Pyrene-Functionalized Fluorescent Nanojars: Synthesis, Mass Spectrometric, and Photophysical Studies.

Nanojars are a class of supramolecular coordination complexes based on pyrazolate, Cu2+, and OH- ions that self-assemble around highly hydrophilic anions and serve as efficient anion binding and extraction agents. In this work, the synthesis, characterization, and photophysical properties of pyrene-functionalized fluorescent nanojars are presented. Three pyrene derivatives, 4-(pyren-1-yl)pyrazole (HL1), 4-(5-(pyren-1-yl)pent-4-yn-1-yl)pyrazole (HL2), and 4-(3-(pyrazol-4-yl)propyl)-1-(pyren-1-yl)-1,2,3-triazole (HL3), and the corresponding nanojars were synthesized and characterized using nuclear magnetic resonance spectroscopy and mass spectrometry. Electronic absorption, steady-state, and time-resolved fluorescence measurements were carried out to understand the interaction between the pyrene fluorophore and copper nanojars. Optical absorption measurements have shown minor ground state interaction between the fluorophore and nanojars. The fluorescence of pyrene is significantly quenched when attached to nanojars, suggesting strong contribution from the paramagnetic Cu2+ ions. Significant static quenching is observed in the case of L1, when pyrene is directly bound to the nanojar, whereas in the case of L2 and L3, when pyrene is attached to the nanojars using flexible tethers, both static and dynamic quenching are observed.

Beads on a Chain Fluorescent Oligomeric Materials: Interactions of Conjugated Organic Cross-Linkers with Silsesquioxane Cages.

Organic electronic materials have advantages over inorganics in terms of versatility, cost, and processability. Recent advancements in organic materials for light-emitting diodes (OLED), field effect transistors (OFET), and photovoltaics have engendered extensive innovation potential on this field. In this research, we focus on synthesizing SQ (silsesquioxane) based oligomers cross-linked by dibromo-aromatic linkers and explore how the cross-linker influences their photophysical properties. Bis-trialkoxy silyl (linker) model compounds were synthesized to compare noncage photophysical properties with the oligomers. Several techniques such as UV/vis, fluorescence, FTIR, and thermal gravimetric analysis (TGA) have been used to characterize the systems. Time-resolved fluorescence and femtosecond transient absorption spectroscopy were used to understand the excited state dynamics of these materials. Studies were carried out to understand the differences between monomers and oligomers and potential energy transfer and charge transfer between the cages and cross-linking chromophores. Transient absorption showed lower energy absorption from the excited states, suggesting short-range communication between moieties. Single photon counting studies have shown distinct lifetime differences between most linkers and cages display possible excitation energy transfer through these materials. Transient absorption anisotropy measurements have shown signatures for excitation energy transfer between linker chromophores for oligomeric compounds. The silsesquioxane (SQ) backbone of the oligomers gives substantial thermal stability as well as solution processability, giving better flexibility for achieving energy transfer between linking chromophores.

Synthesis and Photophysical Properties of Light-Harvesting Gold Nanoclusters Fully Functionalized with Antenna Chromophores.

The development of efficient light-harvesting systems is important to understand the key aspects of solar-energy conversion processes and to utilize them in various photonic applications. Here, atomically well-defined gold nanoclusters are reported as a new platform to fabricate artificial light-harvesting systems. An efficient amide coupling method is developed to synthesize water-soluble Au22 clusters fully protected with pyrene chromophores by taking advantage of their facile phase-transfer reaction. The synthesized Au22 clusters with densely packed 18 pyrene chromophores (Au22 -PyB18 ) exhibit triple-emission in blue, green, and red wavelength regions arising respectively from pyrene monomer, pyrene excimer, and Au22 emission, producing bright white light emission together. The photoluminescence of Au22 is enhanced by more than tenfold, demonstrating that pyrenes at the periphery efficiently channel the absorbed energy to the luminescent Au22 at the center. A combination of femtosecond transient absorption and anisotropy measurements of Au22 -PyB18 explicitly reveals three main decay components of 220 fs, 3.5 ps, and 160 ps that can be assigned to energy migration between pyrenes and energy transfer processes from pyrene monomer and excimer to the central Au22 , respectively.

