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The elusive PcFe(DABCO)2 (Pc = phthalocyaninato(2-) ligand; DABCO = 1,4-diazabicyclo[2.2.2]octane) complex was prepared and characterized by UV-Vis, MCD, 1H NMR, and Mössbauer spectroscopies. The X-ray crystal structure of this complex indicates the longest Fe-N(DABCO) bond distance among all known PcFeL2 complexes with nitrogen donors as the axial ligands. The target compound is only stable in the presence of large access of the axial ligand and rapidly converts into the (PcFe)2O [Formula: see text]-oxo dimer even at a modest temperature. The electronic structure of the PcFe(DABCO)2 complex was elucidated by DFT and TDDFT methods. The DFT calculations predicted a very small singlet-triplet gap in this compound. The femtosecond transient absorption spectroscopy is indicative of extremely fast ([Formula: see text]200 fs) deactivation of the first excited state in PcFe(DABCO)2 with a lack of formation of the long-lived low-energy triplet state.

Metal-free, magnesium, titanyl, and vanadyl tetrapyrazinoporphyrazines substituted with eight 2,6-diisopropylphenoxy groups at the peripheral positions were prepared and characterized by NMR, UV-Vis, magnetic circular dichroism (MCD), and mass spectrometry methods. In addition, the Pc(2,6iPrPhO)8VO complex was characterized by EPR spectroscopy and X-ray crystallography. Reaction between TiCl4 with 4,5-(2,6-diisopropylphenoxy)phthalonitrile in N,N-dimethylaminoethanol resulted in the formation of a red open-chain trimer, which was characterized by mass spectrometry and X-ray crystallography. Electronic structures of new compounds and their excited state properties were probed by Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) methods.

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.

It is well-known that treatment of β-octaethylporphyrin with H2 O2 /conc. H2 SO4 converts it to a β-oxochlorin as well as all five constitutional isomers of the corresponding β,β'-dioxo-derivatives: two bacteriochlorin-type isomers (β-oxo groups at opposite pyrrolic building blocks) and three isobacteriochlorin-type isomers (β-oxo-groups at adjacent pyrrolic building blocks). By virtue of the presence of the strongly electronically coupled β-oxo auxochromes, none of the chromophores are archetypical chlorins, bacteriochlorins, or isobacteriochlorins. Here the authors present, inter alia, the single crystal X-ray structures of all free-base diketone isomers and a comparative description of their UV-vis absorption spectra in neutral and acidic solutions, and fluorescence emission and singlet oxygen photosensitization properties, Magnetic Circular Dichroism (MCD) spectra, and singlet excited state lifetimes. DFT computations uncover underlying tautomeric equilibria and electronic interactions controlling their electronic properties, adding to the understanding of porphyrinoids carrying β-oxo functionalities. This comparative study lays the basis for their further study and utilization.

The reduction of iron(II) phthalocyanine (Pc(2-)Fe

1,3-Diiminoisoindoline (DII) and the closely related molecule, iminoisoindolinone are important precursors in the synthesis of macrocycles and chelates such as phthalocyanines, and bis(arylimino)isoindolines, as well as chromophores including aza-BODIPY dyes. A series of seven ylideneisoindolinones are presented in this report. The reaction of various organic CH acids and iminoisoindolinone produce compounds that show strong [Formula: see text]* transitions in the UV region. The chromophores have been characterized spectroscopically and the X-ray structures show electronic delocalization across the chromophore. Additionally, DFT and time-dependent DFT calculations confirm the lower energy absorbances are primarily HOMO-LUMO transitions.

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.

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.

A one-step synthetic pathway for the preparation of fully conjugated β-isoindigo-azaDIPY hybrid chromophores comprised of β-isoindigo and azadipyrromethene moieties is reported. The target compounds were characterized by spectroscopic, crystallographic, and theoretical methods and show unprecedented broad absorption across the visible region of the electromagnetic spectrum. The X-ray crystal structure of the octa(n-butyl)-β-isoindigo-azaDIPY derivative revealed that a trans-configuration of the β-isoindigo fragment accompanies a planar conjugated core.

