Light-Controlled Switching of Perylene Bisimide Assemblies.

Light-driven changes in supramolecular interactions in perylene bisimides (PBIs) with pendant sulfur-containing functional groups at the bay position are demonstrated. In the ground state, a noncovalent S···X interaction between the σ-hole on sulfur and a heteroatom, X (X = O, N, S), of a neighboring molecule is the main driving force for intermolecular interactions, while in the excited state it is the π-π interaction between PBI scaffolds which drives assembly. The presence of heteroatoms in the solvent results in acceleration of the π-stacking process via the formation of a PBI-solvent complex. The excited-state dynamics involved in the assembly process were revealed via time-resolved fluorescence and transient absorption spectroscopies, while steady-state spectroscopy was used to evaluate the structure of the supramolecular assembly.

Restricted rotation and tunable fluorescence in atropisomeric naphthyl pyridine chromophores.

Enhanced fluorescence quantum yields are enabled by simple reactions at the heterocyclic nitrogen in naphthyl-pyridine chromophores in which the electronic properties can be tuned through protonation, oxidation, and alkylation at the nitrogen center. Fluorescence quantum yield is increased by reacting the pyridine lone pair with either a proton or an alkyl group. Restricted intramolecular rotation (RIR) was observed upon alkylation, as evidenced by the presence of atropisomers. These simple structural changes allow application-driven tuning of electronic properties.

The unexpected effect of ferrocenyl substituents on the photochemistry of dianthryl sulfoxides.

Photoexcitation of ferrocenyl substituted dianthryl sulfoxide results in photochemical reaction products that differ from all known compounds of this class. This is enabled by energy transfer to a low-lying state, even in the case of the oxidized ferrocenium-containing compound.

Rhenium(I) Complexes with Sulfur-Bridged Dipyridyl Ligands: Structural, Photophysical, and Computational Studies.

A series of six new rhenium(I) tricarbonyl complexes [Re(CO)3(N-N)Br] bearing sulfur-bridged dipyridyl (N-N) ligands with three different oxidation states (sulfide (S), sulfoxide (SO), and sulfone (SO2)) are described. Spectroscopic studies show that changing the oxidation state of the ligands influences the photophysical properties of the complexes, with complexes 3 and 6 containing the sulfone ligand exhibiting a lower energy MLCT absorption band tailing into the visible region. Solution-state emission measurements show that these complexes exhibit readily tunable emission energies from 480 to 610 nm, depending on the oxidation state of the sulfur bridge and the presence of substituents on the pyridyl rings. Solid-state emission measurements show that the emission is significantly red-shifted upon oxidation of the sulfur bridge to sulfone with enhanced photoluminescence quantum yield.

Effect of Oxidation on the Chiroptical Properties of Sulfur-Bridged Binaphthyl Dimers.

A series of axially chiral sulfur-bridged dimers were prepared from 1,1'-binaphthyl-2,2'-diol and subsequently oxidized to the respective sulfones. The chiroptical properties of the chiral chromophores were studied as a function of the oxidation state. Upon oxidation, an increase in quantum yields was observed for directly linked sulfur bridged binaphthyls (0.04 to 0.32), and a modest increase in dissymmetry factor was observed for diphenylsulfide-bridged binaphthyls (-8.9 × 10-4 to -1.4 × 10-3). Computational calculations were used to elucidate the changes in photophysical properties.

Control of photoluminescence quantum yield and long-lived triplet emission lifetime in organic alloys.

Two-component crystalline organic alloys with a wide range of compositional ratios (from 30% to 90% of one component) are employed to tune excited-state lifetimes and photoluminescence quantum yields (PLQYs). Alloy crystals exhibit homogeneous distribution of parent compounds by X-ray crystallography and differential scanning calorimetry. The alloys display a 1.5- to 5-fold enhancement in thermally activated delayed fluorescence (TADF) lifetime, compared to the parent compounds. PLQYs can also be tuned by changing alloy composition. The reverse intersystem crossing and long-lived lifetime of the parent compounds give rise to long-lived TADF in the alloys. Organic alloys enable tunability of both lifetime and efficiency, providing a new perspective on the development of organic long-lived emissive materials beyond the rules established for host-guest doped systems.

Sulfur-bridged chromophores for photofunctional materials: using sulfur oxidation state to tune electronic and structural properties.

