Electron transfer and intersystem crossing in Bodipy dimers: a study of their photophysical properties using steady state and transient optical and electron paramagnetic resonance spectroscopic methods.

The photophysical properties of two new Bodipy dimers are investigated using a variety of techniques, including steady-state UV-vis absorption and fluorescence spectroscopy, femtosecond and nanosecond transient absorption spectroscopy, and pulse laser-excited time-resolved electron paramagnetic resonance (TREPR) spectroscopic methods. The dimers are formed by the Bodipy units rigidly linked by the orthogonal phenylene bridge. One of the dimers is composed of iodinated units, and the other is not.

An excitation-wavelength-dependent organic photoluminescent molecule with high quantum yield integrating both ESIPT and PCET mechanisms.

Excitation wavelength-dependent (Ex-De) chromophores, which exhibit changes in spectral composition with varying excitation wavelengths, have garnered significant interest. However, the pursuit of novel photoluminescence (PL) mechanisms and high luminescence quantum yields is facing huge challenges. Here, we discover that the introduction of a spinacine moiety to 2-(2-hydroxy-5-methylphenyl)benzothiazole, a traditional excited-state intramolecular proton transfer (ESIPT) fluorophore, results in a novel Ex-De PL molecule.

Thionated Perylenebisimides as Heavy-Atom-Free Triplet Photosensitizers: Intersystem Crossing, Electron Spin Dynamics, and Application in Photodynamic Therapy.

The thionation induced intersystem crossing (ISC) in perylenebisimide (PBI) derivatives was studied. The triplet state lifetimes of the thionated PBIs are substantially shortened (0.12-0.

Thionated Coumarins: Study of the Intersystem Crossing and the Zero-field Splitting of the Triplet State Using Time-Resolved Transient Optical and Electron Paramagnetic Resonance Spectroscopies.

To study the effect of thionation of the carbonyl groups in a chromophore, i. e. replacing the O atom with S atom, on the photophysics, we studied two thionated coumarin derivatives (Cou-S and Cou-6-S) with various steady state and transient spectroscopic methods.

Excited state dynamics of a Bodipy derivative with a twisted molecular structure: Combined experimental and theoretical studies.

The photophysical properties of a boron dipyrromethene (Bodipy, BDP) derivative (BDP-SA) in which one F atom at the BDP core was replaced by an O atom and condensed with salicylaldehyde were investigated. This compound has a twisted molecular structure and unusually low fluorescence quantum yield (1% in toluene). No intersystem crossing was observed with a nanosecond transient absorption study.

Time-resolved transient optical and electron paramagnetic resonance spectroscopic studies of electron donor-acceptor thermally activated delayed fluorescence emitters based on naphthalimide-phenothiazine dyads.

The photophysics of naphthalimide (NI)-phenothiazine (PTZ) dyads were investigated as electron donor-acceptor (D-A) thermally activated delayed fluorescence (TADF) emitters. Femtosecond transient absorption (fs-TA) spectra show that the photophysical processes in non-polar solvents are in singlet localized state (LE, = 0.8 ps) → Franck-Condon singlet charge separation state (CS, = 7.

The Photophysics of Naphthalimide-Phenoselenazine Electron Donor-Acceptor Dyads: Revisiting the Heavy-Atom Effect in Thermally Activated Delayed Fluorescence.

We prepared thermally activated delayed fluorescence (TADF) emitter dyads, NI-PTZ, NI-PTZ-2Br and NI-PSeZ, with naphthalimide (NI) as electron acceptor and 10H-phenothiazine (PTZ) or 10H-phenoselenazine (PSeZ) as electron donor to study the heavy-atom effect on the intersystem crossing (ISC) and reverse ISC (rISC) in the TADF emitters. The delayed fluorescence lifetimes of the dyads containing heavy atoms ( =5.9 μs for NI-PSeZ and =16.

Intersystem Crossing, Photo-Induced Charge Separation and Regioisomer-Specific Excited State Dynamics in Fully Rigid Spiro Rhodammine-Naphthalene/Anthraquinone Electron Donor-Acceptor Dyads.

We prepared a series fully rigid spiro electron donor-acceptor orthogonal dyads, with closed form of rhodamine (Rho) as electron donor and naphthalene (Np)/anthraquinone (AQ) as electron acceptor, to access the long-lived triplet charge separation (CS) state, via the electron spin control method. We found strong dependency of the photophysical property of the dyads on the amino substitution positions of the Np chromophores in the dyads 1,8-DaNp-Rho and 2,3-DaNp-Rho. Nanosecond transient absorption (ns-TA) spectra show the population of the LE state (lifetime: 47 μs) for 2,3-DaNp-Rho, however, long-lived CS state was observed (τ=0.

