Intersystem Crossing in Naphthalenediimide–Oxoverdazyl Dyads: Synthesis and Study of the Photophysical Properties. Issue 68 (6th November 2019) - Hussain, Mushraf
Abstract: Oxoverdazyl (Vz) radical units were covalently linked to the naphthalenediimide (NDI) chromophore to study the effect of the radical on the photophysical properties, especially the radical enhanced intersystem crossing (REISC), which is a promising approach to develop heavy‐atom‐free triplet photosensitizers. Rigid phenyl or ethynylphenyl linkers between the two moieties were used, thus REISC and formation of doublet (D1, total spin quantum number S =1/2) and quartet states (Q1, S =3/2) are anticipated. The photophysical properties of the dyads were studied with steady‐state and femtosecond/nanosecond transient absorption (TA) spectroscopies and DFT computations. Femtosecond transient absorption spectra show a fast electron transfer (<150 fs), and ISC (ca. 1.4–1.85 ps) is induced by charge recombination (CR, in toluene). Nanosecond transient absorption spectra demonstrated a biexponential decay of the triplet state of the NDI moiety. The fast component (lifetime: 50 ns; population ratio: 80 %) is assigned to the D1 →D0 decay, and the slow decay component (2.0 μs; 20 %) to the Q1 →D0 ISC. DFT computations indicated ferromagnetic interactions between the radical and chromophore ( J= 0.07–0.13 eV). Reversible formation of the radical anion of the NDI moiety by photoreduction of the radical‐NDI dyads in the presence of sacrificial electron donor triethanolamine (TEOA) is achieved. This work is useful for design of new triplet photosensitizers based on the REISC effect. Abstract : Get radical ! Naphthalenediimide (NDI)–verdazyl dyads are synthesized to study the effect of radicals on the photophysical properties. Fluorescence quenching and ultrafast electron transfer were observed, followed by charge recombination‐induced intersystem crossing. Spin–spin interactions of the NDI triplet state with the verdazyl radical results in doublet (D1 ) and quartet states (Q1 ). Reversible formation of the radical anion of the NDI moiety was also achieved (see figure).