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-β-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 β-isoindigo synthesis resulting either in the selective formation of dithio- or diamino-β-isoindigo chromophores. The

A bridging carbon analog of the well-studied bis(pyridyl)iminoisoindoline (BPI) can be produced via a one step reaction between diiminoisoindoline and pyridine-2-acetonitrile. The resultant bis(pyridineylidene)isoindoline (BPYI) is structurally analogous to BPI and can readily form metal complexes. However, it exhibits a markedly different electronic structure with intense absorption bands in the visible region of the spectrum.

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 PcFeL

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-sp

The electronic communication between two ferrocene groups in the electron-deficient expanded aza-BODIPY analogue of zinc manitoba-dipyrromethene (MB-DIPY) was probed by spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods. The excited-state dynamics involved sub-ps formation of the charge-separated state in the organometallic zinc MB-DIPYs, followed by recovery of the ground state via charge recombination in 12 ps. The excited-state behavior was contrasted with that observed in the parent complex that lacked the ferrocene electron donors and has a much longer excited-state lifetime (670 ps for the singlet state). Much longer decay times observed for the parent complex without ferrocene confirm that the main quenching mechanism in the ferrocene-containing 4 is reflective of the ultrafast ferrocene-to-MB-DIPY core charge transfer (CT).

A series of PtII-based monometallic (H2PtL), homobimetallic (Pt2L), and heterobimetallic (NiPtL and PdPtL) group 10 complexes of the previously established expanded twin porphyrin (H4L) were prepared. Structural characterization of the bimetallic PtII series (Pt2L, NiPtL, and PdPtL) revealed their similar general structures, with slight differences correlated to the ion size. An improvement of the metal-ion insertion process also allowed efficient preparation of the known Pd2L complex, and the novel heterobimetallic NiPdL complex was also structurally characterized. UV-vis spectroscopy, NMR spectroscopy, magnetic circular dichroism (MCD), and (spectro)electrochemistry were used to characterize the complexes; the electronic properties followed largely established lines for metal complexes of the twin porphyrin, except that the PtII-based systems exhibited more complex UV-vis spectral signatures. MCD spectra accompanied by density functional theory (DFT)/time-dependent DFT computations (TDDFT) rationalize the origins of the optical features of the twin porphyrin. The presence of the nonplanar, nonaromatic macrocyclic π system with conjugation pathways confined to each half of the molecule could be visualized. Significant pyrazole(π) → pyrrole(π*) charge-transfer character was predicted for several transitions in the visible region. This study adds to our fundamental understanding of the formation, structure, and electronic structure of bimetallic complexes of this class of expanded metalloporphyrins containing nonpyrrolic moieties.

The electronic structures of a set of PcFe(azole)2 complexes (azole = imidazole, [Formula: see text]-methylimidazole, pyrazole, isoxazole, thiazole, 1,2,4-triazole, 3-amino-1,2,4,-triazole, and 5-amino-1,2,3,4-tetrazole) were examined by Mössbauer spectroscopy and Density Functional Theory (DFT) calculations. In addition, the geometric distortions in these compounds were elucidated by X-ray crystallography for imidazole, pyrazole, and thiazole-containing compounds. Predicted by DFT calculations, Mössbauer hyperfine parameters for all compounds are in reasonable agreement with experimental results, and the influence of the [Formula: see text]-donor and [Formula: see text]-acceptor properties of the axial azoles on the electronic structure of the PcFe(azole)2 complexes is demonstrated by comparison with the reference PcFePy2 compound.