The use of a heteroatom, such as sulfur, as a linker or bridge, in π-conjugated materials has advantages over purely carbon-based ones due to the accessibility of higher oxidation states as a result of hypervalence. Materials containing a sulfide bridge (S) can be systemically oxidized into sulfoxides (SO) and sulfones (SO2), each of which can then influence how a material interacts with light, playing a large role in dictating the photophysical and sometimes photochemical properties. In this perspective, we summarize the progress that our group and others have made, showing how oxidation of a sulfur bridge in symmetric bichromophoric dimers and in diimine ligands can influence the excited state behavior in organic π-conjugated materials and metal complexes.

Lewis Pair-Functionalized Pt(II) Complexes with Tunable Emission Color and Triplet-State Properties.

Two emissive Pt(II) complexes containing dynamic "flexible" Lewis pair (FlexLP) ligands are reported. The FlexLP ligand encompasses a diphenylphosphine oxide Lewis base and a dimesitylborane Lewis acid attached to a bithiophene scaffold, which can switch between an open unbound Lewis pair and a bound P-O-B Lewis adduct depending on the hydrogen bond-donating (HBD) strength of the solvent. [Pt(FlexLP)2] contains two FlexLP ligands, and [Pt(FlexLP)(Py)] contains one FlexLP ligand and one pyrene ligand. UV-vis absorption and fluorescence studies demonstrate that the FlexLP ligands switch between the open Lewis pair and the closed Lewis adduct in MeOH, a strong HBD solvent, and acetone, a weak HBD solvent, respectively, and exhibit tunable emission color depending on the acetone/MeOH solvent ratio. Transient absorption spectroscopy reveals a large difference in the triplet-state lifetime depending on the conformation of the FlexLP ligands for both complexes. In the closed form, the triplet-state lifetimes of the two complexes are over an order of magnitude longer compared to that of the complexes in the open conformation. Calculations of optimized geometries suggest that this difference in triplet-state lifetime is due to a difference in the thiophene-thiophene torsion angle between the two conformations.

Photodynamic and Contact Killing Polymeric Fabric Coating for Bacteria and SARS-CoV-2.

The development of low-cost, non-toxic, scalable antimicrobial textiles is needed to address the spread of deadly pathogens. Here, we report a polysiloxane textile coating that possesses two modes of antimicrobial inactivation, passive contact inactivation through amine/imine functionalities and active photodynamic inactivation through the generation of reactive oxygen species (ROS). This material can be coated and cross-linked onto natural and synthetic textiles through a simple soak procedure, followed by UV cure to afford materials exhibiting no aqueous leaching and only minimal leaching in organic solvents. This coating minimally impacts the mechanical properties of the fabric while also imparting hydrophobicity. Passive inactivation of Escherichia coli (E. coli) and methicillin-resistant Staphylococcus aureus (MRSA) is achieved with >98% inactivation after 24 h, with a 23× and 3× inactivation rate increase against E. coli and MRSA, respectively, when green light is used to generate ROS. Up to 90% decrease in the infectivity of SARS-CoV-2 after 2 h of irradiated incubation with the material is demonstrated. These results show that modifying textiles with dual-functional polymers results in robust and highly antimicrobial materials that are expected to find widespread use in combating the spread of deadly pathogens.

Switching between TADF and RTP: anion-regulated photoluminescence in organic salts and co-crystals.

Thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) are two photophysical phenomena which utilize triplet excitons. In this work, we demonstrate how variation of the anion in organic salts with carbazole and phenothiazine-5,5-dioxide donors and pyridinium and quinolinium acceptors may be used to switch between TADF and RTP. These compounds adopt similar molecular structures and packing modes with different anions and exhibit different types of photophysical behavior due to the electronic effects of the anions. With bromide anions, the salts exhibit TADF with some RTP. These compounds show fast reverse intersystem crossing and a short delayed lifetime, which is key to application in efficient and robust OLEDs. With BF4 - and PF6 - anions, RTP with long-lived lifetimes and afterglow are observed by eye. This behavior can be utilized for data encryption and anti-counterfeiting applications. Emission wavelengths and lifetimes are also anion-dependent. These results open up an avenue for developing novel luminescent materials through anion tuning and present a molecular model to understand the interplay of RTP and TADF.

Photocross-Linked Antimicrobial Amino-Siloxane Elastomers.

