"Stapled" Bis(phthalocyaninato)niobium(IV), Pc2Nb: X-ray Crystal Structure, Chemical and Electrochemical Behavior, and Theoretical Studies. Perspectives for the Use of Pc2Nb (Thin Films) as an "Optically Passive Electrode" in Electrochromic Devices

Recrystallization of the previously reported monosolvated bis(phthalocyaninato)niobium(IV), [Pc2Nb]-CINP (CINP = 1-chloronaphthalene), has allowed isolation of a single crystal of a new solvated form, i.e. [Pc2Nb]3.5CINP, whose structure has been elucidated by X-ray work: space group P2/n (No. 14); a = 16.765(3), b = 23.800(4), c = 19.421(4) A: (alpha) = (gamma) = 90°, (beta) = 92.51(2)°; Z = 4. The sandwiched material is a "stapled" molecule, characterized by the presence of two intramolecular interligand C-C (sigma) bonds and highly strained phthalocyanine units, as formerly observed by crystallographic work for its Ti(IV) analogue, [Pc2Ti], and the +1 corresponding fragment, [Pc2Nb], present in the species [Pc2Nb](l3)(l2)o.5.3.5CINP. [Pc2Nb] appears to be reluctant to undergo further oxidation above the +1 oxidation state. Detailed theoretical studies by DFT and TDDFT methods have been developed on [Pc2Nb] and [Pc2Nb], also extended for comparison to the Ti(IV) complex [Pc2Ti], and an adequate picture of the ground-state electronic structure of these species has been achieved. Moreover, the excitation energies and oscillator strengths calculated for the closed-shell systems, [Pc2Ti] and [Pc2Nb]+, provide a satisfactory interpretation of their characteristic visible optical spectra and help to rationalize the similar features observed in the visible spectrum of the open-shell "stapled" complex, [Pc2Nb]. Thin solid films (100-250 nm) of [Pc2Nb] deposited on ITO (indium-doped tin oxide) show a reversible redox process in neutral or acidic aqueous electrolytes. The etectrochemical and electrochromic properties of the sandwiched complex, combined with impedance and UV/visible spectral measurements, are presented and discussed. The achieved etectrochemical information, while substantially in keeping with the observed chemical redox behavior and theoretical predictions, qualifies [Pc2Nb] as an "optically passive" electrode and a promising material for its use in electrochromic devices.