Two sets of FeIII/II dithione complexes [FeII(iPr2Dt0)3][PF6]2 ([1][PF6]2), [FeII(Me2Dt0)3][PF6]2 ([2][PF6]2), and [FeIII(iPr2Dt0)3][PF6]3 ([3][PF6]3), [FeIII(Me2Dt0)3][PF6]3 ([4][PF6]3), and compound [FeIII(iPr2Dt0)3][FeCl4][PF]2 ([3][FeCl4][PF6]2) were synthesized from N,N′-diisopropyl piperazine-2,3-dithione (iPr2Dt0) and N,N′-dimethyl piperazine-2,3-dithione (Me2Dt0) ligands. Complexes [1][PF6]2–[4][PF6]3 have been characterized by NMR, IR, and UV-visible spectroscopies, and by electrochemistry. The molecular structures of [2][PF6]2 and [3][FeCl4][PF6]2 have been determined by X-ray crystallography. Complexes [2][PF6]2 and [3][FeCl4][PF6]2 both crystallized in the monoclinic space group P21/n. Both complexes exhibit distorted octahedral geometry and the three coordinated ligands in each complex exhibit different dithione folding. Complexes [1][PF6]2–[4][PF6]3 exhibit a single FeIII/II based couple and three quasi-reversible ligand-based redox couples. The electronic spectra of [1][PF6]2–[4][PF6]3 show intense MLCT bands that indicate strong mixing between metal and ligand orbitals. DFT calculations were used to provide a framework for understanding the electronic origin of their redox chemistry and spectroscopic features.

The hemiporphyrazine type chelate and phthalocyaninine analog biliazine (H2BlzH) and its metal complexes can be synthesized in one-step from a monosubstituted diiminisoindoline (DII). This singly substituted precursor is produced from the reaction of unsubstituted DII and 2-aminopyrazole. The biliazine macrocycle is a tetradentate chelate where the ring is closed via a strong hydrogen bond at the meso position. Although the hydrogen bond closes the ring, there is little evidence for 18-electron type annulene aromaticity across the macrocycle, as seen in the UV-visible and MCD spectra and supported by DFT calculations.

The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL

The impact of the porphyrinoid macrocycle, central-metal ion, and substituent-based electron-transfer processes under electro- and spectroelectrochemical conditions are discussed in this chapter. Potential applications are highlighted.

The chemically or spectroelectrochemically generated formation and aggregation of zinc(II) tetra-tert-butylphthalocyanine cation radical [ZnPctBu]+•, which was highly soluble in common organic solvents, were investigated using UV-vis and magnetic circular dichroism (MCD) spectroscopies with an emphasis on the influence of the axial ligand on the fingerprint (∼500 nm) and NIR (720∼1000 nm) spectral envelopes. MCD spectroscopy is suggestive that the NIR band at ∼1000 nm observed for the antiferromagnetically coupled cation radical dimer, [ZnPctBu]22+, has no degeneracy, the monomer-dimeric equilibrium is temperature dependent, and higher degree aggregates can be formed at specific conditions. Sixteen different exchange-correlation functionals were tested to accurately predict the energies, intensities, and profiles of the UV-vis and MCD spectra of the phthalocyanine cation radical monomer and dimer. It was found that the M05 exchange-correlation functional (along with several other functionals that include 27-42% of Hartree-Fock exchange) provided an excellent agreement (∼0.1 eV for the degenerate excited states observed by MCD spectroscopy) between theory and experiment for the phthalocyanine cation-radical monomer and dimer. Not only did time-dependent density functional theory (TDDFT) calculations with M05 exchange-correlation functional correctly predict the nondegenerate NIR charge-transfer band at ∼1000 nm, all degenerate excited states, monomer and dimer energies, and oscillator strengths, but also they correctly described the nature of the experimentally observed at ∼500 nm MCD B-term (fingerprint band) detected for both the monomeric and dimeric phthalocyanine cation radicals. The TDDFT data explain the similarities in the UV-vis and MCD spectra of the monomeric and dimeric species observed between the UV and fingerprint spectral envelopes as well as correctly predicted the antiferromagnetic coupling between the two singly oxidized phthalocyanine macrocycles in the dimer.

We developed a simple methodology for the preparation of stable meso-(nitrile oxide)-substituted BODIPYs, which were characterized by spectroscopic methods and X-ray crystallography. These compound...