IBODIPY as a new photoswitchable spin label for light-induced pulsed EPR dipolar spectroscopy exploiting magnetophotoselection.

Electron paramagnetic resonance (EPR) pulsed dipolar spectroscopy (PDS) using triplet states of organic molecules is a growing area of research due to the favourable properties that these transient states may afford over stable spin centers, such as switchability, increased signal intensity when the triplet is formed in a non-Boltzmann distribution and the triplet signal is used for detection, and high orientation selection, when the triplet signal is probed by microwave pulses. This arises due to the large spectral width at low fields, a result of the large zero field splitting, and limited bandwidth of microwave pulses used. Here we propose the triplet state of a substituted BODIPY moiety as a spin label in light induced PDS, coupled to a nitroxide, in a model peptide with a rigid structure.

Electron Spin Dynamics of the Intersystem Crossing in Aminoanthraquinone Derivatives: The Spectral Telltale of Short Triplet Excited States.

We studied the excited state dynamics of two bis-amino substituted anthraquinone (AQ) derivatives, with absorption in the visible spectral region, which results from the attachment of a electron-donating group to the electron-deficient AQ chromophore. Femtosecond transient absorption spectra show that intersystem crossing (ISC) takes place in 190-320 ps, and nanosecond transient absorption spectra demonstrated an unusually short triplet state lifetime (2.06-5.

Origin of Intersystem Crossing in Red-Light Absorbing Bodipy Derivatives: Time-Resolved Transient Optical and Electron Paramagnetic Resonance Spectral Studies with Twisted and Planar Compounds.

We studied the intersystem crossing (ISC) property of red-light absorbing heavy atom-free dihydronaphtho[]-fused Bodipy derivatives (with phenyl group attached at the lower rim via ethylene bridge, taking constrained geometry, i.e., and the half-oxidized product ) and dispiroflourene[]-fused Bodipy () that have a twisted π-conjugated framework.

Platinum(II) bis(arylacetylide) complexes bearing diarylamino-substituted bipyridine ligands for solution-processable phosphorescent OLED applications.

A comprehensive investigation has been carried out on a series of complexes of the type (N^N)Pt(-CC-Ar), where N^N represents diarylamino-substituted 2,2'-bipyridine (bpy) ligands and -CC-Ar refers to the substituted arylacetylide ligands. The introduction of trifluoromethyl and methoxy substituents to the phenylacetylide unit results in color tuning of the phosphorescence energy in these complexes. The bulky diarylamino substituents on the bipyridine ligand showed distinctive electronic properties, resulting in improved hole-transporting characteristics.

Photophysics and photochemistry of thermally activated delayed fluorescence emitters based on the multiple resonance effect: transient optical and electron paramagnetic resonance studies.

The photochemistry of two representative thermally activated delayed fluorescence (TADF) emitters based on the multiple resonance effect (MRE) (DABNA-1 and DtBuCzB) was studied. No significant TADF was observed in fluid solution, although the compounds have a long-lived triplet state ( 30 μs). We found that these planar boron molecules bind with Lewis bases, , 4-dimethylaminopyridine (DMAP) or an -heterocyclic carbene (NHC).

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the LE state (LE: locally excited state).

Radical enhanced intersystem crossing mechanism, electron spin dynamics of high spin states and their applications in the design of heavy atom-free triplet photosensitizers.

Heavy atom-free triplet photosensitizers (PSs) can overcome the high cost and biological toxicity of traditional molecular systems containing heavy atoms (such as Pt(II), Ir(III), Ru(II), Pd(II), Lu(III), I, or Br atoms) and, therefore, are developing rapidly. Connecting a stable free radical to the chromophore can promote the intersystem crossing (ISC) process through electron spin exchange interaction to produce the triplet state of the chromophore or the doublet (D) and quartet (Q) states when taking the whole spin system into account. These molecular systems based on the radical enhanced ISC (REISC) mechanism are important in the field of heavy atom-free triplet PSs.

Multiple Pathways in the Triplet States Population for a Naphthalenediimide-C Dyad.

