RESUMEN
The utilization of aluminum, an abundant and inexpensive element, for the synthesis of novel functional complexes is extremely important, but the design and control of photofunctionality are still unexplored. In this study, we focused on our previously developed dinuclear triple-stranded helicates incorporating two aluminum ions (ALPHY) to synthesize both homoleptic and heteroleptic complexes with bromine atoms at the 3-position of the pyrrole moiety in the Schiff base ligands. The brominated Schiff base ligands were reacted with AlCl3 to synthesize homoleptic complexes, while different ligands were mixed to prepare heteroleptic complexes. Single-crystal X-ray structural analysis revealed the structures of these novel complexes. We found that increasing the degree of bromination resulted in a tunable emission color, shifting progressively from 550 (yellow) to 566 nm (orange). Optical resolution of the complexes facilitated the observation of mirror-image circular dichroism and circularly polarized luminescence. Furthermore, employing ultrafast spectroscopy techniques, we have elucidated that the optical properties are governed by the interligand charge transfer (ILCT) among the three ligands. The formation of heteroleptic complexes induces the ILCT state even in nonpolar environments, thereby accelerating nonradiative decay and intersystem crossing. These findings mark significant advancements in photofunctional materials based on multinuclear complexes.
RESUMEN
This study explored the development of functional dyes using aluminum, focusing on aluminum-based dinuclear triple-stranded helicates, and examined the effects of substituent variations on their structural and optical properties. Key findings revealed that the modification of methyl groups to the pyrrole positions significantly extended the conjugation system, resulting in a red shift in the absorption and emission spectra. Conversely, the modification of methyl groups at the methine positions due to steric hindrances increased the torsion angle of the ligands, leading to a blue shift in the absorption and emission spectra. A common feature across all complexes was that in the excited state, one of the three ligands underwent significant structural relaxation. This led to a pronounced Stokes shift and minimal spectra overlap with high photoluminescence behaviors. Moreover, our research extended to the optical resolution of the newly synthesized complexes by analyzing the chiroptical properties of the resulting enantiomers, including their circular dichroism and circularly polarized luminescence. These insights offer valuable contributions to the design and application of novel aluminum-based functional dyes, potentially influencing a range of fields, from materials science to optoelectronics.
RESUMEN
Self-inclusion complexes consisting of host-guest conjugates are one of the unique supramolecular structures because they form in-state and out-state depending on the external stimuli. Despite many reports of the stimuli-responsive self-inclusion complex formation, study of the structural relaxation from out-state to in-state by photoexcitation has been unexplored. Herein, we report that an electron-donating host and an electron-accepting guest conjugate exhibits the structural relaxation from out-state to in-state by photoexcitation. Formation of the in-state in the excited state resulted in exciplex emission along with the locally excited emission from the out-state. Moreover, this structural relaxation by photoexcitation was suppressed not only by temperature, but also by the presence of guest molecules, resulting in changes in the ratio of the dual emission intensities.
RESUMEN
This study reports an effective peripheral decoration of organic donor-acceptor diads with B(C6 F5 )3 for stabilizing electrogenerated radical ions. By employing a common p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156-fold increase compared to that of the parent diad. The unprecedented Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C6 F5 )3 : 1)â redistributing frontier orbitals, 2)â facilitating electrochemical excitation, and 3)â restricting molecular motions. Furthermore, B(C6 F5 )3 converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π-stacks. This robust, highly ordered columnar nanostructure allowed red-shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal-free ECL systems.
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This study reports the facile syntheses of tetra-boron difluoride (tetra-BF2 ) complexes, flag-hinge-like molecules that exhibit intense green-to-orange luminescence in solution and yellow-to-red emission in the solid states. Single-crystal structure analysis and density functional theory calculations suggested a bent structure of this series of compounds. The complexes also exhibited excellent optical properties, with quantum yields reaching 100 % and a large Stokes shift. These properties were attributed to the altered bending angle of the molecule in the S1 excited state. As the rotational motion was suppressed around the 2,2'-bipyrrole axis, atropisomers with axial chirality were formed, which are optically resolvable into (R) and (S)-enantiomers through a chiral column. The atropisomers thus function as circularly polarized luminescent (CPL) materials, in which the color (green, green-yellow, and yellow) can be varied by controlling the aggregation state. This rational design of multi-BF2 complexes can potentially realize novel photofunctional materials.