The Missing Link: Au191(SPh-tBu)66 Janus Nanoparticle with Molecular and Bulk-Metal-like Properties.

Understanding the evolution of the structure and properties in metals from molecule-like to bulk-like has been a long sought fundamental question in science, since Faraday's 1857 work. We report the discovery of a Janus nanomolecule, Au191(SPh-tBu)66 having both molecular and metallic characteristics, explored crystallographically and optically and modeled theoretically. Au191 has an anisotropic, singly twinned structure with an Au155 core protected by a ligand shell made of 24 monomeric [-S-Au-S-] and 6 dimeric [-S-Au-S-Au-S-] staples. The Au155 core is composed of an 89-atom inner core and 66 surface atoms, arranged as [Au3@Au23@Au63]@Au66 concentric shells of atoms. The inner core has a monotwinned/stacking-faulted face-centered-cubic (fcc) structure. Structural evolution in metal nanoparticles has been known to progress from multiply twinned, icosahedral, structures in smaller molecular sizes to untwinned bulk-like fcc monocrystalline nanostructures in larger nanoparticles. The monotwinned inner core structure of the ligand capped Au191 nanomolecule provides the critical missing link, and bridges the size-evolution gap between the molecular multiple-twinning regime and the bulk-metal-like particles with untwinned fcc structure. The Janus nature of the nanoparticle is demonstrated by its optical and electronic properties, with metal-like electron-phonon relaxation and molecule-like long-lived excited states. First-principles theoretical explorations of the electronic structure uncovered electronic stabilization through the opening of a shell-closing gap at the top of the occupied manifold of the delocalized electronic superatom spectrum of the inner core. The electronic stabilization together with the inner core geometric stability and the optimally stapled ligand-capping anchor and secure the stability of the entire nanomolecule.

Intrinsically fluorescent gold nanoclusters stabilized within a copper storage protein that follow the Irving-Williams trend in metal ion sensing.

Creating new environmentally friendly and non-toxic biomaterials with novel properties is required for numerous applications in healthcare and sensing. Protein bound gold nanoclusters constitute one such class of materials that offer promise in fluorescence imaging and sensing applications. However, unlike alkane thiol-protected gold nanoclusters, the number of protein-templated gold nanoclusters with such properties is limited and there is a need to expand the repertoire of such attractive hybrid quantum clusters. Herein, we report the synthesis, characterization, and applications of new fluorescent gold nanoclusters with tunable emission properties including blue, orange, and red, within a four-helix bundle copper storage protein (Csp1). The template protein consists of 13 cysteines along the length of the helix, which are suitable ligands to template Au and stabilize the resulting 14-19 atom clusters within the protein. The resulting clusters were extensively characterized by employing spectroscopic, microscopic and other analytical methods. The optical emission, relative quantum yields, and the excited state lifetime of the clusters are shown to depend on synthetic conditions. The clusters were found to be sensitive to the ppm level of transition metal ions with the quenching capabilities following the Irving-Williams series of metals (Co2+ < Ni2+ < Cu2+), which is rationalized based on the relative affinities of transition metals for a given set of ligands. The clusters were also found to be stable across the pH range 4-8.5 which, along with tunable emission properties paves the path for live bio-imaging and bio-sensing applications under physiological conditions.

Theoretical investigation of size, shape, and aspect ratio effect on the LSPR sensitivity of hollow-gold nanoshells.

