Tailoring Transition Metal Complexes for Nonlinear Optics Applications. 2. A Theoretical Investigation of the Second-Order Nonlinear Optical Properties of M(CO)5L Complexes (M = Cr, W; L = Py, PyCHO, Pyz, PyzBF3, BPE, BPEBF3)

The authors report an ab initio study of 2nd-order nonlinear optical (NLO) properties and absorption electronic spectra of push-pull transition metal chromophores [M(CO)5L] (M = Cr, W; L = pyridine (Py), 4-formyl-pyridine (PyCHO), pyrazine (Pyz), trans-1,2-bis(4-pyridyl)ethylene (BPE)). Pyz and BPE are considered either with 1 N atom free or interacting with the strong acceptor BF3. All of the mol. properties were calcd. using 2 different and methodol. independent approaches: the time dependent and coupled perturbed d. functional theories (TDDFT and CPDFT) and the sum-over-states (SOS) approach, where the excited states are obtained via the single CI (SCI) ab initio method. DFT results are in acceptable agreement with the exptl. energy values of electronic transitions (with the exception of chromophores with the large greek p-delocalization, like BPE); SCI calcns. overestimate excitation energies and produce an inversion in the order of dM greek pi*L and dM greek p*CO transitions. The SCI-SOS approach gives 1st-order hyperpolarizabilities, basically in agreement as trend and values with the expts. and seems to be a tool generally suitable for the evaluation of these properties also for transition metal complexes. However, the 1st-order hyperpolarizabilities computed using the CPDFT approach are consistently overestimated in comparison with the exptl. results, esp. in the case of a ligand with large greek p-delocalization. Also the 2-level approxn. taking into account only the lowest energy charge transfer excitation (e.g., dM greek p*L) is not applicable to chromophores with the extended greek p-delocalized ligand (BPE) coordinated to a transition metal, due to significant contributions originating from intraligand greek pL greek p*L transitions. This study reports a detailed anal. and comparison of electronic NLO effects of transition metal complexes computed with DFT and ab initio SCI-SOS methodol.