Metal-Cluster-Based Colloidal Excimer Superstructures
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Luminescent network: Colloidal excimer superstructures with unique optical and electronic properties have recently been described. Ground-state gold cluster cores were held together by the hydrogen-bonding network formed by their capping ligands, which enabled excimer formation.Keywords:
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Abstract Two novel pyrene‐based isocyanide gold(I) complexes have been designed and synthesized. The different structures lead to distinct and diverse photophysical properties both in solution and in the aggregate state. Multiple photoluminescence, involving monomer emission, locally excited emission and excimer emission, are observed. Notably, an excimer is formed by aggregation in solution and external mechanical stimulation in the solid state, showing aggregation‐ and mechano‐induced excimer emission.
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Abstract Exciplex (DA)* and triple exciplex (DDA)* formation between 1,4-dicyanobenzene (DCB) and alkylnaphthalenes was investigated by steady-state and nanosecond time-resolved fluorescence spectroscopies at room temperature. Typical two-component decay of the exciplex and the fluorescence rise of the triple exciplex were observed in dioxane solutions of DCB and several alkylnaphthalenes. The results imply a significant dissociation process of (DDA)* to (DA)*. Triple exciplex formation via excimer (DD)* was proposed to be significant in a concentrated solution of alkylnaphthalene (>10−1 M), while the triple exciplex was formed via the exciplex in a dilute solution of the electron donor.
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Emission and Quenching of the Pyrenesulfonate Excimer on a Dodecyltrimethylammonium Micellar Surface
Abstract The excimer formation and decay dynamics of pyrenesulfonate on a cationic micellar surface have been studied by measuring the decay of monomer fluorescence as well as the rise and decay of the excimer emission. The excimer formation rate constant, lifetime, and quenching rate constant by the monomer were found to be 2.1 × 107 s−1, 46.2 ns, and 2.6 × 106 s−1, respectively.
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This article reports the alteration of the excited state photophysics of a molecular rotor, namely 9-(dicyano-vinyl)julolidine (DCVJ), which has been extensively used to report protein aggregation and protein conformational changes, by the various cavity sizes of cyclodextrin (CD) macrocyclic hosts, with the help of steady state, time-resolved fluorescence techniques. It is observed that, in the presence of α-CD, the characteristic features of both the monomer and excimer emissions of DCVJ are almost unperturbed. However, in the presence of β-CD, the excited photophysics of the molecule is significantly perturbed, and it is noted that β-CD inhibits the excimer formation drift of DCVJ by incorporation of a DCVJ monomer inside its cavity. The most striking findings are observed in the case of γ-CD. Initially, the excimer peak intensity drops and the monomer intensity increases, due to the 1 : 1 DCVJ/γ-CD inclusion complex formation. Above a certain concentration, another DCVJ molecule is accommodated inside the γ-CD cavity and forms an excimer, which is reflected in the intensification of the excimer peak. At higher γ-CD concentration the fluorescence intensity of the excimer shoots up, due to the formation of 2 : 2 host-guest complex, in which an additional γ-CD molecule provides extra stabilization to the excimer. Insight on the molecular picture of this host-guest interaction has been provided by docking studies followed by quantum chemical calculations.
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Synthesis of a novel pyrene derivative sensor (1) and its intermolecular binding pattern to Cu(2+) in CH(3)CN were investigated. Upon Cu(2+) binding, the sensor exhibited a strong static excimer emission at 460 nm, along with a weak monomer emission at 388 nm. The excimer emission intensity induced by the Cu(2+) ion declined as the spacer length between the pyrene and quinolinylamide unit increased. The Cu(2+) ion-induced self-assembled pyrenyl excimer formation is rationalized by fluorescence experiments and theoretical DFT calculations.
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