Characterization of Excited-State Electronic Structure in Diblock π-Conjugated Oligomers with Adjustable Linker Electronic Coupling.

Diblock conjugated oligomers are π-conjugated molecules that contain two segments having distinct frontier orbital energies and HOMO-LUMO gap offsets. These oligomers are of fundamental interest to understand how the distinct π-conjugated segments interact and modify their excited state properties. The current paper reports a study of two series of diblock oligomers that contain oligothiophene (Tn) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) segments that are coupled by either ethynyl (-C≡C-) or trans-(-C≡C-)2Pt(II)(PBu3)2 acetylide linkers. In these structures, the Tn segment is electron rich (donor), and the TBT is electron poor (acceptor). The diblock oligomers are characterized by steady-state and time-resolved spectroscopy, including UV-visible absorption, fluorescence, fluorescence lifetimes, and ultrafast transient absorption spectroscopy. Studies are compared in several solvents of different polarity and with different excitation wavelengths. The results reveal that the (-C≡C-) linked oligomers feature a delocalized excited state that takes on a charge transfer (CT) character in more polar media. In the (-C≡C-)2Pt(II)(PBu3)2-linked oligomers, there is weak coupling between the Tn and TBT segments. Consequently, short wavelength excitation selectively excites the Tn segment, which then undergoes ultrafast energy transfer (~1 ps) to afford a TBT-localized excited state.

Linker Engineering toward Tunable Emission Behavior of Porous Interpenetrated Zr-Organic Frameworks.

Conjugated molecules with donor-acceptor-donor (D-A-D) moieties have garnered significant attention for their ability to form luminescent metal-organic frameworks (LMOFs). D-A-D molecules feature tunable bandgaps, which can be varied systematically to control the fluorescence wavelength of LMOFs. In this study, we prepared and characterized the fluorescence properties of two porous interpenetrated Zr-organic frameworks (PIZOFs) constructed using 4,4'-(benzo[c][1,2,5]selenadiazole-4,7-diylbis(ethyne-2,1-diyl))dibenzoic acid (L-Se) or 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl))dibenzoic acid (L-S) as linkers. The corresponding MOFs are denoted as PIZOF-Se and PIZOF-S, respectively. Through our investigation, we explored the correlation between the structure of the frameworks and their respective optical properties. Our findings revealed that there are distinct differences in the fluorescence properties of the two PIZOFs. Specifically, the fluorescence of PIZOF-S is red-shifted from that characteristic of the corresponding linker, L-S. By contrast, the fluorescence of PIZOF-Se is substantially blue-shifted from that of linker L-Se. The emission of mixed-linker MOFs is explored by combining L-S or L-Se with structurally analogous, but nonfluorescent linker, 4,4'-((perfluoro-1,4-phenylene)bis(ethyne-2,1-diyl))dibenzoic acid (L-F). Based on steady-state and time-resolved photoluminescence experiments, as well as confocal fluorescence microscopy combined with fluorescence lifetime imaging (FILM), we demonstrated that linker engineering is an effective method to tune the emission behavior of LMOFs.

A Perspective Looking Backward and Forward on the 25th Anniversary of Conjugated Polyelectrolytes.

Conjugated polyelectrolytes are π-conjugated polymers that contain ionic charged groups such as sulfonate (R-SO3-), carboxylate (R-COO-), or ammonium (R-NR3+) combined with a π-conjugated backbone. This perspective provides a summary review of the key developments in the field, starting from the first reports of their synthesis and properties to application-focused developments. The applications include optical sensors for molecular and biomolecular targets, organic electronic applications, and specific biological applications including cellular imaging and photodynamic therapy. This perspective concludes with a discussion of where the field of conjugated polyelectrolytes is expected to lead in the coming years.

Phosphonium-Substituted Conjugated Polyelectrolytes Display Efficient Visible-Light-Induced Antibacterial Activity.

