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).

Bubble Printing of TiCT MXene for Patterning Conductive and Plasmonic Nanostructures.

MXenes represent a novel class of 2D materials with unique properties and have great potential for diverse applications in sensing and electronics; however, their directed assembly at interfaces has not yet been achieved. Herein, the plasmonic heating of MXenes was exploited to achieve the controlled deposition of MXene assemblies via a laser-directed microbubble. The influence of various factors such as solvent composition, substrate surface chemistry, MXene concentration, and laser fluence was investigated, establishing the optimal conditions for rapid patterning with good fidelity.

Layered silicate edge-linked perylene diimides: Synthesis, self-assembly and energy transfer.

The control over intermolecular interactions between chromophores at nanomaterial interfaces is important for sensing and light-harvesting applications. To that aim, inorganic nanoparticles with anisotropic shape and surface chemistry can serve as useful supports for organic modification. Herein, novel asymmetric perylene diimides with aspartic acid and oleyl terminal groups were grafted to the edges of the layered silicate clay Laponite, a water-dispersible discoidal nanoparticle.

Photoinduced Intramolecular Electron Transfer in Phenylene Ethynylene Naphthalimide Oligomers.

This paper reports a photophysical investigation of a series of phenylene ethynylene oligomers (OPE) that are end-substituted with a 1,8-naphthalene imide (NI) acceptor. The NI acceptor is attached to the terminus of the OPEs an ethynylene (-C≡C-) unit that is linked at the 4-position of the NI unit. A series of three oligomers is investigated, OPE1-NI, OPE3-NI, and OPE5-NI, which contain 1, 3, and 5 phenylene ethynylene repeat units, respectively.

Ultrafast Excited-State Dynamics in -(N-Heterocyclic carbene)platinum(II) Acetylide Complexes.

This study probes femto- and picosecond excited-state dynamics of a series of N-heterocyclic carbene (NHC) ligand-containing platinum(II) complexes of the type -(NHC)Pt(CC-Ar), where CC-Ar is an arylacetylide. By using femtosecond transient absorption spectroscopy, two dynamic processes are observed: an ultrafast singlet → triplet intersystem crossing (<0.3 ps), followed by geometric/electronic relaxation that takes place on a 2-10 ps time scale.

High-Purity and Saturated Deep-Blue Luminescence from -NHC Platinum(II) Butadiyne Complexes: Properties and Organic Light Emitting Diode Application.

Two new platinum(II) compounds with -(NHC)Pt(C≡C-C≡C-R) (where NHC = N-heterocyclic carbene and R = phenyl or trimethylsilyl) architecture exhibit sharp blue-green or saturated deep-blue phosphorescence with high color purity. The photoluminescence of both compounds is dominated by an intense 0-0 band with distinct but weaker vibronic progressions in both tetrahydrofuran (THF) and poly(methyl methacrylate) (PMMA) matrix. The full width at half-maximum (fwhm) of the photoluminescence of -(NHC)Pt(C≡C-C≡C-trimethylsilyl) are 10 nm at room temperature and 4 nm at 77 K, while the -(NHC)Pt(C≡C-C≡C-phenyl) shows a fwhm of 14 nm at room temperature and 8 nm at 77 K.

Aggregation-Enhanced Two-Photon Absorption of Anionic Conjugated Polyelectrolytes.

The two-photon absorption properties of anionic poly(phenylene ethynylene)-type conjugated oligo- and polyelectrolytes are studied in molecularly dissolved and aggregated forms in aqueous solution. Several different polyvalent cations are used to induce aggregation. It is found that both materials in the aggregated form exhibit enhanced two-photon excited fluorescence (2PEF) and two-photon cross section (σ) compared with the molecularly dissolved structures.

Structure of a Zinc Porphyrin-Substituted Bacterioferritin and Photophysical Properties of Iron Reduction.

The iron storage protein bacterioferritin (Bfr) binds up to 12 hemes at specific sites in its protein shell. The heme can be substituted with the photosensitizer Zn(II)-protoporphyrin IX (ZnPP), and photosensitized reductive iron release from the ferric oxyhydroxide {[FeO(OH)]} core inside the ZnPP-Bfr protein shell was demonstrated [Cioloboc, D., et al.

Preparation of platinum nanoparticles using iron(ii) as reductant and photosensitized H generation on an iron storage protein scaffold.

The quest for efficient solar-to-fuel conversion has led to the development of numerous homogeneous and heterogeneous systems for photochemical stimulation of 2H + 2e → H. Many such systems consist of a photosensitizer, an H-evolving catalyst (HEC), and sacrificial electron donor often with an electron relay between photosensitizer and HEC. Colloidal platinum remains a popular HEC.

Stereochemical Effects on Platinum Acetylide Two-Photon Chromophores.

A series of -platinum(II) acetylide complexes containing two-photon-absorbing chromophores have been synthesized and characterized to explore the effects of stereochemistry on the nonlinear absorption properties. The molecules feature 4-(phenylethynyl)phenylethynylene (PE2), diphenylaminofluorene (DPAF), and benzothiazolylfluorene (BTF) ligands. The photophysical properties were investigated under one- and two-photon conditions and compared to the known analogues via UV-visible absorption, photoluminescence, femtosecond and nanosecond transient absorption (TA), nanosecond z-scan, and femtosecond two-photon absorption (2PA).

Blue Phosphorescent -N-Heterocyclic Carbene Platinum Acetylides: Dependence on Energy Gap and Conformation.

A series of 11 complexes of the type -(NHC)Pt(CC-Ar) (where NHC = N-heterocyclic carbene) have been synthesized and their photophysics characterized. The complexes display moderately efficient deep blue to green phosphorescence from a triplet excited state that is localized mainly in the aryl acetylide ligand (CC-Ar). The emission energy varies with the substituent on CC-Ar, with the highest energy emission for Ar = 4-pyridyl.

Adenosine Triphosphate Templated Self-Assembly of Cationic Porphyrin into Chiral Double Superhelices and Enzyme-Mediated Disassembly.

Self-assembly of small molecules through noncovalent interactions into nanoscale architectures has been extensively studied in supramolecular chemistry. However, it is still challenging to develop a biologically inspired self-assembly system that functions in water with complex structure and dynamics by analogy with those found in nature. Here, we report a new water-soluble cationic porphyrin that undergoes adenosine triphosphate (ATP)-templated self-assembly into right-handed double-helical supramolecular structures.

Photophysical Behavior of Isocyanine/Clay Hybrids in the Solid State †.

In the present study, we have attempted to investigate, for the first time, the photophysical behavior of 1,1'-diethyl-2,4'-cyanine (ICY)/clay mineral hybrids in the solid state. The effects promoted by ICY loading and clay type on the spectroscopic properties were studied by UV-vis diffuse reflectance spectroscopy (DR) and different fluorescence techniques. The hybrids were characterized by X-ray diffraction (XRD) and thermogravimetric analysis (TGA).

Optical devices for the detection of cyanide in water based on ethyl(hydroxyethyl)cellulose functionalized with perichromic dyes.

Films of three polymers, based on ethyl(hydroxyethyl)cellulose functionalized with protonated perichromic dyes, were used for anion sensing. The polymer functionalized with protonated Brooker's merocyanine acts as a chromogenic/fluorogenic system for the selective detection of cyanide in water. An increase of >28 times was verified for the fluorescence lifetime of the sensing units in the polymer in comparison with protonated Brooker's merocyanine in water.