Impact of ligand fields on Kubas interaction of open copper sites in MOFs with hydrogen molecules: an electronic structural insight.

We investigate hydrogen sorption on open copper sites in various ligand coordinations of metal-organic frameworks (MOFs), including the triangular T(CuL) in MFU-4l, the linear L(CuL) in NU2100, and the paddlewheel P(CuL) in HKUST-1 from an electronic structure perspective using DFT calculations. The ligand-field-induced splitting of d states and spd hybridizations in copper are thoroughly examined. The hybridization between Cu s, p, and d orbitals occurs in various forms to optimize the Coulomb repulsion of different ligand fields. Despite the Cu oxidation state, which is typically conducive to strong Kubas interactions with hydrogen molecules, the vacant spd hybrid orbitals of the open copper site in the L(CuL) coordination are unsuitable for facilitating electron forward donation, thereby preventing effective hydrogen adsorption. In contrast, the vacant spd hybrid orbitals in the T(CuL) and P(CuL) coordinations can engage in electron forward donations, forming bonding states between the Cu spd and H σ bonding orbitals. The forward donation in the T(CuL) configuration is significantly stronger than in the P(CuL) configuration due to both the lower energy of the vacant orbitals and the larger contributions of p and d characters to the hybrid orbital. Additionally, the occupied Cu pd and pd hybrid orbitals in the T(CuL) configuration promote electron back donation to the H σ* antibonding orbital, leading to the formation of π bonding states. In the P(CuL) coordination, the repulsion from the electron density distributed over the surrounding ligands prevents the H molecule from approaching the copper center closely enough for the back donation to occur. The complete Kubas interaction, involving both forward and back electron donations, results in a large dihydrogen-copper binding energy of 37.6 kJ mol in the T(CuL) coordination. In contrast, the binding energy of 10.6 kJ mol in the P(CuL) coordination is primarily driven by electrostatic interactions with a minor contribution of the Kubas-like forward donation interaction. This analysis highlights the pivotal role of coordination environments in determining the hydrogen sorption properties of MOFs.