We report the light-activated antibacterial activity of a new class of phosphonium (R-PMe3+)-substituted conjugated polyelectrolytes (CPEs). These polyelectrolytes feature a poly(phenylene ethynylene) (PPE) conjugated backbone substituted with side groups with the structure -O-(CH2)nPMe3+, where n = 3 or 6. The length of the side groups has an effect on the hydrophobic character of the CPEs and their propensity to interact with bacterial membranes. In a separate study, these phosphonium-substituted PPE CPEs were demonstrated to photosensitize singlet oxygen (1O2) and reactive oxygen species, a key factor for the photoinduced inactivation of bacteria. In this study, in vitro antibacterial assays against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus were performed by employing the series of polyelectrolytes under both dark and illumination conditions. In general, the phosphonium-substituted CPEs displayed profound light-activated biocidal activity, with >99% colony forming unit (CFU) reduction after 15 min of light exposure (16 mW cm-2) at a ≤20 µM CPE concentration. Strong biocidal activity was also observed in the dark for a CPE concentration of 20 µM against S. aureus; however, higher concentrations (200 µM) were needed to enable dark inactivation of E. coli. The dark activity is ascribed to bacterial membrane disruption by the CPEs, supported by a correlation of dark biocidal activity with the chain length of the side groups. The light-activated biocidal activity is associated with the ability of the CPEs to sensitize ROS, which is cytotoxic to the microorganisms. Serial dilution bacterial plating experiments revealed that the series of CPEs was able to induce a >5-log kill versus E. coli with 15 min of exposure to a blue LED source (16 mW cm-2).

Excitation-Wavelength-Dependent Charge Injection and Hole Localization in Diblock Oligomers Anchored to TiO2.

A series of diblock oligomers containing oligothiophene (Tn, n = 4, 5) and 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadizole (TBT) segments, functionalized with carboxylic acid anchoring groups, were prepared and anchored to mesoporous TiO2 films to study wavelength-dependent interfacial electron transfer mechanisms. Thin films of the surface-anchored diblock oligomers contained two absorption bands centered at 400 and 500 nm, corresponding to the Tn and TBT blocks, respectively. Pulsed-laser excitation of the oligomer-sensitized films yielded local excited-states that promoted electron injection into TiO2. The injection pathway was dependent on the excitation wavelength, as electron injection occurred from the oligomer block that was locally excited. Recombination between the injected electron and the oxidized oligomer was sensitive to the bridging unit that separates the oligomer conjugated segments (-C≡C- vs trans-Pt(PBu3)2-). When the bridge facilitated strong coupling between the two blocks (-C≡C- bridge), the excitation wavelength had no effect on the recombination pathway, as the hole was delocalized over the entire oligomer. However, in the weak coupling case (Pt(PBu3)2- bridge), selective excitation resulted in wavelength-dependent hole localization that persisted to the µs time scale, providing control over the recombination pathway by varying the excitation wavelength. Dye-sensitized solar cells (DSSCs) were fabricated by using the diblock oligomers as sensitizers. The photocurrent action spectra were measured, and the absorbed photon-to-current efficiency (APCE) provided further insight into the electron-transfer mechanisms that are operative under continuous illumination.

Photophysics and charge transfer in oligo(thiophene) based conjugated diblock oligomers.

