It was recently discovered that (Ph2PPrPDI)Mn (PDI = pyridine diimine) exists as a superposition of low-spin Mn­(II) that is supported by a PDI dianion and intermediate-spin Mn­(II) that is antiferromagnetically coupled to a triplet PDI dianion, a finding that encouraged the synthesis and electronic structure evaluation of late first row metal variants that feature the same chelate. The addition of Ph2PPrPDI to FeBr2 resulted in bromide dissociation and the formation of [(Ph2PPrPDI)­FeBr]­[Br]. Reduction of this precursor using excess sodium amalgam afforded (Ph2PPrPDI)­Fe, which possesses an Fe­(II) center that is supported by a dianionic PDI ligand. Similarly, reduction of a premixed solution of Ph2PPrPDI and CoCl2 yielded the cobalt analog, (Ph2PPrPDI)­Co. EPR spectroscopy and density functional theory calculations revealed that this compound features a high-spin Co­(I) center that is antiferromagnetically coupled to a PDI radical anion. The addition of Ph2PPrPDI to Ni­(COD)2 resulted in ligand displacement and the formation of (Ph2PPrPDI)­Ni, which was found to possess a pendent phosphine group. Single-crystal X-ray diffraction, CASSCF calculations, and EPR spectroscopy indicate that (Ph2PPrPDI)Ni is best described as having a Ni­(II)-PDI2– configuration. The electronic differences between these compounds are highlighted, and a computational analysis of Ph2PPrPDI denticity has revealed the thermodynamic penalties associated with phosphine dissociation from 5-coordinate (Ph2PPrPDI)­Mn, (Ph2PPrPDI)­Fe, and (Ph2PPrPDI)­Co.

We employed the chemical potential equalization principle to demonstrate that fractional electrons are involved in the electro-inductive effect as well as the vibrational Stark effect. By the chemical potential model, we were able to deduce that the frontier molecular orbitals of immobilized molecules can provide valuable insight into these effects. To further understand and quantify these findings, we introduced fractional charge density functional theory (FC-DFT), a canonical ensemble approach for open systems. This method allows for the calculation of electronic energies, nuclear gradients, and the Hessian matrix of fractional electronic systems. To correct the spurious delocalization error commonly found in approximate density functionals for small systems, we imposed the Perdew−Parr−Levy−Balduz (PPLB) condition through linear interpolation of two adjacent integer points (LI-FC-DFT). Although this approach is relatively simple in terms of molecular modeling, the results obtained through LI-FC-DFT calculations predict the same trend seen in experimental reactivity and the frequency change of immobilized molecules.

We employed the chemical potential neutralization principle to demonstrate that fractional electrons are involved in the electro-inductive effect as well as the vibrational Stark effect. By the chemical potential model, we were able to deduce that the frontier molecular orbitals of immobilized molecules can provide valuable insight into these effects. To further understand and quantify these findings, we introduced fractional charge density functional theory (FC-DFT), a canonical ensemble approach for open systems. This method allows for the calculation of electronic energies, nuclear gradients, and the Hessian matrix of fractional electronic systems. To correct the spurious delocalization error commonly found in approximate density functionals for small systems, we imposed the Perdew-Parr-Levy-Balduz (PPLB) condition through linear interpolation of two adjacent integer points (LI-FC-DFT). Although this approach is relatively simple in terms of molecular modeling, the results obtained through LI-FC-DFT calculations predict the same trend seen in experimental reactivity and the frequency change of immobilized molecules.