The link of an antenna dye with an electron spin converter, in this case naphthalenediimide and C, produces a system with a rich photophysics including the detection of more than one triplet state on the long timescale (tens of μs). Beside the use of optical spectroscopies in the ns and in the fs time scale, we used time-resolved Electron Paramagnetic Resonance (TREPR) to study the system evolution following photoexcitation. TREPR keeps track of the formation path of the triplet states through specific spin polarization patterns observed in the spectra.

Tuning Excited State Character in Iridium(III) Photosensitizers and Its Influence on TTA-UC.

A series of mixed ligand, photoluminescent organometallic Ir(III) complexes have been synthesized to incorporate substituted 2-phenyl-1-naphtho[2,3-]imidazole cyclometalating ligands. The structures of three example complexes were categorically confirmed using X-ray crystallography each sharing very similar structural traits including evidence of interligand hydrogen bond contacts that account for the shielding effects observed in the H NMR spectra. The structural iterations of the cyclometalated ligand provide tuning of the principal electronic transitions that determine the visible absorption and emission properties of the complexes: emission can be tuned in the visible region between 550 and 610 nm and with triplet lifetimes up to 10 μs.

Red-light operable photosensitizer with symmetry-breaking charge transfer induced intersystem crossing for polymerization of methyl methacrylate.

We present a red light-activated zinc bis(dipyrrin) symmetry breaking charge transfer (SBCT) architecture, showing a large molar absorption coefficient ( = 15.4 × 10 M cm), high reactive singlet oxygen generation efficiency ( ≈ 0.8) and long-lived triplet state ( = 150 μs) compared to the donor-acceptor analogue dipyrrin-BF complex, highlighting the superiority of the SBCT approach.

Near-IR-Absorbing Bis-Donor Functionalized Aza-BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy.

A series of near-IR absorbing 2,6-diarylated BF-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λ=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λ=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties.

A Rational Way to Control the Triplet State Wave Function Confinement of Organic Chromophores: Effect of the Connection Sites and Spin Density Distribution-Guided Molecular Structure Design Principles in Bodipy Dimers.

To study the intersystem crossing (ISC) and the spatial confinement of the triplet excited states of organic chromophores, we prepared a series of Bodipy dimers. We found that the connection position of the two units has a significant effect on the absorption and fluorescence. Singlet oxygen quantum yields of 3.

Tailoring flavin-based photosensitizers for efficient photooxidative coupling of benzylic amines.

Photooxidative coupling of benzylic amines using naturally abundant O as an oxidant under visible light irradiation is an alternative green approach to synthesis imines and is of both fundamental and practical significance. We investigated the photophysical properties of flavin (FL) that is a naturally available sensitizer and its derivatives, 9-bromoflavin (MB-FL), 7,8-dibromoflavin (DB-FL) and 10-phenylflavin (Ph-FL), as well as the performance of these FL-based sensitizers (FLPSs) in the photooxidative coupling of benzylic amines to imines combining experimental and theoretical efforts. We showed that chemical functionalization with Br and phenyl effectively improves the photophysical properties of these FLPSs, in terms of absorption in the visible light range, singlet oxygen quantum yields, triplet lifetime, Apart from nearly quantitative selectivity for the production of imines, the performance of DB-FL is superior to those of other FLPSs, and it is among the best photocatalysts for imine synthesis.

The effect of thionation of the carbonyl group on the photophysics of compact spiro rhodamine-naphthalimide electron donor-acceptor dyads: intersystem crossing, charge separation, and electron spin dynamics.

Herein, a spiro rhodamine (Rho)-thionated naphthalimide (NIS) electron donor-acceptor orthogonal dyad (Rho-NIS) was prepared to study the formation of a long-lived charge separation (CS) state the electron spin control approach. The transient absorption (TA) spectra of Rho-NIS indicated that the intersystem crossing (ISC) occurs within 7-42 ps to produce the NIS state the spin orbit coupling ISC (SOC-ISC). The energy order of CS (2.

Efficient Spin-Orbit Charge-Transfer Intersystem Crossing and Slow Intramolecular Triplet-Triplet Energy Transfer in Bodipy-Perylenebisimide Compact Dyads and Triads.

Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). For BDP-PBI-3, in which BDP was attached at the imide position of PBI, higher singlet oxygen quantum yield (Φ =85 %) was observed than the bay-substituted derivative BDP-PBI-1 (Φ =30 %). Femtosecond transient absorption spectra indicate slow Förster resonance energy transfer (FRET; 40.