This paper reports an investigation of the electronic structure and photophysical properties of two "diblock" π-conjugated oligomers (T4-TBT and T8-TBT) that feature electron rich tetra(thiophene) (T4) or octa(thiophene) (T8) segments linked to an electron poor 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) moiety. Electrochemistry and UV-visible absorption spectroscopy reveals that the diblock oligomers display redox and absorption features that can be attributed to the Tn and TBT units. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations support the experimental electrochemistry and optical spectroscopy results, suggesting that the frontier orbitals on the diblock oligomers retain characteristics of the individual π-conjugated segments. However, low energy optical transitions are anticipated to arise from Tn to TBT charge transfer. Fluorescence spectroscopy on the diblock oligomers reveals that the oligomers feature strongly solvent dependent fluorescence. In non-polar solvents (hexane, toluene), the emission is structured with a moderate Stokes shift; however, in more polar solvents the emission becomes broader, and red-shifts significantly. Transient absorption spectroscopy on timescales from femtoseconds (fs) to microseconds (µs) reveals that in non-polar solvents excitation produces a singlet excited state (LE) that decays uniformly to the ground state in parallel with intersystem crossing to a triplet state. By contrast, in more polar solvents, excitation produces a very short-lived excited state (1-3 ps) which evolves rapidly into a second excited state that is attributed to the charge transfer (CT) state. The fast dynamics are associated with crossing from the LE state, which is populated initially by photoexcitation, into the CT state, which then decays to the ground state. The photophysical properties and dynamics of the LE and CT excited states are very similar for T4-TBT and T8-TBT, suggesting that the length of the oligo(thiophene) segment does not have a strong influence on the energy, structure or dynamics of the LE and CT excited states.

Effect of bromine substitution on blue phosphorescent trans-(N-heterocyclic carbene)Pt(II) acetylide complexes.

N-heterocyclic carbene complexes of the type trans-(NHC)2PtII(CC-Ar)2 (where Ar = phenyl or substituted phenyl) are of interest as violet and blue phosphors. These complexes emit efficient phosphorescence in solution and in the solid state, and they have been applied as phosphors in organic light emitting diodes. This study explores the effect of bromine substitution on the trans-(NHC)2PtII(CC-Ar)2 chromophore through photophysical studies of a pair of complexes in which the phenyl groups feature either 3,5-dibromo- or 4-monobromo-substituents (IPt-DB and IPt-MB, respectively). The Br atoms were introduced as heavy atom(s) with the aim to enhance spin-orbit coupling and increase the radiative and non-radiative decay rates of the phosphorescent triplet state. Both IPt-MB and IPt-DB exhibit sky-blue phosphorescence in solution and in PMMA matrix. Interestingly, the emission quantum yield and lifetime of IPt-MB are substantially lower compared to IPt-DB in solution. This effect is attributed to a substantially larger non-radiative decay rate in the mono-bromo complex. Analysis of the photophysical data, combined with DFT and TD-DFT calculations, suggest that the difference in photophysical properties of the two complexes is related to the position of the Br-substituents on the phenyl acetylide rings. In short, in IPt-MB, the Br-substituents are located para-to the Pt-CC-unit, and this gives rise to stronger electron-vibrational coupling in the excited state, enhancing the rate of non-radiative decay.

Ultrasensitive Determination of Trypsin in Human Urine Based on Amplified Fluorescence Response.

The determination of trypsin activity in human urine is important for evaluating pancreatic disease. We designed an effective fluorescence sensing strategy based on a self-assembled amphiphilic pyrene/protamine complex system that provides an amplified fluorescence response for highly sensitive and selective detection of trypsin. In aqueous solution, the functionalized pyrene formed fluorescent, π-extended aggregates inside micelles, which were effectively quenched by protamine (a trypsin substrate). However, this quenched fluorescence was very sensitively recovered by the trypsin's enzymatic reaction, and this was attributed to a marked reduction in enhanced exciton migration caused by protamine in π-delocalized pyrene aggregates. The devised sensing platform was successfully utilized to selectively and sensitively detect trypsin at very low concentrations (0.03-0.5 µg mL-1) in non-pretreated human urine and to screen for trypsin inhibitors at concentrations of 0.1-5.0 µg mL-1.

Phosphates Induced H-Type or J-Type Aggregation of Cationic Porphyrins with Varied Side Chains.

