in-chain metallo-poly(triazolate) synthesized by CuAAC is reported. Azido-platinum-acetylide (A-M-B) monomers are catalytically polymerized with copper(i) acetate to yield 1,2,3-triazolate linked Pt(ii) units. The metallopolymers are characterized by multinuclear NMR, IR, UV/Vis, GPC, and MS.
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