Use of Unprecedented Intramolecular 1,3-Dipolar Cycloaddition Reaction in meso-Nitrile Oxide-Containing BODIPY as a New Pathway for the Preparation of Fused NIR Platforms.

Meso-nitrile oxide group in 1,7-Diphenyl-containing BODIPYs can be involved in highly unusual [3+2] intramolecular cycloaddition reaction with the formation of the dihydrobenzo[d]isoxazole-containing BODIPYs. Oxidation of these compounds results in the formation of unprecedented either benzisoxazole- or benzo[b]azepine-fused fully conjugated NIR absorbing BODIPYs. The photophysical properties and electronic structures of the target compounds were studied by an array of experimental and theoretical methods.

Photophysical Exploration of Two Isomers of Octaethyltrioxopyrrocorphin.

The introduction of three ß-oxosubstituents to octaethylporphyrin by means of an oxidation/rearrangement reaction generates the trioxopyrrocorphin chromophore. Pyrrocorphins (hexahydroporphyrins) are generally nonaromatic, but we recently demonstrated trioxopyrrocorphins to possess considerable aromatic character. This contribution explores the photophysical characteristics of these unusual chromophores. In agreement with density functional theory modeling, the UV-vis and magnetic circular dichroism spectra of the two─out of the four possible─triketone regioisomers investigated conform to the Gouterman model of porphyrinoid optical spectra, in alignment with their aromaticity. Their excited-state dynamics shed further light on the degree to which ß-oxo substitutions tune the photophysical properties of porphyrinoids. Introduction of ß-oxo functionalities increases the rate and yield of intersystem crossing and shortens the triplet state lifetime. Unexpectedly, the singlet oxygen generation yield of both pyrrocorphins remains relatively high, with modes of distortion from planarity likely enhancing triplet energy transfer. This work thus expands our understanding of a rare class of porphyrinoids and further characterizes them as sustaining aromatic porphyrinic π-systems. Our findings suggest triple ß-oxo substitution as a viable route toward the development of novel, high-singlet oxygen yield porphyrinic photosensitizers.

The fascinating story of axial ligand dependent spectroscopy and redox-properties in iron(II) phthalocyanines.

Iron phthalocyanines play crucial fundamental and applied roles ranging from bulk colorants to components of advanced materials. In this Frontier article, we discuss four aspects concerning the influence of the axial ligands on spectroscopic and redox properties of iron(II) phthalocyanines: (i) iron versus macrocycle oxidation cite as a function of Lever's EL parameter; (ii) energy of the metal-to-ligand charge-transfer transitions as a function of Lever's EL parameter; (iii) iron versus macrocycle reduction in iron(II) phthalocyanines; (iv) Mössbauer quadrupole splitting as a function of axial ligand binding through the prism of dz2 orbital population.

Magnetic Circular Dichroism of Porphyrinoid Silver Complexes: Evidence of the Electronic Structure Inversion upon Protonation of the N-Confused Core.

We report a systematic investigation of a series of Ag(II) and Ag(III) complexes of porphyrins and their analogues using UV-vis magnetic circular dichroism (MCD) spectroscopies and theoretical calculations. Ag(II) and Ag(III) octaethyl- and tetraarylporphyrins show the usual sign sequence in the Q-band region (i.e., negative to positive intensities with increasing energy) of their MCD spectra, indicative of the ΔHOMO > ΔLUMO relationship (ΔHOMO is the energy difference between Michl's a and s orbitals, and ΔLUMO is the energy difference between Michl's -a and -s pair of MOs). In contrast, Ag(II) complexes of ß,ß'-pyrrole-modified porphyrins (with an effective chlorin-type π-system) and Ag(III) corroles have sign reverse features in the MCD spectra of their Q-band region (ΔHOMO < ΔLUMO relationships). The Ag(III) complex of N-confused porphyrin shows the ΔHOMO > ΔLUMO relationship in the neutral state and the ΔHOMO < ΔLUMO relationship in the protonated form.

Role of MCD and Mössbauer Spectroscopy in the Explanation of the Properties of a Highly Soluble (µ-Oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] Complex, Its Pyridine Adduct, and Redox Forms Oxidized under Anaerobic Conditions in Non-Coordinating Solvents.