RESUMEN
The construction of novel complexes can lead to the manifestation of unexpected structures and properties, thereby making chemical exploration in experiments a potential source for novel discoveries. In this study, by reacting 6,6'-dihydrazineyl-2,2'-bipyridine with acyl chlorides and subsequently coordinating with boron trifluoride, two different boron-tetradentate ligand complexes were simultaneously generated. One of these complexes exhibited a unique structure in which tetra-BF2 moieties coordinated to all four coordination sites of the ligand molecule, forming a flag-hinged structure around the bipyridine part. The second complex featured a helical structure formed by the hybridization of two BF2 and one B-O-B moieties, representing a highly unusual form of the complex. The structures of these two boron complexes were consistently observed when various substituted acyl chlorides were employed. Furthermore, it was found that enhancing electron-donor properties could induce a redshift in emissions. Utilizing the dimethylamino group as the proton receptor promoted a yellow-to-blue fluorescence switch in the tetra-BF2 complex and an OFF/ON fluorescence in the B-O-B bridged complex upon protonation. The helical chirality observed in the latter complex resulted in stable (P)/(M)-enantiomers after optical resolution. This complex exhibited circular dichroism with a |gabs| of up to 1.2 × 10-2 and circularly polarized luminescence with a |glum| on the order of 10-3 in solution and polymer film.
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Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes as guests into a host molecule combining benzophenone with naphthalene diimide. This approach led to the creation of fascinating fluorescence and RTP properties dependent on the guest molecules. Notably, crystals containing chlorobenzene showed cyan fluorescence, while those with iodobenzene displayed red RTP. This difference highlights the impact of the guest molecule on the luminescent properties, with the significant external heavy-atom effect of iodobenzene playing a key role in promoting efficient intersystem crossing between the excited singlet and triplet states. Crystals with bromobenzene exhibited a unique blend of fluorescence and RTP, both from benzophenone and naphthalene diimide, highlighting the moderate heavy-atom effect. These findings reveal composite materials with remarkably diverse and interesting optical characteristics.
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Imine/Oxime-type cobalt complexes, regarded as simple vitamin B12 model complexes, were utilized as catalysts for direct C-H perfluoroalkylations of indole and aniline derivatives with nonafluorobutyl iodide (n-C4F9I) as the readily available perfluoroalkyl source. The synthetic approach described herein was performed under mild reaction conditions driven by controlled-potential electrolysis at -0.8 V vs. Ag/AgCl in organic solvents. The mechanistic investigations suggest that a nonafluorobutyl radical is mediated by homolytic cleavage of the cobalt(iii)-carbon bond in the catalytic cycle. This is the first report concerning a fluoroalkylation reaction of (hetero)aromatics catalyzed by the simple vitamin B12 model complex. The convenient electrocatalytic method employing a simple cobalt complex provides a facile synthesis method toward novel fluoroalkylated compounds, demonstrating potential applications in the fields of pharmaceutical chemistry and materials science.
RESUMEN
A proof-of-concept for the one-step, synthetically challenging cyclic and acyclic perfluoroalkylation of (hetero)arenes driven by the valence change of a vitamin B12 derivative as a cobalt catalyst in the presence of fluoroalkylating reagents (X(CF2)4X) is presented. The consecutive formation of cobalt-carbon bonds and generation of fluoroalkyl radicals by homolysis are the key steps for the reaction to proceed.
RESUMEN
Spinel Li4Ti5O12 (LTO) and reduced graphene oxide (rGO) are attractive anode materials for lithium-ion batteries (LIBs) because of their unique electrochemical properties. Herein, we report a facile one-step hydrothermal method in preparation of a nanocomposite anode consisting of well-dispersed mesoporous LTO particles onto rGO. An important reaction step involves glucose as a novel linker agent and reducing agent during the synthesis. It was found to prevent the aggregation of LTO particles, and to yield mesoporous structures in nanocomposites. Moreover, GO is reduced to rGO by the hydroxyl groups on glucose during the hydrothermal process. When compared to previously reported LTO/graphene electrodes, the newly prepared LTO/rGO nanocomposite has mesoporous characteristics and provides additional surface lithium storage capability, superior to traditional LTO-based materials for LIBs. These unique properties lead to markedly improved electrochemical performance. In particular, the nanocomposite anode delivers an ultrahigh reversible capacity of 193 mA h g(-1) at 0.5 C and superior rate performance capable of retaining a capacity of 168 mA h g(-1) at 30 C between 1.0 and 2.5 V. Therefore, the newly prepared mesoporous LTO/rGO nanocomposite with increased surface lithium storage capability will provide a new opportunity to develop high-power anode materials for LIBs.