Directional Energy Transfer in Mixed-Metallic Copper(I)–Silver(I) Coordination Polymers with Strong Luminescence

Abstract

Strongly luminescent mixed-metallic copper(I)-silver(I) coordination polymers with various Cu/Ag ratio were prepared by utilizing the isomorphous relationship of the luminescent parent homometallic coordination polymers (Φ(em) = 0.65 and 0.72 for the solid Cu and Ag polymers, respectively, at room temperature). The mixed-metallic polymer with the mole fraction of copper even as low as 0.005 exhibits a strong emission (Φ(em) = 0.75) from only the copper sites as the result of the efficient energy migration from the silver to the copper sites. The migration rates between the two sites were evaluated from the dependence of emission decays upon the mole fraction of copper.

Mechanochromic Switching between Delayed Fluorescence and Phosphorescence of Luminescent Coordination Polymers Composed of Dinuclear Copper(I) Iodide Rhombic Cores

“…Such emission via energy migration through 1D coordination chains has been previously reported by Tsuge et al. ; the Cu I –Ag I mixed metal luminescent coordination polymer, [Ag 2‐ x Cu x I 2 (PPh 3 ) 2 (bpy)] n , exhibited emissions that originated from the Cu I site as the dominant species even in the extremely low Cu I dopant concentration ( x =0.005) . Thus, in the emission of ground samples of Cu‐ m ‐tpyb ( m =3, 4), the (M+X)LCT excitons generated in the 1D coordination chains could migrate and get captured by the impurity site with the lower‐energy 3 CC emissive state.…”

“…Such emissionvia energy migration through 1D coordination chains has been previously reported by Ts uge et al;t he Cu I -Ag I mixed metal luminescent coordination polymer,[ Ag 2-x Cu x I 2 (PPh 3 ) 2 (bpy)] n ,e xhibited emissions that originated from the Cu I site as the dominant speciese ven in the extremely low Cu I dopant concentration (x = 0.005). [49] Thus, in the emission of ground samples of Cu-m-tpyb (m = 3, 4), the (M + X)LCT excitons generatedi nt he 1D coordination chains could migrate and get captured by the impurity site with the lower-energy 3 CC emissive state. In fact, the mechanochromic switching behavior of Cu-4-tpyb strongly depended on the degree of manual grinding;t he lightly ground sample exhibited al ong emission lifetime comparable to that of the as-synthesized sample ( Figure S12), implying that the breaking of 1D coordination chains by manual grinding is an important step to generate the lower-energy 3 CC emissive state.…”

Structurally Precise Silver Sulfide Nanoclusters Protected by Rhodium(III) Octahedra with Aminothiolates

“…When 3equiv of [Cu(CH 3 CN) 4 ]BF 4 was added to an aqueous solution of 1, the absorption band shifted to ah igher energy to give an absorption shoulder at approximately l = 480 nm with aHO-MO-LUMO gap of 2.25 eV (Figure 3b), accompanied by ac hange in the solution color from deep red to orange;t he further addition of [Cu(CH 3 CN) 4 ]BF 4 resulted in very little change.T he reaction product was successfully isolated as orange block crystals (3)a fter purification using an anionexchange column (QAE-Sephadex A-25, NO 3 À form). However,t hree of the four MÀSb ond lengths of the tetrahedral core in 3 (av.2 .17 )a re much shorter than the corresponding Ag À Sbond lengths of the [Ag 4 S] 2+ tetrahedral core in 1b (av.2 .41 ), while the other M À Sb ond length is comparable to the corresponding distances in 1b.S ince the average MÀSdistance of 2.17 is within the range normally observed for the bonds between Cu I and sulfide, [35,36] it is reasonable to assume that the three Ag I atoms of the [Ag 4 S] 2+ core in 1b are replaced by Cu I atoms in 3,thereby producing the [Ag 43 Cu 3 S 13 {Rh(aet) 3 } 14 ] 20+ nanocluster with ah eterometallic [AgCu 3 S] 2+ core.A lthough several low-nuclear sulfide metal complexes with mixed Cu I and Ag I ions have been reported, [37][38][39] such as tructurally characterized sulfide nanocluster containing both Cu I and Ag I ions is rare. In addition, the chiral configurations for the [Rh(aet) 3 ]m olecules in 3 are the same as those in 1b.…”

“…In addition, the chiral configurations for the [Rh(aet) 3 ]m olecules in 3 are the same as those in 1b. However,t hree of the four MÀSb ond lengths of the tetrahedral core in 3 (av.2 .17 )a re much shorter than the corresponding Ag À Sbond lengths of the [Ag 4 S] 2+ tetrahedral core in 1b (av.2 .41 ), while the other M À Sb ond length is comparable to the corresponding distances in 1b.S ince the average MÀSdistance of 2.17 is within the range normally observed for the bonds between Cu I and sulfide, [35,36] it is reasonable to assume that the three Ag I atoms of the [Ag 4 S] 2+ core in 1b are replaced by Cu I atoms in 3,thereby producing the [Ag 43 Cu 3 S 13 {Rh(aet) 3 } 14 ] 20+ nanocluster with ah eterometallic [AgCu 3 S] 2+ core.A lthough several low-nuclear sulfide metal complexes with mixed Cu I and Ag I ions have been reported, [37][38][39] such as tructurally characterized sulfide nanocluster containing both Cu I and Ag I ions is rare. [40,41]…”

High‐performance reactive silver‐ion adsorption and reductive performance of poly(N‐methylaniline)

“…As a precious metal, silver has been widely used in functional nanomaterials for antibacterial materials, self‐erasable, and rewritable materials, luminescent materials, and catalysts . Consequently, excessive industrial wastewater containing silver ions has become a serious worldwide problem that endangers the environment and health of human beings .…”