Photophysical Processes in a Novel Porphyrin-perylene Metallosupramolecule with a Long-lived Triplet State†

doi:10.7503/cjcu20140081

Abstract

Abstract:

A new porphyrin-perylene supramolecule, TPPZn-BPHPDI, was obtained by axial coordination of N-pyridyl-N-(1-hexyl)heptylperylene-3,4,9,10-tetracarboximides(BPHPDI) to the zinc ion center of porphyrin metallacycle(TPPZn). The supramolecular system was confirmed by ¹H NMR and ¹H-¹H COSY spectra. The fluorescence titration experiments show that the equilibrium constant of the coordination reaction is 5.32×10⁴L/mol. The analysis of transient nanosecond fluorescence spectra and transient absorption spectra indicates that a long-lived perylene triplet state(101 μs) can form via triplet-triplet energy transfer from the porphyrin to the perylene moiety. Moreover, all above photophysical processes are shown very clearly by means of the energy-level diagram in the paper.

Key words: Porphyrin, Perylene, Supramolecule, Triplet state, T-T energy transfer

CLC Number:

O641.3

TrendMD:

WANG Tianyang, HU Xiaoxia, SUN Haiya, GUO Jianfeng, LIU Dongzhi, LI Wei, WANG Lichang, ZHOU Xueqin. Photophysical Processes in a Novel Porphyrin-perylene Metallosupramolecule with a Long-lived Triplet State^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1753.

Figures/Tables 10

Scheme 1 Formation of the target compound TPPZn-BPHPDI

Fig.1 1H-1H COSY spectrum of TPPZn-BPHPDI

Fig.2 1H NMR spectra of BPHPDI(a), TPPZn- BPHPDI(b) and TPPZn(c)

Fig.3 Absorption spectra(A), fluorescence emission spectra excited at 423 nm(B) and 491 nm(C) of TPPZn, BPHPDI and TPPZn-BPHPDI in dichloromethane with concentration 5×10-6 mol/L and fluorescence emission quenching spectra of BPHPDI(5×10-6 mol/L) with different TPPZn concentrations in dichloromethane(D, λex=491 nm)

Fig.4 Job’s plot of BPHPDI and TPPZn(A), plot of 1/ΔI against 1/[TPPZn](B) and plot of the coordination ratio θ against the TPPZn concentrations in supramolecular system(C) (A) c(BPHPDI)+c(TPPZn)=1×10-4 mol/L in dichloromethane, the excitation wavelength is 491 nm and the discussing emission wavelength is 532 nm. (B) the solid line is the linear fitting result of the experimental data.

Fig.5 Time-resolved fluorescence spectra of TPPZn, BPHPDI and TPPZn-BPHPDI in dichloromethane (A) λex=366 nm, λem=671 nm; (B) λex=457 nm, λem=671 nm. The concentration is 1×10-4 mol/L.

Table 1 Emission lifetimes and fractions(in parentheses) of TPPZn, BPHPDI and TPPZn-BPHPDI in dichloromethane by fitting transient spectra with exponential decay equations

Sample	Emission lifetime, τ/ns(%)
Sample	λ_ex=366 nm, λ_em=671 nm	λ_ex=457 nm, λ_em=671 nm
BPHPDI	5.23(100%)	5.28(100%)
TPPZn	1.69(100%)
TPPZn-BPHPDI	1.50(15.9%), 5.10(81.0%), 18.2(3.1%)	5.22(95.7%), 16.2(4.3%)

Fig.6 Transient absorption difference spectra(A) and time-resolved absorption difference spectra at 470 nm(B) of TPPZn(1×10-5 mol/L) in toluene following excitation with 532 nm, 8 ns laser pulses

Fig.7 Transient absorption difference spectra(A) and time-resolved absorption difference spectra at 529 nm(B) of dyad TPPZn-BPHPDI(1×10-5 mol/L) in toluene following excitation with 532 nm, 8 ns laser pulses

Fig.8 Energy-level diagram and photophysical processes of TPPZn-BPHPDI

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