The development of energy efficient process for the CO2 capture and reduction to valuable hydrocarbon chemicals could help reduce atmospheric CO2 levels and partly fulfill energy demands within the present hydrocarbon based fuel infrastructure.In an effort to impact the carbon economy, metal-organic frameworks(MOFs) have emerged as promising materials for CO2 capture.Although such materials have demonstrated a capacity for adsorption of CO2 molecules, very little is known about their molecular scale interactions with CO2 molecules.Such knowledge is essential for designing optimized materials for CO2 capture.Our research inaugurates molecule-resolved investigationsof the interaction, electronic structure and chemical activity of CO2 molecules and MOF structures.We imaged for the first time, by low-temperature scanning tunneling microscopy (LT-STM) theself-assembly of MOF structures on atomically smooth surfaces, and the interaction of isolated CO2 molecules with MOFs.In our preliminary research, we employ 1D metal containing chains to form 1D MOF structures on noble metal surfaces.With the STM experiments, wedemonstrate that: 1) it is possible to self-assemble stable but highly flexible 1D arrays of single molecular wide MOF structures on Au and Cu surfaces; 2) CO2 molecules have a high affinity for such MOF structures and attach to them at a single molecule level as well as in aggregates at cryogenic temperatures.We observe remarkable tendency of CO2molecules to coalesce into clusters surrounding chemisorbed CO2-δ(likely interactions of MOF chains with CO2 molecules include interplay between frustrated Lewis acid-base pairs which favor the CO2-δ formation)molecular seeding sites on the MOF chains.Although large (CO2)n-clusters have been studied in the gas phase, we believe our study presents the first STM image of such clusters at the molecular scale.3) MOF lines respond dynamically to force CO2 molecular condensation into closely packed islands.The observations indicate that imaging of the interaction between CO2 molecules and MOF structures, as well as among CO2molecules in condensed islands with single molecular resolution provides a unique opportunity to investigate the complex physical and chemical interactions that determine the ability of MOF materials to selectively adsorb and reduce CO2 molecules.Density functional theory (DFT) calculations and model calculations arecombinedto explainthe underlying atomic scale interactions that enable theCO2capture.We expect to use the metal supported MOF structures as platforms for investigating the ultrafast electron induced processes in CO2reduction.