Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled ...Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials?Herein we present a first principles study featuring three analogous polyazacyclophanes(L,L-Me,L-Me_(3)),differing only in the extent of N-methylation.We demonstrate(potentiometry,ITC)how they all form the same CuL^(2+)(L=L,L-Me,L-Me_(3))complex as prevalent species in solution,so that a level playing field exists where only N-methylation distinguishes them.Then we use them as countercations for polyiodide growth.XRD analysis of the resulting crystals clearly shows that methylation is a valuable tool to gradually shift directional control of subtending pairing preferences from H-bond to I…I interactions:this affects global packing and actively incorporates metal centres into polyiodide chains,setting the scene for further developments.展开更多
基金supported by the Spanish MINECO and the FEDER and COST from the European Union(CTQ2016-78499-C6-1-R,CTQ2017-90852-REDC,Unidad de Excelencia María de Maeztu CEX2019-000919-N and NECTAR CA18202 COST Action)A.M.-C.wants to thank Spanish Ministry of Science,Research and Universities for the PhD grants FPU14/05098 and EST17/00666.
文摘Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials?Herein we present a first principles study featuring three analogous polyazacyclophanes(L,L-Me,L-Me_(3)),differing only in the extent of N-methylation.We demonstrate(potentiometry,ITC)how they all form the same CuL^(2+)(L=L,L-Me,L-Me_(3))complex as prevalent species in solution,so that a level playing field exists where only N-methylation distinguishes them.Then we use them as countercations for polyiodide growth.XRD analysis of the resulting crystals clearly shows that methylation is a valuable tool to gradually shift directional control of subtending pairing preferences from H-bond to I…I interactions:this affects global packing and actively incorporates metal centres into polyiodide chains,setting the scene for further developments.
