Strain-Induced Isomerization in One-Dimensional Metal-Organic Chains

. 2019 Dec 16 ; 58 (51) : 18591-18597. [epub] 20191104

Status PubMed-not-MEDLINE Jazyk angličtina Země Německo Médium print-electronic

Typ dokumentu časopisecké články, přehledy

Perzistentní odkaz   https://www.medvik.cz/link/pmid31608578

Grantová podpora
FT160100207 Australian Research Council
R-143-000-A06-112, R-143-000-682-112 , R-143-000-A75-114 Ministry of Education - Singapore
MOE2014-T3-1-004 Ministry of Education - Singapore
LM2015087 Akademie Věd České Republiky
project No. 18-09914S. Grantová Agentura České Republiky

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal-organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures.

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