4.8 Article

Two-Photon Absorbing Phosphorescent Metalloporphyrins: Effects of π-Extension and Peripheral Substitution

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 48, 页码 15648-15662

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b09157

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资金

  1. National Institutes of Health, USA [EB018464, NS092986, GM103591]
  2. U.S. National Science Foundation through the Penn MRSEC [DMR11-20901]
  3. U.S. National Science Foundation through its optical microscopy SEF
  4. Swiss National Science Foundation
  5. Russian Science Foundation [14-43-00052]
  6. Government of the Russian Federation [02.A03.21.0011]

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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 3r-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. pi-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 Qstates than fully symmetric (D-4h) 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 (phi(phos) = 0.45), strong 2PA makes Pt(II) complexes of pi-extended porphyrins a valuable class of chromophores for 2P applications. Another important advantage of these porphyrinoids is their compact size and easily scalable synthesis.

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