Solid-state Mössbauer spectra of a highly soluble (µ-oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] complex 1 ((PctBuFe)2O) consist of two doublets that represent bent geometry in µ-oxo(1) (1a, ΔEQ = 0.43 mm/s, T = 10 K) and linear geometry in µ-oxo(2) (1b, ΔEQ = 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 PctBu(1-)FeIIIX2 complexes 5X (X = Cl- or CF3CO2-). The pyridine adduct of 1a ((PyPctBuFe)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.

Influence of the ligand-field on EPR parameters of cis- and trans-isomers in MoV systems relevant to molybdenum enzymes: Experimental and density functional theory study.

The electron paramagnetic resonance (EPR) investigation of mononuclear cis- and trans-(L1O)MoOCl2 complexes [L1OH = bis(3,5-dimethylpyrazolyl)-3-tert-butyl-2-hydroxy-5-methylphenyl)methane] reveals a significant difference in their spin Hamiltonian parameters which reflect different equatorial and axial ligand fields created by the heteroscorpionate donor atoms. Density functional theory (DFT) was used to calculate the values of principal components and relative orientations of the g and A tensors, and the molecular framework in four pairs of isomeric mononuclear oxo­molybdenum(V) complexes (cis- and trans-(L1O)MoOCl2, cis,cis- and cis,trans-(L-N2S2)MoOCl [L-N2S2H2 = N,N'-dimethyl-N,N'-bis(mercaptophenyl)ethylenediamine], cis,cis- and cis,trans-(L-N2S2)MoO(SCN), and cis- and trans-[(dt)2MoO(OMe)]2- [dtH2 = 2,3-dimercapto-2-butene]). Scalar relativistic DFT calculations were conducted using three different exchange-correlation functionals. It was found that the use of hybrid exchange-correlation functional with 25% of the Hartree-Fock exchange leads to the best quantitative agreement between theory and experiment. A simplified ligand-field approach was used to analyze the influence of the ligand fields in all cis- and trans-isomers on energies and contributions of molybdenum d-orbital manifold to g and A tensors and relative orientations. Specifically, contributions that originated from the spin-orbit coupling of the dxz, dyz, and dx2-y2 orbitals into the ground state have been discussed. The new findings are discussed in the context of the experimental data of mononuclear molybdoenzyme, DMSO reductase.

Resolving a Half-Century-Long Controversy between (Magneto)optical and EPR Spectra of Single-Electron-Reduced [PcFe]-, [PcFeL]-, and [PcFeX]2- Complexes: Story of a Double Flip.

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 [Taube, R. Pure Appl. Chem.1974, 38, 427-438]. The solid-state EPR spectrum of the [PcFe]- anion is close to that recorded by Konarev et al. [ Dalton Trans.2012, 41, 13841-13847]. 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.1978, 17, 1145-1151]. 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 (dxy)2(dxz,yz)3(dz2)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.

Outsourcing Intersystem Crossing without Heavy Atoms: Energy Transfer Dynamics in PyridoneBODIPY-C60 Complexes.

The excited state dynamics in two fully characterized pyridoneBODIPY-fullerene complexes were investigated using time-resolved spectroscopy. Photoexcitation was initially localized on the pyridoneBODIPY chromophore. The energy was rapidly transferred to the fullerene, which subsequently underwent ISC to form a triplet state and returned the energy to the pyridoneBODIPY via triplet-triplet energy transfer. This ping-pong energy transfer mechanism resulted in efficient (>85%) overall conversion of the excited state pyridoneBODIPY constituent despite a complete lack of ISC in the pyridoneBODIPY in the absence of the fullerene partner. The small difference in attachment chemistry for the fullerene did not impact the initial singlet energy transfer. However, the N-methylpyrrolidine bridge did slow both the triplet-triplet energy transfer and the ultimate relaxation rate of the final triplet state when compared to an isoxazole-based bridge. The rates of each step were quantified, and computational predictions were used to complement the proposed mechanism and energetics. The result demonstrated efficient triplet sensitization of a strong chromophore that lacks significant spin-orbit coupling.

Meso-Carbon Atom Nucleophilic Attack Susceptibility in the Sterically Strained Antiaromatic Bis-BODIPY Macrocycle and Extended Electron-Deficient BODIPY Precursor.

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-C-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-sp3 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.

Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300†nm.