Two isomeric ruthenium(II)/5,10,15,20-tetraphe-nylporphyrin complexes featuring axially coordinated redox-active, low-optical gap 2- or 6-isocyanoazulene ligands have been isolated and characterized by NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopic methods, high-resolution mass spectrometry, and single-crystal X-ray crystallography. The UV-vis and MCD spectra support the presence of the low-energy, azulene-centered transitions in the Q band region of the porphyrin chromophore. The first coordination sphere in new L2RuTPP complexes reflects compressed tetragonal geometry. The redox properties of the new compounds were assessed by electrochemical and spectroelectrochemical means and correlated with the electronic structures predicted by density functional theory and CASSCF calculations. Both experimental and theoretical data are consistent with the first two reduction processes involving the axial azulenic ligands, whereas the oxidation profile (in the direction of increasing potential) is exerted by the ruthenium ion, the porphyrin core, and the axial azulenic moieties.

A series of covalent ferrocene-BODIPY-fullerene triads with the ferrocene groups conjugated to the BODIPY π-system and the fullerene acceptor linked at the boron hub by a common catecholpyrrolidine bridge were prepared and characterized by 1D and 2D NMR, UV/Vis, steady-state fluorescence spectroscopy, high-resolution mass spectrometry, and, for one of the derivatives, X-ray crystallography. Redox processes of the new compounds were investigated by electrochemical (CV and DPV) methods and spectroelectrochemistry. DFT calculations indicate that the HOMO in all triads was delocalized between ferrocene and BODIPY π-system, the LUMO was always fullerene-centered, and the catechol-centered occupied orbital was close in energy to the HOMO. TDDFT calculations were indicative of the low-energy, low-intensity charge-transfer bands originated from the ferrocene-BODIPY core to fullerene excitation, which explained the similarity of the UV/Vis spectra of the ferrocene-BODIPY dyads and ferrocene-BODIPY-fullerene triads. Photophysical properties of the new triads as well as reference BODIPY-fullerene and ferrocene-BODIPY dyads were investigated by pump-probe spectroscopy in the UV/Vis and NIR spectral regions following selective excitation of the BODIPY-based antenna. Initial charge transfer from the ferrocene to the BODIPY core was shown to outcompete sub-100 fs deactivation of the excited state mediated by the catechol bridge. However, no subsequent electron transfer to the fullerene acceptor was observed. The initial charge separated state relaxes by recombination with a time constant of 150-380 ps.

A series of a fully conjugated ferrocene-containing coumarins and B,O-chelated coumarins was prepared and characterized by a variety of spectroscopic (UV–vis, NMR, and mass spectrometry), electrochemical (CV and DPV) and spectroelectrochemical methods. The photophysical properties of the target compounds were investigated by steady-state fluorescence and ultrafast transient absorption spectroscopy methods. Selective photoexcitation of the coumarin core was followed by ultrafast electron transfer from the ferrocene fragment, resulting in formation of a charge-separated Fc+-coumarin-. state. This charge-separated state undergoes ultrafast ground state recovery in 20–25 ps, shortening the excited state lifetime of the organic coumarin precursors (1.2–1.5 ns) by almost two orders of magnitude. Formation of the charge-separated states was supported by the experimental (steady-state fluorescence oxidative titrations) and theoretical DFT and TDDFT calculations.

A ditriflate derivative of 2-iodoxybenzoic acid (IBX) was prepared by the reaction of IBX with trifluoromethanesulfonic acid and characterized by single crystal X-ray crystallography. IBX-ditriflate is the most powerful oxidant in a series of structurally similar IBX derivatives which is best illustrated by its ability to readily oxidize hydrocarbons and the oxidation resistant polyfluoroalcohols.

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 β-β β-β 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.

Density Functional Theory (DFT) calculations coupled with several exchange-correlation functionals were used for the prediction of Mossbauer 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 Mossbauer 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.

The direct borylation of two bis(pyrazolylimino)isoindoline chelates with BF3 and base under dry conditions results in the formation of two boron adducts. These are ring-contracted analogs of biliazine and can be considered as subbiliazines, as they have bowl-shaped structures similar to subphthalocyanine. Additionally, a new iminooxoisoindoline BF2 complex was made from hydrolysis of the free base in the presence ofBF3. The electronic structures of the free bases and subbiliazines were probed by density functional theory (DFT) and time-dependent DFT (TDDFT) methods.