Mechanically robust bulk antimicrobial polymers are one way to address disease transmission via contaminated surfaces. Here, we demonstrate the visible light photo-oxidative cross-linking of amine-containing PDMS using a single-component, solvent-free system where amines have a dual role as antimicrobial functionalities and cross-linking sites. Rose Bengal, a xanthene dye used as a fluorescent stain, is thermally reacted with the polymer to give a solvent-free liquid siloxane that can generate reactive singlet oxygen upon aerobic green light irradiation, coupling the amine functionalities into imine cross-links. Photorheological experiments demonstrate that light intensity is the largest kinetic factor in the photo-oxidative curing of these polymers. Room temperature irradiation under an ambient atmosphere results in free-standing elastic materials with mechanical properties that depend on the amount of Rose Bengal present. An ultimate elongation strain of 117% and Young's modulus of 2.15 MPa were observed for the highest dye loading, with both mechanical properties found to be higher than those for the same solution-based dye amounts. We demonstrate that the solvent-free nature of the material can be exploited to generate 3D structures using low-temperature deposition as well as direct-write patterning and photolithography on glass substrates. The antimicrobial activity was investigated, with the cross-linked material demonstrating greater efficacy against E. coli (Gram negative) compared with MRSA (Gram positive) bacterial strains and inducing complete cell lysis of incubated CHO-K1 mammalian cells, demonstrating applicability as a mechanically robust single-component antimicrobial elastomer.

Controlling photocatalytic reduction of CO2 in Ru(II)/Re(I) dyads via linker oxidation state.

Electronic communication between the linked metal centers in Ru(ii)-Re(i) dyads is tuned using the oxidation state (S and SO2) of sulfur-bridged ligands. Higher catalytic activity is seen for the SO2-bridged dyad in the photocatalytic reduction of CO2.

Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated AuIII Compounds: New Mechanistic Insights.

To gain more insight into the factors controlling efficient cysteine arylation by cyclometallated AuIII complexes, the reaction between selected gold compounds and different peptides was investigated by high-resolution liquid chromatography electrospray ionization mass spectrometry (HR-LC-ESI-MS). The deduced mechanisms of C-S cross-coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.

Stimuli-responsive flexible Lewis pair-modified nanoparticles for fluorescence imaging.

A stimuli-responsive fluorophore, encompassing a Lewis acid-base pair, binds to primary amines on mesoporous silica nanoparticles, which may serve as environment-sensitive drug carriers. The fluorophore switches conformation, exhibiting different emission color and lifetimes, allowing for the detection of the water content of the nanoparticles' surroundings through fluorescence spectroscopy and microscopy.

Quinoline-containing diarylethenes: bridging between turn-on fluorescence, RGB switching and room temperature phosphorescence.

Simple structural modifications using oxidation and methylation of a quinoline-containing diarylethene result in dramatic variation of photophysical properties. Turn-on fluorescence, room temperature phosphorescence (RTP) and red-green-blue (RGB) switching were achieved in three different related compounds. Photoswitchable diarylethenes (DAEs) that exhibit turn-on fluorescence are in high demand for super-resolution microscopy, and the development of purely organic phosphorescent materials in the amorphous state is attractive but challenging. The findings reported here provide a novel toolkit for designing turn-on fluorescence DAEs for super-resolution microscopy and extending the scope of amorphous RTP materials. More importantly, we bridge between these two fundamentally significant photochemical and photophysical phenomena, and reveal structure-property relationships between DAE photochromism and RTP.

Room temperature crystallization of amorphous polysiloxane using photodimerization.

Bulk crystallization in flexible polymeric systems is difficult to control due to the random orientation of the chains. Here we report a photo cross-linking strategy that results in simultaneous cross-linking and crystallization of polysiloxane chains into millimeter sized leaf-like polycrystalline structures. Polymers containing pendant anthracene groups are prepared and undergo [4+4] photocycloaddition under 365 nm irradiation at room temperature. The growth and morphology of the crystalline structures is studied using polarized optical microscopy (POM) and atomic force microscopy and is found to progress through three unique stages of nucleation, growth, and constriction. The mobility of the individual chains is probed using pulsed-field gradient (PFG) NMR to provide insights into the diffusion processes that may govern chain transport to the growing crystal fronts. The room temperature crystallization of this conventionally amorphous polymer system may allow for a new level of morphological control for silicone materials.

Controlling ultralong room temperature phosphorescence in organic compounds with sulfur oxidation state.

