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Enhancing chalcogen bonding by metal coordination.

Rosa Maria GomilaAntonio BauzáAntonio Frontera
Published in: Dalton transactions (Cambridge, England : 2003) (2022)
This manuscript shows that chalcogen bonding (ChB) interactions are enhanced by the coordination of the chalcogen atom to metal centers as evidenced using DFT calculations (PBE0-D3/def2-TZVP level of theory). X-ray structures retrieved from the Cambridge Structural Database (CSD) are used to support the enhanced ability of Se and Te-atoms coordinated to transition metals to participate in ChBs, eliminating the necessity to use strong electron-withdrawing groups bonded to the Ch atom. Orbital analysis performed using the natural bond orbital (NBO) technique discloses a large LP → σ* contribution, especially for anionic electron donors. In one example, the new σ-hole that is generated upon complexation (opposite to the Ch-M bond) plays a crucial role in the solid state, promoting the formation of infinite 1D polymers.
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