Dataset Information

NIR-Absorbing ?-Extended Azulene: Non-Alternant Isomer of Terrylene Bisimide.

ABSTRACT: The first planar ?-extended azulene that retains aromaticity of odd-membered rings was synthesized by [3+3] peri-annulation of two naphthalene imides at both long-edge sides of azulene. Using bromination and subsequent nucleophilic substitution by methoxide and morpholine, selective functionalization of the ?-extended azulene was achieved. Whilst these new azulenes can be regarded as isomers of terrylene bisimide they exhibit entirely different properties, which include very narrow optical and electrochemical gaps. DFT, TD-DFT, as well as nucleus-independent chemical shift calculations were applied to explain the structural and functional properties of these new ??scaffolds. Furthermore, X-ray crystallography confirmed the planarity of the reported ?-scaffolds and aromaticity of their azulene moiety.

SUBMITTER: Pigulski B

PROVIDER: S-EPMC7540366 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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NIR-Absorbing π-Extended Azulene: Non-Alternant Isomer of Terrylene Bisimide.

Pigulski Bartłomiej B Shoyama Kazutaka K Würthner Frank F

Angewandte Chemie (International ed. in English) 20200625 37

The first planar π-extended azulene that retains aromaticity of odd-membered rings was synthesized by [3+3] peri-annulation of two naphthalene imides at both long-edge sides of azulene. Using bromination and subsequent nucleophilic substitution by methoxide and morpholine, selective functionalization of the π-extended azulene was achieved. Whilst these new azulenes can be regarded as isomers of terrylene bisimide they exhibit entirely different properties, which include very narrow optical and e ...[more]

PMID: 32441847

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Project description:The ability to form triplet excited states upon two-photon excitation is important for several applications of metalloporphyrins, including two-photon phosphorescence lifetime microscopy (2PLM) and two-photon photodynamic therapy (PDT). Here we analyzed one-photon (1P) and degenerate two-photon (2P) absorption properties of several phosphorescent Pt (II) porphyrins, focusing on the effects of aromatic π-extension and peripheral substitution on triplet emissivity and two-photon absorption (2PA). Our 2PA measurements for the first time made use of direct time-resolved detection of phosphorescence, having the ability to efficiently reject laser background through microsecond time gating. π-Extension of the porphyrin macrocycle by way of syn-fusion with two external aromatic fragments, such as in syn-dibenzo- (DBP) and syn-dinaphthoporphyrins (DNP), lowers the symmetry of the porphyrin skeleton. As a result, DBPs and DNPs exhibit stronger 2PA into the one-photon-allowed B (Soret) and Q states than fully symmetric (D4h) nonextended porphyrins. However, much more 2P-active states lie above the B state and cannot be accessed due to the interfering linear absorption. Alkoxycarbonyl groups (CO2R) in the benzo-rings dramatically enhance 2PA near the B state level. Time-dependent density functional theory (TDDFT) calculations in combinations with the sum-over-states (SOS) formalism revealed that the enhancement is due to the stabilization of higher-lying 2P-active states, which are dominated by the excitations involving orbitals extending onto the carbonyl groups. Furthermore, calculations predicted even stronger stabilization of the 2P-allowed gerade-states in symmetric Pt octaalkoxycarbonyl-tetrabenzoporphyrins. Experiments confirmed that the 2PA cross-section of PtTBP(CO2Bu)8 near 810 nm reaches above 500 GM in spite of its completely centrosymmetric structure. Combined with exceptionally bright phosphorescence (ϕphos = 0.45), strong 2PA makes Pt(II) complexes of π-extended porphyrins a valuable class of chromophores for 2P applications. Another important advantage of these porphyrinoids is their compact size and easily scalable synthesis.

Dataset Information

NIR-Absorbing ?-Extended Azulene: Non-Alternant Isomer of Terrylene Bisimide.

Publications

NIR-Absorbing π-Extended Azulene: Non-Alternant Isomer of Terrylene Bisimide.

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