The change in refractive index around plasmonic nanoparticles upon binding to biomolecules is routinely used in localized surface plasmon resonance (LSPR)-based biosensors and in biosensing platforms. In this study, the plasmon sensitivity of hollow gold (Au) nanoshells is studied using theoretical modeling where the influence of shape, size, shell thickness, and aspect ratio is addressed. Different shapes of hollow Au nanoshells are studied that include sphere, disk, triangular prism, rod, ellipsoid, and rectangular block. Multilayered Mie theory and discrete dipole approximation were used to determine the LSPR peak position and LSPR sensitivity as a function of size, shell thickness, shape, and aspect ratio. The change in LSPR peak wavelength per unit refractive index is defined as the sensitivity, and interesting results were obtained from the analysis. The rectangular block and rod-shaped Au nanoshells have shown maximum LSPR sensitivity when compared to other shaped Au nanoshells. In addition, increased sensitivity was observed for higher aspect ratio as well as for smaller shell thicknesses. The results are rationalized based on the inner and outer surface plasmonic coupling.

Unique Energy Transfer in Fluorescein-Conjugated Au22 Nanoclusters Leading to 160-Fold pH-Contrasting Photoluminescence.

Accurate measurements of intracellular pH are of crucial importance in understanding the cellular activities and in the development of intracellular drug delivery systems. Here we report a highly sensitive pH probe based on a fluorescein-conjugated Au22 nanocluster. Steady-state photoluminescence (PL) measurements have shown that, when conjugated to Au22, fluorescein exhibits more than 160-fold pH-contrasting PL in the pH range of 4.3-7.8. Transient absorption measurements show that there are two competing ultrafast processes in the fluorescein-conjugated Au22 nanocluster: the intracore-state relaxation and the energy transfer from the nonthermalized states of Au22 to fluorescein. The latter becomes predominant at a higher pH, leading to dramatic PL enhancement of fluorescein. In addition to the intrinsically low toxicity, fluorescein-conjugated Au22 nanoclusters exhibit high pH sensitivity, wide dynamic range, and excellent photostability, providing a powerful tool for the study of intracellular processes.

Au279(SR)84: The Smallest Gold Thiolate Nanocrystal That Is Metallic and the Birth of Plasmon.

We report a detailed study on the optical properties of Au279(SR)84 using steady-state and transient absorption measurements to probe its metallic nature, time-dependent density functional theory (TDDFT) studies to correlate the optical spectra, and density of states (DOS) to reveal the factors governing the origin of the collective surface plasmon resonance (SPR) oscillation. Au279 is the smallest identified gold nanocrystal to exhibit SPR. Its optical absorption exhibits SPR at 510 nm. Power-dependent bleach recovery kinetics of Au279 suggests that electron dynamics dominates its relaxation and it can support plasmon oscillations. Interestingly, TDDFT and DOS studies with different tail group residues (-CH3 and -Ph) revealed the important role played by the tail groups of ligands in collective oscillation. Also, steady-state and time-resolved absorption for Au36, Au44, and Au133 were studied to reveal the molecule-to-metal evolution of aromatic AuNMs. The optical gap and transient decay lifetimes decrease as the size increases.

Energy Gap Law for Exciton Dynamics in Gold Cluster Molecules.

The energy gap law relates the nonradiative decay rate to the energy gap separating the ground and excited states. Here we report that the energy gap law can be applied to exciton dynamics in gold cluster molecules. Size-dependent electrochemical and optical properties were investigated for a series of n-hexanethiolate-protected gold clusters ranging from Au25 to Au333. Voltammetric studies reveal that the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps of these clusters decrease with increasing cluster size. Combined femtosecond and nanosecond time-resolved transient absorption measurements show that the exciton lifetimes decrease with increasing cluster size. Comparison of the size-dependent exciton lifetimes with the HOMO-LUMO gaps shows that they are linearly correlated, demonstrating the energy gap law for excitons in these gold cluster molecules.

Au21S(SAdm)15: An Anisotropic Gold Nanomolecule. Optical and Photoluminescence Spectroscopy and First-Principles Theoretical Analysis.

We introduce a class of gold nanomolecules exhibiting anisotropy as a major feature by reporting steady-state and time-resolved photoluminescence and anisotropy measurements and in-depth theoretical analysis of energetics and optical response of a recently synthesized Au21S(SAdm)15 nanomolecule (SAdm = adamantanethiol). Starting from single-crystal X-ray data showing that Au21S(SAdm)15 exhibits a symmetry-broken structure, we unambiguously demonstrate how this translates into a striking anisotropy of its properties, for example, of its (chiro)optical absorption spectrum of great promise for sensing, optoelectronic, and electrochemical applications, and argue about the abundance and general significance of this class of compounds.