Sulfur oxidation state is used to tune organic room temperature phosphorescence (RTP) of symmetric sulfur-bridged carbazole dimers. The sulfide-bridged compound exhibits a factor of 3 enhancement of the phosphorescence efficiency, compared to the sulfoxide and sulfone-bridged analogs, despite sulfone bridges being commonly used in RTP materials. In order to investigate the origin of this enhancement, temperature dependent spectroscopy measurements and theoretical calculations are used. The RTP lifetimes are similar due to similar crystal packing modes. Computational studies reveal that the lone pairs on the sulfur atom have a profound impact on enhancing intersystem crossing rate through orbital mixing and screening, which we hypothesize is the dominant factor responsible for increasing the phosphorescence efficiency. The ability to tune the electronic state without altering crystal packing modes allows the isolation of these effects. This work provides a new perspective on the design principles of organic phosphorescent materials, going beyond the rules established for conjugated ketone/sulfone-based organic molecules.

Using sulfur bridge oxidation to control electronic coupling and photochemistry in covalent anthracene dimers.

Covalently tethered bichromophores provide an ideal proving ground to develop strategies for controlling excited state behavior in chromophore assemblies. In this work, optical spectroscopy and electronic structure theory are combined to demonstrate that the oxidation state of a sulfur linker between anthracene chromophores gives control over not only the photophysics but also the photochemistry of the molecules. Altering the oxidation state of the sulfur linker does not change the geometry between chromophores, allowing electronic effects between chromophores to be isolated. Previously, we showed that excitonic states in sulfur-bridged terthiophene dimers were modulated by electronic screening of the sulfur lone pairs, but that the sulfur orbitals were not directly involved in these states. In the bridged anthracene dimers that are the subject of the current paper, the atomic orbitals of the unoxidized S linker can actively mix with the anthracene molecular orbitals to form new electronic states with enhanced charge transfer character, different excitonic coupling, and rapid (sub-nanosecond) intersystem crossing that depends on solvent polarity. However, the fully oxidized SO2 bridge restores purely through-space electronic coupling between anthracene chromophores and inhibits intersystem crossing. Photoexcitation leads to either internal conversion on a sub-20 picosecond timescale, or to the creation of a long-lived emissive state that is the likely precursor of the intramolecular [4 + 4] photodimerization. These results illustrate how chemical modification of a single atom in the covalent bridge can dramatically alter not only the photophysics but also the photochemistry of molecules.

Influence of Sulfur Oxidation State and Substituents on Sulfur-Bridged Luminescent Copper(I) Complexes Showing Thermally Activated Delayed Fluorescence.

Copper(I) complexes are seen as more sustainable alternatives to those containing metal ions such as iridium and platinum for emitting devices. Copper(I) complexes have the ability to radiatively decay via a thermally activated delayed fluorescence (TADF) pathway, leading to higher photoluminescent quantum yields. In this work we discuss six new heteroleptic Cu(I) complexes of the diphosphine-diimine motif. The diphosphine ligands employed are (oxidi-2,1-phenylene)bis(diphenylphosphine) (DPEPhos), and the diimine fragments are sulfur-bridged dipyridyl ligands (DPS) which are functionalized at the 6,6'-positions of the pyridyl rings (R = H, Me, Ph) and have varying oxidation states at the bridging sulfur atom (S, SO2). The proton (Cu-DPS, Cu-DPSO2) and phenyl (Cu-Ph-DPS, Cu-Ph-DPSO2) substituted species are found to form monometallic complexes, while those with methyl substitution (Cu-Me-DPS, Cu-Me-DPSO2) are found to have a "Goldilocks" degree of steric bulk leading to bimetallic species. All six Cu(I) complexes show emission in the solid state, with the photophysical properties characterized by low temperature steady-state and time-resolved spectroscopies and variable temperature time-correlated single photon counting. Cu-DPS, Cu-DPSO2, Cu-Me-DPS, Cu-Me-DPSO2, and Cu-Ph-DPSO2 were shown to emit via a TADF mechanism, while Cu-Ph-DPS showed photoluminescence properties consistent with triplet ligand-centered (3LC) emission.

Fluorescence Switching of Intramolecular Lewis Acid-Base Pairs on a Flexible Backbone.

A class of intramolecular Lewis acid-base pairs containing Lewis acidic dimesitylboranes paired with phosphine oxide, sulfoxide, and sulfone Lewis basic groups are explored. The absorption and emission properties of the compounds are investigated in different solvent environments, and switching of the photophysical behavior between the Lewis acid-base adducts and free acid-base pairs is examined. We find that phosphine oxide Lewis base groups are effective partners in flexible Lewis pairs; however, the analogous sulfoxide and sulfone groups are not. Additionally, the absorption and emission wavelengths can be systematically tuned by varying the conjugation length and electron-donating and -accepting substituents on the backbone.