Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N Pt^II–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Abstract

Room-temperature long-lived near-IR phosphorescence of boron-dipyrromethene (BODIPY) was observed (λ(em) = 770 nm, Φ(P) = 3.5 %, τ(P) = 128.4 μs). Our molecular-design strategy is to attach Pt(II) coordination centers directly onto the BODIPY π-core using acetylide bonds, rather than on the periphery of the BODIPY core, thus maximizing the heavy-atom effect of Pt(II). In this case, the intersystem crossing (ISC) is facilitated and the radiative decay of the T(1) excited state of BODIPY is observed, that is, the phosphorescence of BODIPY. The complex shows strong absorption in the visible range (ε = 53,800 M(-1) cm(-1) at 574 nm), which is rare for Pt(II)-acetylide complexes. The complex is dual emissive with (3)MLCT emission at 660 nm and the (3)IL emission at 770 nm. The T(1) excited state of the complex is mainly localized on the BODIPY moiety (i.e. (3)IL state, as determined by steady-state and time-resolved spectroscopy, 77 K emission spectra, and spin-density analysis). The strong visible-light-harvesting ability and long-lived T(1) excite state of the complex were used for triplet-triplet annihilation based upconversion and an upconversion quantum yield of 5.2 % was observed. The overall upconversion capability (η = ε×Φ(UC)) of this complex is remarkable considering its strong absorption. The model complex, without the BODIPY moiety, gives no upconversion under the same experimental conditions. Our work paves the way for access to transition-metal complexes that show strong absorption of visible light and long-lived (3)IL excited states, which are important for applications in photovoltaics, photocatalysis, and upconversions, etc.

Recent advance of photochromic diarylethenes-containing supramolecular systems

“…Especially, when BTEPy interacts with a carboxyl-containing Bodipy dye (Fig. 1), which is an attractive chromophore been extensively used for light-harvesting molecular arrays and fluorescent molecular probes [28], the ''concentration quenching'' in the solid state can be alleviated due to the hydrogen bond formation and energy transfer process [23]. The use of phototriggered conformational change of diarylethenes has been used to tune the physical properties of self-assembled supramolecular systems.…”

Broadband Visible‐Light‐Harvesting trans‐Bis(alkylphosphine) Platinum(II)‐Alkynyl Complexes with Singlet Energy Transfer between BODIPY and Naphthalene Diimide Ligands

“…We previously prepared a series of Ru II , Pt II , Ir III , and Re I complexes to explore this method and the complexes showed strong absorption of visible light and long‐lived triplet excited states 23. 27, 28, 36, 37…”

Difluoroboranyl derivatives as efficient panchromatic photoinitiators in radical polymerization reactions

“…The triplet-state lifetimes were determined as 2.3, 2.7, 2.3, and 2.1 ls, for 1, 2, 3 and 4, respectively, which is much shorter than a classical BODIPYs, e.g. trans-bis(trialkylphosphine) bisacetylide complex with BODIPY ligand (not styrylBODIPY ligand, s T = 128 ls) [51] or a C 60 -styrylBODIPY dyad (71-123 ls) [52]. However, this lifetime is close to that observed with heavy atom effect (s T = 1.8 ls) [53] or trans-bis-(trialkylphosphine) Pt(II) bisacetylide binuclear complex with BODIPY ligand (s T = 5.8 ls) [54].…”