Enhanced luminescence of Au22(SG)18 nanoclusters via rational surface engineering.

We report design strategies for the preparation of highly luminescent Au22(SG)18 clusters, where SG is glutathione, by the functionalization of the cluster shell. In these strategies, the cluster shell was covalently modified with small aromatic molecules and pyrene chromophores that led to a 5-fold PL enhancement by rigidifying the shell-gold. Highly luminescent water-soluble gold clusters with a PL quantum yield of 30% were obtained at room temperature. To further enhance the luminescence, the pyrene chromophores in the functionalized Au22 clusters were photoexcited at 350 nm to induce energy transfer from pyrene to the Au22 cluster. Steady-state and time-resolved PL measurements have shown evidence of enhanced rigidity with increased PL lifetimes for the functionalized Au22 clusters. However, the energy transfer efficiency was found to be only 14% because of the competing electron transfer deactivation pathway as evidenced by the formation of the pyrene anion radical revealed in the ultrafast transient absorption measurements. To suppress the electron transfer pathway, the pyrene functionalized Au22 clusters were ion-paired with tetraoctylammonium (TOA) cations that could break the electron transfer pathway, leading to a dramatic 37-fold increase in PL brightness with the resonance energy transfer efficiency of ca. 80%. This work presents effective design strategies for the preparation of highly luminescent gold clusters by the combination of rigidifying effect and energy transfer sensitization.

Ultrabright Luminescence from Gold Nanoclusters: Rigidifying the Au(I)-Thiolate Shell.

Luminescent nanomaterials have captured the imagination of scientists for a long time and offer great promise for applications in organic/inorganic light-emitting displays, optoelectronics, optical sensors, biomedical imaging, and diagnostics. Atomically precise gold clusters with well-defined core-shell structures present bright prospects to achieve high photoluminescence efficiencies. In this study, gold clusters with a luminescence quantum yield greater than 60% were synthesized based on the Au22(SG)18 cluster, where SG is glutathione, by rigidifying its gold shell with tetraoctylammonium (TOA) cations. Time-resolved and temperature-dependent optical measurements on Au22(SG)18 have shown the presence of high quantum yield visible luminescence below freezing, indicating that shell rigidity enhances the luminescence quantum efficiency. To achieve high rigidity of the gold shell, Au22(SG)18 was bound to bulky TOA that resulted in greater than 60% quantum yield luminescence at room temperature. Optical measurements have confirmed that the rigidity of gold shell was responsible for the luminescence enhancement. This work presents an effective strategy to enhance the photoluminescence efficiencies of gold clusters by rigidifying the Au(I)-thiolate shell.

Two-photon absorption properties of chromophores in micelles: electrostatic interactions.

Two-photon absorption (2PA) cross sections of neutral Coumarin 485 (C485) and anionic Coumarin 519 (C519(-)) solubilized in Triton X-100 (Tx-100, neutral), sodium dodecyl sulfate (SDS, anionic), and cetyltrimethylammonium bromide (CTAB, cationic) are reported. The objective of the study is to probe the influence of local electrostatic fields in micelles on the 2PA properties of chromophores. The 2PA measurements have shown that the cross sections of neutral C485 are unchanged in different micellar environments, although the local micropolarities of chromophores are different. On the other hand, the 2PA cross sections of C519(-) are unchanged or slightly decreased in Tx-100 and SDS micelles when compared to water while 100% increase in 2PA cross sections was observed for C519(-) in CTAB micelles. The enhancement in 2PA cross section is attributed to the electrostatic fields arising in the Stern layer of CTAB, where C519(-) is solubilized. The titration measurements have shown that the 2PA enhancement is due to the organized medium only and not because of the simple association of C519(-) and the quaternary ammonium group of CTAB. From the analysis, local electric field of 0.7 ± 0.3 MV/cm is estimated for the Stern layer of CTAB.

