An efficient and chemoselective mechanochemical synthesis of a bright TADF-emitting CuI-based compound is reported.The reaction of 2-(ethylsulfanyl)-6-methylpyridine(L)with CuI under solvent-free conditions or in solu...An efficient and chemoselective mechanochemical synthesis of a bright TADF-emitting CuI-based compound is reported.The reaction of 2-(ethylsulfanyl)-6-methylpyridine(L)with CuI under solvent-free conditions or in solution results in a non-emissive complex,[Cu_(2)I_(2)L_(2)](1)or a 1-D coordination polymer(CP),[Cu_(3)I_(3)L_(2)]_(n)(CP 2),respectively.Meanwhile,the simple manual grinding of the reactants in the presence of a few drops of MeCN for 1-2 min chemoselectively gives the structurally different 1-D CP,[Cu_(3)I_(3)L_(2)]_(n)(CP 3),as a single product isolated in 87%yield.Remarkably,both complex 1 and CP 2 under the mechanochemical conditions easily(1-2 min)undergo polymerization or isomerisation,accordingly,to afford CP 3.The structure of the latter is formed by cuprophilic interaction-free(-Cu-I-)_(n)chains ligated by 2-(ethylsulfanyl)-6-methylpyridines in aμ_(2)-N,S manner.At room temperature,CP 1 exhibits highly efficient blue-green TADF with a short lifetime(4.0μs)and a high photoluminescence performance(PLQY being 70%).展开更多
文摘An efficient and chemoselective mechanochemical synthesis of a bright TADF-emitting CuI-based compound is reported.The reaction of 2-(ethylsulfanyl)-6-methylpyridine(L)with CuI under solvent-free conditions or in solution results in a non-emissive complex,[Cu_(2)I_(2)L_(2)](1)or a 1-D coordination polymer(CP),[Cu_(3)I_(3)L_(2)]_(n)(CP 2),respectively.Meanwhile,the simple manual grinding of the reactants in the presence of a few drops of MeCN for 1-2 min chemoselectively gives the structurally different 1-D CP,[Cu_(3)I_(3)L_(2)]_(n)(CP 3),as a single product isolated in 87%yield.Remarkably,both complex 1 and CP 2 under the mechanochemical conditions easily(1-2 min)undergo polymerization or isomerisation,accordingly,to afford CP 3.The structure of the latter is formed by cuprophilic interaction-free(-Cu-I-)_(n)chains ligated by 2-(ethylsulfanyl)-6-methylpyridines in aμ_(2)-N,S manner.At room temperature,CP 1 exhibits highly efficient blue-green TADF with a short lifetime(4.0μs)and a high photoluminescence performance(PLQY being 70%).
