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Enhanced electronic coupling gives rise to many intriguing properties in π–d conjugated metal–organic frameworks (CMOFs). By low-temperature scanning tunneling microscopy and density functional theory calculation, we investigate the electronic coupling in one-dimensional (1D) π–d conjugated FeQDI polymers. Our experiments have resolved the bulk and end states stemming from Fe atoms in different coordination environments and their spatial extension due to π–d conjugation. By fitting the band structure by Wannier functions in an energy range of −0.5 eV to 0 eV, the Fe–Fe, QDI–QDI and Fe–QDI hopping integrals are determined to be 15 meV, 121 meV and 24 meV, respectively. Our work provides experimental and theoretical insights into the electronic coupling in 1D CMOFs. [ABSTRACT FROM AUTHOR]

A DFT comparative mechanistic study unveils that the TBD-catalyzed reactions of amines with CO2 and hydrosilanes may either undergo a neutral mechanism or a mechanism involving free ions, depending on the polarity of the solvent. The nucleophilicity of the amines is an important factor to determine the chemoselectivities of the reactions to give formamide or aminal/N-methylated amine. [ABSTRACT FROM AUTHOR]

We herein report a new H2 activation mechanism to elucidate the N-formylation of amines with CO2 and H2, catalyzed by Ru(ii) pincer complexes in the absence of exogenous additives. Furthermore, we show that the mechanism could be applied to other types of Ru(ii) pincer complexes and computed iron analogs. [ABSTRACT FROM AUTHOR]