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax ∼1300 nm and can be either oxidized to regular [MII (MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII (MB-DIPY)]- compounds. The radical nature of the stable [MII (MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.

Charge-Transfer Spectroscopy of Bisaxially Coordinated Iron(II) Phthalocyanines through the Prism of the Lever's EL Parameters Scale, MCD Spectroscopy, and TDDFT Calculations.

The position of the experimentally observed (in the UV-vis and magnetic circular dichroism (MCD) spectra) low-energy metal-to-ligand charge-transfer (MLCT) band in low-spin iron(II) phthalocyanine complexes of general formula PcFeL2, PcFeL'L″, and [PcFeX2]2- (L, L', or L″ are neutral and X- is an anionic axial ligand) was correlated with the Lever's electrochemical EL scale values for the axial ligands. The time-dependent density functional theory (TDDFT)-predicted UV-vis spectra are in very good agreement with the experimental data for all complexes. In the majority of compounds, TDDFT predicts that the first degenerate MLCT band that correlates with the MCD A-term observed between 360 and 480 nm is dominated by an eg (Fe, dπ) → b1u (Pc, π*) single-electron excitation (in traditional D4h point group notation) and agrees well with the previous assignment discussed by Stillman and co-workers[ Inorg. Chem. 1994, 33, 573-583]. The TDDFT calculations also suggest a small energy gap for b1u/b2u (Pc, π*) orbital splitting and closeness of the MLCT1 eg (Fe, dπ) → b1u (Pc, π*) and MLCT2 eg (Fe, dπ) → b2u (Pc, π*) transitions. In the case of the PcFeL2 complexes with phosphines as the axial ligands, additional degenerate charge-transfer transitions were observed between 450 and 500 nm. These transitions are dominated by a2u (Pc + L, π) → eg (Pc, π*) single-electron excitations and are unique for the PcFe(PR3)2 complexes. The energy of the phthalocyanine-based a2u orbital has large axial ligand dependency and is the reason for a large energy deviation for B1 a2u (Pc + L, π) → eg (Pc, π*) transition. The energies of the axial ligand-to-iron, axial ligand-to-phthalocyanine, iron-to-axial ligand, and phthalocyanine-to-axial ligand charge-transfer transitions were discussed on the basis of TDDFT calculations.

Unsymmetric Pentacene- and Pentacenequinone-Fused Porphyrins: Understanding the Effect of Cross- and Linear-Conjugation.

Unsymmetric pentacenequinone-fused (cross-conjugated) and pentacene-fused (linear-conjugated) porphyrins were designed and synthesized. The cross-conjugated (AM 1 -AM 3 ) and linear-conjugated (AM 5 -AM 7 ) porphyrins displayed strikingly different sets of optical and electronic properties, both of which are unusual and nontypical of porphyrins. MCD, DFT, and TDDFT calculations suggest that multiple charge transfer states exist in both π-conjugated systems, which contributes to the complex absorption and MCD spectra of these molecular systems. The general Gouterman's four-orbital model used to explain porphyrin spectroscopy led to contradicting theoretical and experimental data, and is thus not applicable for these molecular systems. The "2 + 4" and "3 + 3" active spaces have been deduced and have proven effective to interpret the absorption and MCD spectra of the pentacenequinone-fused (cross-conjugated) and pentacene-fused (linear-conjugated) porphyrins, respectively. Spectroelectrochemistry of AM 5 -AM 7 revealed broad and intense IR absorptions in the range of 1500-2500 nm, illustrating the exceptional ability of these pentacene-fused systems to accommodate positive charges. A pronounced metal effect was observed for pentacene-fused porphyrins. While pentacene-fused Ni(II) porphyrin (AM6 ) demonstrated an abnormal ability to stabilize pentacene with a half-life of >28.3 days, the half-life of the free base and Zn(II) counterparts were normal, similar to those of pentacene analogues. This work provides important and useful information on guiding new material designs.

Application of Lever's EL Parameter Scale toward Fe(II)/Fe(III) versus Pc(2-)/Pc(1-) Oxidation Process Crossover Point in Axially Coordinated Iron(II) Phthalocyanine Complexes.

