The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL 2 , PcFeL′L″, and [PcFeX 2 ] 2− complexes (Pc = phthalocyaninato(2-) ligand; L = NH 3 , n-BuNH 2 , imidazole (Im), pyridine (Py), PMe 3 , PBu 3 , t-BuNC, P(OBu) 3 , and DMSO; L′ = CO; L″ = NH 3 or n-BuNH 2 ; X = NCO − , NCS − , CN − , imidazolate (Im − ), or 1,2,4triazolate(Tz − )) were probed by electrochemical, spectroelectrochemical, and chemical oxidation as well as theoretical (density functional theory, DFT) studies. In general, energies of the metal-centered occupied orbitals in various six-coordinate iron phthalocyanine complexes correlate well with Lever Electrochemical Parameter E L and intercross the phthalocyaninecentered a 1u orbital in several compounds with moderate-to-strong π-accepting axial ligands. In these cases, an oxidation of the phthalocyanine macrocycle (Pc(2-)/Pc(1-)) rather than the central metal ion (Fe(II)/Fe(III)) was theoretically predicted and experimentally confirmed.

The reduction of iron(II) phthalocyanine (Pc(2−)FeII) or its bisaxially coordinated complexes results in the formation of the purple/red [PcFe]−, [PcFeL]−, and [PcFeX]2– (L is neutral and X is anionic ligand) species. The X-ray structure of the [K(DME)4][PcFe] complex exhibits a square-planar [PcFe]− anion. 1H NMR spectra of the reduced species have one or two phthalocyanine broad peaks between 15 and 17 ppm. Solution magnetic moments are consistent with the presence of a single unpaired electron. A solid-state Mössbauer spectrum of [K(DME)4][PcFe] is consistent with an early report [Pure Appl. Chem.197438427438]. The solid-state EPR spectrum of the [PcFe]− anion is close to that recorded by Konarev et al. [Dalton Trans.2012411384113847]. Solution EPR spectra of reduced species have axial symmetry (g ⊥ ∼ 2.08–2.17 and g || ∼ 1.95–1.96) and correlate well with spectra reported by Lever and Wilshire in 1978 [Inorg. Chem.19781711451151]. The UV–vis spectra of pentacoordinated [PcFeL]− and [PcFeX]2– anions consist of the characteristic bands around 810, 690, and 515 nm. These bands correlate well with the set of MCD pseudo A-terms and resemble transitions in the [Pc(3−)M]− and [Pc(3−)ML]− compounds. The UV–vis and MCD spectra of [PcFeL]− and [PcFeX]2– complexes are in stark contrast to the crystallographically characterized reference [Pc(2−)CoI]− anion, which is EPR silent, has a regular diamagnetic 1H NMR spectrum, and has an intense Q-band at 699 nm, which correlates well with the strong MCD A-term. The DFT and TDDFT calculations are suggestive of the iron(II) center in a (d xy )2(d xz , yz )3(d z 2 )1 (s = 1) electronic configuration that is antiferromagnetically coupled with the one-electron-reduced Pc(3−) ligand (i.e., [Pc(3−)FeII]−, [Pc(3−)FeIIL]−, and [Pc(3−)FeIIX]2–). The calculated EPR, Mössbauer, and UV–vis spectra of [PcFe]−, [PcFeL]−, and [PcFeX]2– complexes are in excellent agreement with the experimental data, thus resolving the controversy between axial s = 1/2 like EPR and Pc(3−)-like UV–vis spectra of these compounds.

Solid-state Mössbauer spectra of a highly soluble (μ-oxo)­bis­[tetra­(tert-butyl)­(phthalocyaninato)­iron­(III)] complex 1 ((Pc tBuFe)2O) consist of two doublets that represent bent geometry in μ-oxo(1) (1a, ΔE Q = 0.43 mm/s, T = 10 K) and linear geometry in μ-oxo(2) (1b, ΔE Q = 1.40 mm/s, T = 10 K) isomers with the ratio between two isomers depending on the purification method. Both isomers were found to be diamagnetic and transform entirely to the 1a isomer in solution. The room- and low-temperature magnetic circular dichroism (MCD) spectra of 1a μ-oxo(1) show one Faraday A- and one B-term between 670 and 720 nm, which correlate with the 690 nm band and 709 nm shoulder observed in the UV–vis spectrum of this compound. UV–vis and MCD spectra of 1a are almost independent of the temperature. Both 1a and 1b are diamagnetic between room temperature and 4 K. Electrochemical experiments show up to three oxidations and up to four reduction processes in 1a. Its oxidation under spectroelectrochemical or chemical (in the absence of oxygen-containing oxidants) conditions in non-coordinating solvents results in the formation of broad NIR bands around 1195 nm (first oxidation) and 1264 nm (second oxidation). The MCD spectra of the redox-active species show a Faraday B-term signal with negative amplitude in this region and are very different from those in the monomeric Pc tBu(1−)­FeIIIX2 complexes 5X (X = Cl– or CF3CO2 –). The pyridine adduct of 1a ((PyPc tBuFe)2O; 2Py) is paramagnetic (μB = 2.19, g = 2.11, and J = −6.1 cm–1) and has a major peak at 627 nm of its UV–vis spectrum, which is associated with a MCD pseudo A-term. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, along with the exciton coupling theory, were used to explain the unusually red-shifted intense transitions in 1a as well as the H-aggregate-like spectra of the pyridine adduct 2Py.

A sterically strained 32π-electron antiaromatic bis-BODIPY macrocycle in which two BODIPY fragments are linked by p-divinylbenzene groups was prepared and characterized. Unlike regular BODIPYs, the fluorescence in this macrocycle is quenched. The broad signals in the NMR spectra of the macrocycle were explained by the vibronic freedom of the p-divinylbenzene fragments. The possible diradicaloid nature of the macrocycle was excluded on the basis of variable-temperature EPR spectra in solution and in solid state, which is indicative of its closed-shell quinoidal structure. The meso-CÀ H bond in the macrocycle and its precursor BODIPY dialdehyde 3 forms a weak hydrogen bond with THF and is susceptible for the nucleophilic attack by organic amines and cyanide anion. The reaction products of such a nucleophilic attack have meso-sp 3 carbon atoms and were characterized by NMR, mass spectrometry and, in one case, X-ray crystallography. Unlike the initial bis-BODIPY macrocycle, the adducts have strong fluorescence in the 400 nm region. The electronic structure and spectroscopic properties of new chromophores were probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations and correlate well with the experimental data.