This mini-review summarizes the synthesis strategies for the preparation and post-functionalization of aza-BODIPYs, BOPHYs, “half-Pcs”, biliazines, MB-DIPYs, semihemiporphyrazines, BOIMPYs, BOPPYs, BOPYPYs, BOAHYs, and BOAPYs.

Several pyrene-boron-dipyrromethene (BODIPY) and pyrene-BODIPY-ferrocene derivatives with a fully conjugated pyrene fragment appended to the α-position(s) of the BODIPY core have been prepared by Knoevenagel condensation reaction and characterized by one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR), UV-vis, fluorescence spectroscopy, high-resolution mass spectrometry as well as X-ray crystallography. The redox properties of new donor-acceptor BODIPY dyads and triads were studied by electrochemical (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)) and spectroelectrochemical approaches. Formation of weakly bonded noncovalent complexes between the new pyrene-BODIPYs and nanocarbon materials (C60, C70, single-walled carbon nanotube (SWCNT), and graphene) was studied by UV-vis, steady-state fluorescent, and time-resolved transient absorption spectroscopy. UV-vis and fluorescent spectroscopy are indicative of the much stronger and selective interaction between new dyes and (6,5)-SWCNT as well as graphene compared to that of C60 and C70 fullerenes. In agreement with these data, transient absorption spectroscopy provided no evidence for any significant change in excited-state lifetime or photoinduced charge transfer between pyrene-BODIPYs and C60 or C70 fullerenes when the pyrene-BODIPY chromophores were excited into the lowest-energy singlet excited state. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations suggest that the pyrene fragments are fully conjugated into the π-system of BODIPY core, which correlates well with the experimental data.

The reaction between MB-DIPY sodium salts and Ag(I) ions results in the formation of unprecedented MB-DIPY2Ag2 dimers in both solution and the solid state. These dimers have a short Ag–Ag contact (∼2.9 A) and orthogonal twist in each of the MB-DIPY chromophores. The electronic structure of the unique dimers was probed by spectroscopic and theoretical methods.

An insight into the electronic structure of the metal-free, unsubstituted, and nonperipherally substituted with electron-donating groups tetraazaporphyrin (H2TAP), phthalocyanine (H2Pc), naphthalocyanine (H2Nc), anthracocyanine (H2Ac) platforms has been gained and discussed on the basis of experimental UV-vis and MCD spectra as well as density functional theory (DFT), time-dependent DFT (TDDFT), and semiempirical ZINDO/S calculations. Experimental data are suggestive of potential crossover behavior between the 1 1B2u and 1 1B3u excited states (in traditional D2h notation) around 800 nm. A large array of exchange-correlation functionals were tested to predict the vertical excitation energies in H2TAPs, H2Pcs, H2Ncs, and H2Acs both in gas phase and solution. In general, TDDFT-predicted energies of the Q x and Q y bands and the splitting between them correlate well with the amount of Hartree-Fock exchange present in a specific exchange-correlation functional with the long-range corrected LC-BP86 and LC-wPBE functionals providing the best agreement between theory and experiment. The pure GGA (BP86) exchange-correlation functional significantly underestimated, while long-range corrected LC-BP86 and LC-wPBE exchange-correlation functionals and semiempirical ZINDO/S method strongly overestimated the intramolecular charge-transfer (ICT) transitions experimentally observed for -OR, -SR, and -NR2 substituted at nonperipheral position phthalocyanines and their analogues in the 450-650 nm region. The hybrid CAM-B3LYP, PBE1PBE, and B3LYP exchange-correlation functionals were found to be much better in predicting energies of such ICT transitions. Overall, we did not find a single exchange-correlation functional that can accurately (MAD < 0.05 eV) and simultaneously predict the energies and the splittings of the Q x and Q y bands as well as energies of the ICT transitions in a large array of substituted and unsubstituted metal-free phthalocyanines and their benzoannulated analogues.