The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL2, PcFeL'L″, and [PcFeX2]2- complexes (Pc = phthalocyaninato(2-) ligand; L = NH3, n-BuNH2, imidazole (Im), pyridine (Py), PMe3, PBu3, t-BuNC, P(OBu)3, and DMSO; L' = CO; L″ = NH3 or n-BuNH2; X = NCO-, NCS-, CN-, imidazolate (Im-), or 1,2,4-triazolate(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 EL and intercross the phthalocyanine-centered a1u 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.

Binding a Meridional Ligand in a Facial Geometry: A Square Peg in a Round Hole.

The bis(pyridylimino)isoindoline (BPI) ligand is a tridentate chelate that binds to metals via a meridional coordination mode. However, when this ligand forms a complex with Re(CO)3, an almost exclusively facial moiety, the BPI ligand deforms to coordinate in a facial mode. We have in-vestigated this deformation via structural and theoretical means, and the non-planar binding mode of the ligand bathochromically shifts the metal to ligand charge transfer (MLCT) transition.

BOSHPY Fluorophores: BODIPY Analogues with Single Atom Controlled Aggregation.

The reaction of diiminoisoindoline and iminoxoisoindoline with aminoazoles results in the formation of bidentate chelates that can be considered a semihemiporphyrazine. These chelates react with BF3 to produce fluorescent compounds that are structurally analogous to the BODIPY dyes. These difluoroboron semihemiporphyrazines (BOSHPYs) aggregate, and the type of aggregation (H or J) is determined by a single atom at the periphery of the ligand (O or N). Notably, the imine terminated compounds remain fluorescent upon aggregation.

Similar, Yet Different: Long-Range Metal-Metal Coupling and Electron-Transfer Processes in Metal-Free 5,10,15,20-Tetra(ruthenocenyl)porphyrin.

The electronic structure, redox properties, and long-range metal-metal coupling in metal-free 5,10,15,20-tetra(ruthenocenyl)porphyrin (H2TRcP) were probed by spectroscopic (NMR, UV-vis, magnetic circular dichroism (MCD), and atmospheric pressure chemical ionization (APCI)), electrochemical (cyclic voltammetry, CV, and differential pulse voltammetry, DPV), spectroelectrochemical, and chemical oxidation methods, as well as theoretical (density functional theory, DFT, and time-dependent DFT, TDDFT) approaches. It was demonstrated that the spectroscopic properties of H2TRcP are significantly different from those in H2TFcP (metal-free 5,10,15,20-tetra(ferrocenyl)porphyrin). Ruthenocenyl fragments in H2TRcP have higher oxidation potentials than the ferrocene groups in the H2TFcP complex. Similar to H2TFcP, we were able to access and spectroscopically characterize the one- and two-electron oxidized mixed-valence states in the H2TRcP system. DFT predicts that the porphyrin π-system stabilizes the [H2TRcP]+ mixed-valence cation and prevents its dimerization, which is characteristic for ruthenocenyl systems. However, formation of the mixed-valence [H2TRcP]2+ is significantly less reproducible than the formation of [H2TRcP]+. DFT and TDDFT calculations suggest the ruthenocenyl fragment dominance in the highest occupied molecular orbital (HOMO) energy region and the presence of the low-energy MLCT (Rc → porphyrin (π*)) transitions in the visible region with energies higher than the predominantly porphyrin-centered Q-bands.

Unveiling KuQuinone Redox Species: An Electrochemical and Computational Cross Study.

The study of the electrochemical properties of variegated quinones is a fascinating topic in chemistry. In fact, redox reactions occurring with quinoid scaffolds are essential for most of their applications in biological systems, in photoelectrochemical devices, and in many other fields. In this paper, a detailed investigation of KuQuinones' redox behavior is presented. The distinctiveness of such molecules is the presence in the structure of two condensed naphthoquinone units, which implies the possibility to undergo multiple one-electron reduction processes. Solvent, supporting electrolyte, and hydrogen bond donor species effects have been elucidated. Changing the experimental parameters provoked significant shift of the redox potential for each reduction process. In particular, additions of 2,2,2-trifluoroethanol as a hydrogen bond donor in solution as well as Lewis acid coordination were crucial to obtain important shifts of the redox potentials toward more favorable values. UV-vis-NIR spectroelectrochemical experiments and DFT calculations are also presented to clarify the nature of the reduced species in solution.

