Magnetic circular dichroism of cyclic .pi.-electron systems. 2. Algebraic solution of the perimeter model for the B terms of systems with a (4N + 2)-electron [n]annulene perimeter

Geometry optimizations and TD-DFT calculations have been carried out on series of fused-ring-expanded phthalonitriles, phthalocyanines, and aza-dipyrromethene boron difluoride (aza-BODIPY) dyes and trends in their optical and redox properties have been analyzed. The potential utility of fused-ring-expanded phthalocyanine and aza-BODIPY analogues for photodynamic therapy and near infrared region sensor applications is assessed on this basis. Recent attempts to prepare fused-ring-expanded aza-BODIPY analogues with benzene, pyrazine, and naphthalene rings have demonstrated that the properties of aza-BODIPYs vary markedly when different fused ring systems are added to the β -carbons of the pyrrole rings. A comparison of the TD-DFT calculations demonstrates that, as has previously been postulated, trends in the optical spectra, redox properties, and electronic structures of aza-BODIPYs follow those observed for the phthalonitrile precursors and the analogous phthalocyanines despite the absence of a fully conjugated macrocyclic perimeter that obeys Hückel's rule.

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“…15 Series of tetraazaporphyrins with peripheral pyrazine (13)(14)(15)(16)(17) and benzopyrazine (18-22) moieties were also studied.…”

Section: Resultsmentioning

confidence: 99%

TD-DFT calculations and MCD spectroscopy of porphyrin and phthalocyanine analogues: rational design of photosensitizers for PDT and NIR region sensor applications

Mack¹,

Wildervanck

Nyokong

2014

Turk J Chem

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“…2) of the a and s MOs (the DHOMO value in Michl's terminology) and the -a and -s MOs (the DLUMO value). Michl [33][34][35][36] has demonstrated that a +/−/+/− sign sequence is observed when DLUMO > DHOMO as is the case with 3a-3c (Fig. 2).…”

Section: Optical Spectra and Td-dft Calculationsmentioning

confidence: 91%

“…The electronic structures and optical spectra of porphyrinoids can be readily rationalized by using Gouterman's 4orbital model [32] and Michl's perimeter model [33][34][35][36]. The electronic structures and optical properties of corroles are reasonably similar to those of porphyrins [37].…”

Section: Optical Spectra and Td-dft Calculationsmentioning

confidence: 99%

“…Since the HOMO and LUMO have M L values of ±4 and ±5, respectively, Gouterman's 4orbital model predicts the presence of an allowed B transition (DM L = ±1) at high energy and a forbidden Q transition (DM L = ±9) at low energy for porphyrins and their analogs such as corroles. Michl [33][34][35][36] referred to the pMOs that are derived from the HOMO and LUMO of the parent perimeter as the a and -a MOs, respectively, if angular nodal planes lie on the yaxis, or as the s and -s MOs for the corresponding MOs that have significant MO coefficients on the yaxis (Fig. 1).…”

Section: Optical Spectra and Td-dft Calculationsmentioning

confidence: 99%

“…Only oneelectron transitions that contribute more than 5% are included. Those associated exclusively with the a, s, -a and -s MOs of Michl's perimeter model [33][34][35][36] since they demonstrate that binding with porphyrinoid chromophores with strong intramolecular charge transfer properties could result in less efficient photocleavage by singlet oxygen and hydroxyl radicals.…”

Section: Ctdna Interactionmentioning

confidence: 99%

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Push–pull type manganese(III)corroles: Synthesis, electronic structures and tunable interactions with ctDNA

Fang

et al. 2017

J. Porphyrins Phthalocyanines

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ABSTRACT:The synthesis of three low symmetry A 2 B type Mn(III)triarylcorroles with mesoaryl substituents that provide push-pull electrondonating and withdrawing properties is reported. An analysis of the structureproperty relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A 2 B type Mn(III)triarylcorroles interact strongly with cellfree circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electrondonating substituent is introduced at the 10position of the mesotriarylcorrole ligand.

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Insight into externally bound 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrinatopalladium(II), PdP(2), with B-form DNA duplexes poly(G-C)2, poly(A-T)2, and CT DNA by using combined MCD, CD, and optical data

et al. 1998

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Magnetic circular dichroism of cyclic .pi.-electron systems. 2. Algebraic solution of the perimeter model for the B terms of systems with a (4N + 2)-electron [n]annulene perimeter

Cited by 162 publications

References 3 publications

TD-DFT calculations and MCD spectroscopy of porphyrin and phthalocyanine analogues: rational design of photosensitizers for PDT and NIR region sensor applications

TD-DFT calculations and MCD spectroscopy of porphyrin and phthalocyanine analogues: rational design of photosensitizers for PDT and NIR region sensor applications

Push–pull type manganese(III)corroles: Synthesis, electronic structures and tunable interactions with ctDNA

Insight into externally bound 5,10,15,20-tetrakis(2-N-methylpyridyl)porphyrinatopalladium(II), PdP(2), with B-form DNA duplexes poly(G-C)2, poly(A-T)2, and CT DNA by using combined MCD, CD, and optical data

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