Hexaphyrin as a Potential Theranostic Dye for Photothermal Therapy and 19F Magnetic Resonance Imaging

Higashino, Tomohiro; Nakatsuji, Hideaki; Fukuda, Ryosuke; Okamoto, Haruki; Imai, Hirohiko; Matsuda, Tetsuya; Tochio, Hidehito; Shirakawa, Masahiro; Tkachenko, Nikolai V.; Hashida, Mitsuru; Murakami, Tatsuya; Imahori, Hiroshi

doi:10.1002/cbic.201700071

Cited by 19 publications

(23 citation statements)

References 59 publications

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“…Expanded porphyrins have attracted considerable attention over the past few decades in view of their large conformational flexibility, facile redox interconversions, novel metal coordination behaviors and versatile electronic states. 1 The rich chemistry of these extended macrocycles has led to diverse applications including near-infrared dyes, 2 nonlinear optical materials, 3 magnetic resonance imaging contrast agents 4 and molecular switches. 5 In contrast to the regular porphyrin, expanded porphyrins are flexible enough to switch between different π-conjugation topologies (Hückel, Möbius and twisted-Hückel), each with different properties (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

Woller¹,

Banerjee²,

Sylvetsky³

et al. 2019

Preprint

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Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. Taking into account its size and huge conformational flexibility, DFT remains the workhorse for modeling such extended macrocycles. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, p···p stacking, steric effects, ring strain and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wavefunction methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a pronouncedly stronger degree of static correlation than the Hückel and figure-eight structures, and as a result the relative energies of singly-twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between MP2/cc-pVDZ and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol-1 with the CCSD(T) relative energies. Regarding DFT methods, only M06-2X provides relative errors close to chemical accuracy with a RMSD of 1.2 kcal mol-1. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended p-systems, the errors drop down to 2 kcal mol-1 for the revised revDSD-PBEP86-NL, again showing that same-spin MP2-like correlation has a detrimental impact on performance like the SOS-MP2 results.

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Section: Introductionmentioning

confidence: 99%

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

Woller¹,

Banerjee²,

Sylvetsky³

et al. 2019

Preprint

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“…Specifically, compounds with greater aromatic character were found to give rise to higher TPA cross-section values, which is a third-order NLO process. Relative to the parent porphyrin, expanded porphyrins exhibit spectacularly high TPA cross-section values [ 7 , 18 , 19 ], so they are very promising candidates for biomedical applications, such as photodynamic therapy [ 20 ]. Moreover, several studies found a close relationship between molecular topology, aromaticity and NLO properties in expanded porphyrins [ 11 , 12 ] and demonstrate that Hückel-to-Möbius topological switches behave as efficient optical switches [ 21 , 22 , 23 ].…”

Section: Introductionmentioning

confidence: 99%

Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids

et al. 2018

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With their versatile molecular topology and aromaticity, porphyrinoid systems combine remarkable chemistry with interesting photophysical properties and nonlinear optical properties. Hence, the field of application of porphyrinoids is very broad ranging from near-infrared dyes to opto-electronic materials. From previous experimental studies, aromaticity emerges as an important concept in determining the photophysical properties and two-photon absorption cross sections of porphyrinoids. Despite a considerable number of studies on porphyrinoids, few investigate the relationship between aromaticity, UV/vis absorption spectra and nonlinear properties. To assess such structure-property relationships, we performed a computational study focusing on a series of Hückel porphyrinoids to: (i) assess their (anti)aromatic character; (ii) determine the fingerprints of aromaticity on the UV/vis spectra; (iii) evaluate the role of aromaticity on the NLO properties. Using an extensive set of aromaticity descriptors based on energetic, magnetic, structural, reactivity and electronic criteria, the aromaticity of [4n+2] π-electron porphyrinoids was evidenced as was the antiaromaticity for [4n] π-electron systems. In agreement with previous studies, the absorption spectra of aromatic systems display more intense B and Q bands in comparison to their antiaromatic homologues. The nature of these absorption bands was analyzed in detail in terms of polarization, intensity, splitting and composition. Finally, quantities such as the average polarizability and its anisotropy were found to be larger in aromatic systems, whereas first and second hyperpolarizability are influenced by the interplay between aromaticity, planarity and molecular symmetry. To conclude, aromaticity dictates the photophysical properties in porphyrinoids, whereas it is not the only factor determining the magnitude of NLO properties.

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“…Under excitation at 445 nm via acw diode laser, at oluene solution of t-Pd 2 -3 exhibited an emission band at l max = 1507 nm, despite the seemingly large nonradiative decay rate in the NIR-III energy region according to the energy-gap law. [45,46] To the best of our knowledge, the emission energy was the lowest among the expanded porphyrins.O ne example of this,c yclo [8]pyrrole,e mits at l em = 1480 nm in toluene. [3] Although we were unable to estimate the accurate emission quantum yield (F:l ess than 0.01 %) because of the lack of reference emitters in this region, the emissive behavior was clearly influenced by the temperature and the choice of solvents.Lowering the temperature resulted in an increased overall emission intensity ( Figure S21).…”

Section: Forschungsartikelmentioning

confidence: 99%

“…Expanded porphyrins,t he p-conjugated analogues [1,2] of naturally occurring tetrapyrrole pigments with larger cores, are promising dyes for use in near-infrared (NIR) bioimaging projects,p hotodynamic/thermal therapies,s ensors,a nd optical devices. [3][4][5][6][7][8][9][10][11][12] Fors uch applications,p recise energy-gap engineering of the highest occupied molecular orbital (HO-MO) and the lowest unoccupied molecular orbital (LUMO) of p-conjugated molecules is critical and has become one of the foremost research topics in the field. Specifically,s uch emerging expanded homologues allow photoresponsivity in the sought-after second NIR window [13] (NIR-II:1 000-1400 nm) beyond the conventional NIR-I energy (l = 700-1000 nm) to meet the growing need for imaging applications that call for higher spatial resolution, improved signal-tobackground ratio,a nd better light-penetration depth in the biological tissues.…”

Section: Introductionmentioning

confidence: 99%

Near‐Infrared‐III‐Absorbing and ‐Emitting Dyes: Energy‐Gap Engineering of Expanded Porphyrinoids via Metallation

et al. 2020

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The synthesis of organometallic complexes of modified 26π‐conjugated hexaphyrins with absorption and emission capabilities in the third near‐infrared region (NIR‐III) is described. Symmetry alteration of the frontier molecular orbitals (MOs) of bis‐PdII and bis‐PtII complexes of hexaphyrin via N‐confusion modification led to substantial metal dπ–pπ interactions. This MO mixing, in turn, resulted in a significantly narrower HOMO–LUMO energy gap. A remarkable long‐wavelength shift of the lowest S0→S1 absorption beyond 1700 nm was achieved with the bis‐PtII complex, t‐Pt2‐3. The emergence of photoacoustic (PA) signals maximized at 1700 nm makes t‐Pt2‐3 potentially useful as a NIR‐III PA contrast agent. The rigid bis‐PdII complexes, t‐Pd2‐3 and c‐Pd2‐3, are rare examples of NIR emitters beyond 1500 nm. The current study provides new insight into the design of stable, expanded porphyrinic dyes possessing NIR‐III‐emissive and photoacoustic‐response capabilities.

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Hexaphyrin as a Potential Theranostic Dye for Photothermal Therapy and ¹⁹F Magnetic Resonance Imaging

Cited by 19 publications

References 59 publications

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids

Near‐Infrared‐III‐Absorbing and ‐Emitting Dyes: Energy‐Gap Engineering of Expanded Porphyrinoids via Metallation

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