Single- and multiphoton turn-on fluorescent Fe(3+) sensors based on bis(rhodamine).

Selective and sensitive turn-on fluorescent Fe(3+) sensors based on novel bis(rhodamine) dye molecules are reported. The compounds are synthesized with very high yields and characterized with NMR, ESI mass spectrometry, and elemental analysis. Single- and two-photon fluorescence enhancement is observed for both molecules in the presence of Fe(3+). High selectivity and sensitivity is observed over other metal ions and is shown to be due mainly to the spirolactam ring-opening power of Fe(3+). All measurements are made in buffer environments simulating biological conditions to facilitate single- and multiphoton fluorescence imaging of Fe(3+) in vivo and in vitro. Larger enhancement of fluorescence for both one- and two-photon excitation makes them suitable candidates for fluorescent labeling of biological systems. Two photon cross-section and time-resolved fluorescence measurements are utilized to understand the selectivity of the present sensors for Fe(3+)-sensing.

Optically excited acoustic vibrations in quantum-sized monolayer-protected gold clusters.

We report a systematic investigation of the optically excited vibrations in monolayer-protected gold clusters capped with hexane thiolate as a function of the particle size in the range of 1.1-4 nm. The vibrations were excited and monitored in transient absorption experiments involving 50 fs light pulses. For small quantum-sized clusters (< or =2.2 nm), the frequency of these vibrations has been found to be independent of cluster size, while for larger clusters (3 and 4 nm), we did not observe detectable optically excited vibrations in this regime. Possible mechanisms of excitation and detection of the vibrations in nanoclusters in the course of the transient absorption are discussed. The results of the current investigation support a displacive excitation mechanism associated with the presence of finite optical energy gap in the quantum-sized nanoclusters. Observed vibrations provide a new valuable diagnostic tool for the investigations of quantum size effects and structural studies in metal nanoclusters.

Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

Critical size for the observation of quantum confinement in optically excited gold clusters.

We present a systematic study of optical properties of a series of hexanethiolate-capped Au clusters of varying sizes using femtosecond transient absorption, time-resolved fluorescence, and two-photon absorption cross-sectional measurements. An abrupt change in optical properties and their trends has been found at the 2.2 nm size. Displacively excited vibrations with a period of 450 fs have been detected in the transient absorption signal for smaller clusters < or = 2.2 nm. These results strongly suggest an emerging optical gap between the highest occupied and lowest unoccupied orbitals in the narrow size range at 2.2 nm.

Quantum-sized gold clusters as efficient two-photon absorbers.

The two-photon absorption properties of Au25 cluster has been investigated with the aid of two-photon excited fluorescence in the communication wavelength region with a cross-section of 2700 GM at 1290 nm. Additional visible fluorescence has been discovered for small gold clusters which is two-photon allowed (after excitation at 800 nm), and the absolute cross-section has been determined for gold clusters with number of gold atoms varying from 25 to all the way up to 2406 using one and two-photon excited time-resolved fluorescence upconversion measurements. Record high TPA cross-sections have been measured for quantum sized clusters making them suitable for two-photon imaging as well as other applications such as optical power limiting and lithography.

Oligothiophene dendrimers as new building blocks for optical applications.

Thiophene branched structures have been proposed as candidates for photon harvesting and electron-hole transporting materials in novel organic light emitting diodes and solar energy conversion devices. To understand the photoinduced processes in a novel thiophene dendrimer system, the excited state dynamics and nonlinear optical properties of 3D oligothiophene dendrimers have been investigated. The key point of this contribution is that we have found that with these thiophene dendrimer systems, the excitation is delocalized over a large number of thiophene units in the dendrimer and there is an ultrafast energy transfer (200-300 fs) to the longest branch of dendrimer, which can be utilized for future optical devices. In terms of nonlinear optics, it was found that a super-linear increase of two-photon absorption cross-section is observed with an increase in thiophene dendrimer generation that can be explained by the increased excitation delocalization. Generation dependent torsional energy redistribution has also been observed, which planarizes the final emissive state on a picosecond time scale.