Environmentally Benign Route for Scalable Preparation of 1-Imino-3-thioisoindolines-The Key Building Blocks for the Synthesis of Dithio- and Diamino-ß-isoindigo Derivatives.

A one-step, gram-scale protocol for the preparation of 1-imino-3-thioisoindolines and a novel one-pot two-step methodology of the synthesis of dithio- or diamino-ß-isoindigo derivatives starting from phthalonitriles and sodium hydrosulfide in an aprotic dipolar solvent have been developed. It was demonstrated that the electronic properties of the substituent(s) in the phthalonitrile core play a critical role in ß-isoindigo synthesis resulting either in the selective formation of dithio- or diamino-ß-isoindigo chromophores. The N-acylated 1-imino-3-thioisoindolines can be used for the direct, easily scalable, and chromatography-free procedure for the preparation of a new class of N,N'-diacylamino-ß-isoindigoid compounds. Properties of the monomeric as well as J-aggregated forms of dithio- and diamino-ß-isoindigo were probed by the absorption and fluorescence spectroscopies. It was demonstrated that the tetracyano-diamino-ß-isoindigo 3f can form a J-aggregate that absorbs at 793 nm and fluoresces at 824 nm. This aggregate is stable in N,N-dimethylformamide solution; however, it slowly dissociates in tetrahydrofuran or under sonication conditions. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to elucidate the electronic structures, spectroscopic properties, and aggregation of new dithio- and diamino-ß-isoindigo derivatives.

Accurate Prediction of Mössbauer Hyperfine Parameters in Bis-Axially Coordinated Iron(II) Phthalocyanines Using Density Functional Theory Calculations: A Story of a Single Orbital Revealed by Natural Bond Orbital Analysis.

Density Functional Theory (DFT) calculations coupled with several exchange-correlation functionals were used for the prediction of Mössbauer hyperfine parameters of 36 bis-axially coordinated iron(II) phthalocyanine complexes with the general formulas PcFeL2, PcFeL'L″, and [PcFeX2]2-, including four new compounds. Both gas-phase and PCM calculations using BPW91 and MN12L exchange-correlation functionals were found to accurately predict both Mössbauer quadrupole splittings and the correct trends in experimentally observed isomer shifts. In comparison, hybrid exchange-correlation functionals underestimated quadrupole splittings, while still accurately predicted isomer shifts. Out of ∼40 exchange-correlation functionals tested, only MN12L was found to correctly reproduce quadrupole splitting trends in the PcFeL2 complexes coordinated with phosphorus-donor axial ligands (i.e., P(OnBu)3 ≈ P(OEt)3 < PMe3 < P[(CH2O)2CH2]-p-C6H4NO2 < PEt3 ≈ PnBu3). Natural Bond Orbital (NBO) analysis was successfully used to explain the general trends in the observed quadrupole splitting for all compounds of interest. In particular, the general trends in the quadrupole splitting correlate well with the axial ligand dependent, NBO-predicted population of the 3dz2 orbital of the Fe ion and are reflective of the hypothesis proposed by Ohya and co-workers ( Inorg. Chem., 1984, 23, 1303) on the adaptability of the phthalocyanine's π-system toward Fe-Lax interactions. The first X-ray crystal structure of a PcFeL2 complex with axial phosphine ligands is also reported.

Accurate Prediction of the Excited States in the Fully Conjugated Porphyrin Tapes across the Full Spectral Range: A Story of the Interplay between π-π* and Intramolecular Charge-Transfer Transitions in Soft Chromophores.

The ability of density functional theory (DFT) and time-dependent DFT (TDDFT) methods for the accurate prediction of the energies and oscillator strengths of the excited states in a series of fully conjugated meso-meso ß-ß ß-ß triple-linked porphyrin oligomers (porphyrin tapes 2-12) was probed in the gas phase and solution using several exchange-correlation functionals. It was demonstrated that the use of the hybrid B3LYP functional provides a good compromise for the accurate prediction of the localized π-π* and intramolecular charge-transfer transitions, thus allowing confident interpretation of the UV-vis-NIR spectra of porphyrin oligomers. The TDDFT-based sum-over-state (SOS) calculations for the porphyrin tape dimer 2 and trimer 3 as well as parent monomer 1 correctly predicted the signs and shapes of the magnetic circular dichroism (MCD) signals in the low-energy region of the spectra.