Two-Photon Absorbing Phosphorescent Metalloporphyrins: Effects Of Π-Extension And Peripheral Substitution

Abstract

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.

Publication Date

12-7-2016

Publication Title

Journal of the American Chemical Society

Volume

138

Issue

48

Number of Pages

15648-15662

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/jacs.6b09157

Socpus ID

85003550711 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/85003550711

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