Non-covalent interactions have been extensively used to fabricate nanoscale architectures in supramolecular chemistry. However, the biomimetic self-assembly of diverse nanostructures in aqueous solution with reversibility induced by different important biomolecules remains a challenge. Here, we report the synthesis and aqueous self-assembly of two chiral cationic porphyrins substituted with different types of side chains (branched or linear). Helical H-aggregates are induced by pyrophosphate (PPi) as indicated by circular dichroism (CD) measurement, while J-aggregates are formed with adenosine triphosphate (ATP) for the two porphyrins. By modifying the peripheral side chains from linear to a branched structure, more pronounced H- or J-type aggregation was promoted through the interactions between cationic porphyrins and the biological phosphate ions. Moreover, the phosphate-induced self-assembly of the cationic porphyrins is reversible in the presence of the enzyme alkaline phosphatase (ALP) and repeated addition of phosphates.

Tunable Photoinduced Charge Transfer at the Interface between Benzoselenadiazole-Based MOF Linkers and Thermally Activated Delayed Fluorescence Chromophore.

Structural modifications to molecular systems that lead to the control of photon emission processes at the interfaces between photoactive materials play a key role in the development of fluorescence sensors, X-ray imaging scintillators, and organic light-emitting diodes (OLEDs). In this work, two donor-acceptor systems were used to explore and reveal the effects of slight changes in chemical structure on interfacial excited-state transfer processes. A thermally activated delayed fluorescence (TADF) molecule was chosen as the molecular acceptor. Meanwhile, two benzoselenadiazole-core MOF linker precursors, Ac-SDZ and SDZ, with the presence and absence of a C≡C bridge, respectively, were carefully chosen as energy and/or electron-donor moieties. We found that the SDZ -TADF donor-acceptor system exhibited efficient energy transfer, as evidenced by steady-state and time-resolved laser spectroscopy. Furthermore, our results demonstrated that the Ac-SDZ-TADF system exhibited both interfacial energy and electron transfer processes. Femtosecond-mid-IR (fs-mid-IR) transient absorption measurements revealed that the electron transfer process takes place on the picosecond timescale. Time-dependent density functional theory (TD-DFT) calculations confirmed that photoinduced electron transfer occurred in this system and demonstrated that it takes place from C≡C in Ac-SDZ to the central unit of the TADF molecule. This work provides a straightforward way to modulate and tune excited-state energy/charge transfer processes at donor-acceptor interfaces.

iClick synthesis of network metallopolymers.

Described is an approach to preparing the first iClick network metallopolymers with porous properties. Treating digoldazido complex 2-AuN3 with trigoldacetylide 3-AuPPh3 or 3-AuPEt3, trialkyne 3-H, tetragoldacetylide 4-AuPPh3, or tetraalkyne 4-H in CH2Cl2 affords five iClick network metallopolymers 5-AuPPh3, 5-AuPEt3, 5-H, 6-AuPPh3, and 6-H. Confirmation of the iClick network metallopolymers comes from FTIR, 13C solid-state cross-coupling magic angle spinning (CPMAS) NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and nitrogen and CO2 sorption analysis. Employing model complexes 7-AuPPh3, 7-AuPEt3, 7-H, 8-AuPPh3, and 8-H provides structural insights due to the insolubility of iClick network metallopolymers.

Functionalization of Water-Soluble Conjugated Polymers for Bioapplications.

Water-soluble conjugated polymers (WS-CPs) have found widespread use in bioapplications ranging from in vitro optical sensing to in vivo phototherapy. Modification of WS-CPs with specific molecular functional units is necessary to enable them to interact with biological targets. These targets include proteins, nucleic acids, antibodies, cells, and intracellular components. WS-CPs have been modified with covalently linked sugars, peptides, nucleic acids, biotin, proteins, and other biorecognition elements. The objective of this article is to comprehensively review the various synthetic chemistries that have been used to covalently link biofunctional groups onto WS-CP platforms. These chemistries include amidation, nucleophilic substitution, Click reactions, and conjugate addition. Different types of WS-CP backbones have been used as platforms including poly(fluorene), poly(phenylene ethynylene), polythiophene, poly(phenylenevinylene), and others. Example applications of biofunctionalized WS-CPs are also reviewed. These include examples of protein sensing, flow cytometry labeling, and cancer therapy. The major challenges and future development of functionalized conjugated polymers are also discussed.