Synthesis, characterization, photophysics, and anion binding properties of gold(i) acetylide complexes with amide groups

Abstract

A series of mononuclear gold(I) acetylide complexes with amide groups, Ph 3 PAuCRCC 6 H 4 NHC(O)C 6 H 4 -R-4 (R = NO 2 (3a), CF 3 (3b), H (3c), and OMe (3d)), has been synthesized and characterized. The crystal structure of Ph 3 PAuCRCC 6 H 4 NHC(O)C 6 H 4 -NO 2 -4 (3a) was determined by X-ray diffraction. The photophysical properties of gold(I) acetylide complexes 3b-3d were studied and the complexes show luminescence both in the solid state and in degassed THF solutions at 298 K. The anion-binding abilities of complexes 3a-3d in CDCl 3 were also studied through 1 H NMR titration experiments. They show similar anion selectivity trends and 3a exhibits the highest binding affinity towards anions due to the strongest electron-withdrawing ability of the NO 2 group. In DMSO, 3a shows a dramatic color change upon addition of F À , which provides access to naked eye detection of F À .

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

“…790 A number of Au(I) acetylides bearing tethering ligand such as an amide have been reported for the sensing of anions (especially F − ). 528,530 With the use of these complexes, naked eye detection of analytes is possible. Complex 443 (Chart 71) showed a promotive and differentiating effect on the binding constant (log K) in THF compared to DMSO.…”

“…d 10 Metal-alkynyls constitute an interesting class of molecules with diverse applications in the area of catalysis, sensing, electronics, and drug discovery. − d 10 Metals (Cu, Ag, and Au) feature metallophilicity and flexible binding modes, which are not so common among metals of other groups. Several homo- and heterometallic cationic and alkynyl clusters based on group 11 metals have been reported in the past and are still being explored, − but literature on σ-acetylide complexes containing Cu­(I) and Ag­(I) is limited. , This is, in part, due to the instability of the compounds, which hampers the handling, characterization, and application of the materials in the devices.…”

Assembly of BF4−, PF6−, ClO4− and F− with trinuclear copper(i) acetylide complexes bearing amide groups: structural diversity, photophysics and anion binding properties

“…Acetylide ligands L1-L4 were obtained by using similar methods reported in our previous paper. 59 The reactions of dinuclear complexes [Cu 2 (m-dppm) 2 (CH 3 CN) 4 ](X) 2 (X ¼ BF The IR spectra of the trinuclear copper(I) acetylide complexes 1$BF 4 -4$BF 4 , 1$PF 6 , and 1$ClO 4 contain three bands at ca. 3368-3399, 2170-2270 and ca.…”

“…Transition metal complexes with amide N-H hydrogen bond donor as anion-binding sites are our group's long-term interest. 59 Complexes with different R substituents exhibit varied affinities toward anions compared with their analogues, 59 we therefore envisaged that the acidity of amide groups could inuence their coordination patterns and selective crystallization to anions. In this work, we have synthesized and characterized a series of trinuclear copper(I) acetylide complexes, [Cu 3 (m-dppm) 3 (m 3 -h 1…”

“…Dihedral angle between plane O(1)-C(9)-N(1) and plane O(4)-C(24)-N(3) is 27.48 , suggesting two amide moieties point to different directions. The C]O distances for 1 are 1.202(6) and 1.214(7) Å, which resemble typical carbonyl groups in analogues amide receptors 50,59. Structures of anion complexes (1) Complexes with NO 2 group.…”