Luis Gutiérrez-Arzaluz

Bio: Luis Gutiérrez-Arzaluz is an academic researcher from King Abdullah University of Science and Technology. The author has contributed to research in topics: Materials science & Excited state. The author has an hindex of 5, co-authored 20 publications receiving 123 citations. Previous affiliations of Luis Gutiérrez-Arzaluz include National Autonomous University of Mexico.

Access to Highly Efficient Energy Transfer in Metal–Organic Frameworks via Mixed Linkers Approach

Abstract: Herein, we report a new light-harvesting mixed-ligand Zr(IV)-based metal-organic framework (MOF),with underlying fcu topology, encompassing the [Zr6(μ3-O)4(μ3-OH)4(O2C-)12] cluster and an equimolar mixture of thiadiazole- and benzimidazole-functionalized ligands. The successful integration of ligands with similar structural features but with notable chemical distinction afforded the attainment of a highly efficient energy transfer (ET). Notably, the very strong spectral overlap between the emission spectrum of benzimidazole (energy donor) and the absorption spectrum of thiadiazole (energy acceptor) provided an ideal platform to achieve very rapid (picosecond time scale) and highly efficient energy transfer (around 90% efficiency), as evidenced by time-resolved spectroscopy. Remarkably, the ultrafast time-resolved experiments quantified for the first time the anticipated close proximity of the two linkers with an average distance of 17 A. This finding paves the way for the design and synthesis of periodic MOFs affording very efficient and fast ET to mimic natural photosynthetic systems.

Ultrafast excited state hydrogen atom transfer in salicylideneaniline driven by changes in aromaticity

Abstract: We investigated two important unresolved issues on excited state intramolecular proton transfer (ESIPT) reactions, i.e., their driving force and the charge state of the transferred species by means of quantum chemical topology. We related changes in the aromaticity of a molecule after electron excitation to reaction dynamics in an excited state. Additionally, we found that the conveyed particle has a charge intermediate between that of a bare proton and a neutral hydrogen atom. We anticipate that the analysis presented in this communication will yield valuable insights into ESIPT and other similar photochemical reactions.

Large-Area Perovskite-Related Copper Halide Film for High-Resolution Flexible Xray Imaging Scintillation Screens

Abstract: : Flexible copper halide fi lms of 400 cm 2 area were fabricated with outstanding mechanical stability, excellent fi lm uniformity, nearly 100% photoluminescence quantum yields, and resistance to water and heat. The re-absorption-free X-ray imaging scintillators engineered based on these fi lms exhibit superior scintillation performance with a detection limit as low as 48.6 nGy/s and 17 lp/mm X-ray imaging resolution, representing the highest imaging resolution for powder-based screens.

Nearly 100% energy transfer at the interface of metal-organic frameworks for X-ray imaging scintillators

Abstract: Summary In this work, we describe a highly efficient and reabsorption-free X-ray-harvesting system using luminescent metal-organic framework (MOF)-fluorescence chromophore composite films. The ultrafast time-resolved experiments and density functional theory calculations demonstrate that a nearly 100% energy transfer from a luminescent MOF with a high atomic number to an organic chromophore with thermally activated delayed fluorescence (TADF) character can be achieved. Such an unprecedented efficiency of interfacial energy transfer and the direct harnessing of singlet and triplet excitons of the TADF chromophore led to remarkable enhancement of radioluminescence upon X-ray radiation. A low detection limit of 256 nGy/s of the fabricated X-ray imaging scintillator was achieved, about 60 times lower than the MOF and 7 times lower than the organic chromophore counterparts. More importantly, this detection limit is about 22 times lower than the standard dosage for a medical examination, making it an excellent candidate for X-ray radiography.

Heavy-atom engineering of thermally activated delayed fluorophores for high-performance X-ray imaging scintillators

Abstract: The architectural design and fabrication of low-cost and reliable organic X-ray imaging scintillators with high light yield, ultralow detection limits and excellent imaging resolution is becoming one of the most attractive research directions for chemists, materials scientists, physicists and engineers due to the devices’ promising scientific and applied technological implications. However, the optimal balance among X-ray absorption capability, exciton utilization efficiency and photoluminescence quantum yield of organic scintillation materials is extremely difficult to achieve because of several competitive non-radiative processes, including intersystem crossing and internal conversion. Here we introduced heavy atoms (Cl, Br and I) into thermally activated delayed fluorescence (TADF) chromophores to significantly increase their X-ray absorption cross-section and maintaining their unique TADF properties and high photoluminescence quantum yield. The X-ray imaging screens fabricated using TADF-Br chromophores exhibited highly improved X-ray sensitivity and imaging resolution compared with the TADF-H counterpart. More importantly, the high X-ray imaging resolution of >18.0 line pairs per millimetre achieved from the TADF-Br screen exceeds most reported organic and conventional inorganic scintillators. This study could help revive research on organic X-ray imaging scintillators and pave the way towards exciting applications for radiology and security screening. Heavy atoms like Cl, Br and I introduced into thermally activated delayed fluorescence chromophores can increase the X-ray absorption cross-section. Light yield of ~20,000 photons MeV–1, detection limit of 45.5 nGy s−1 and imaging resolution of >18.0 line pairs per millimetre is demonstrated.

Programmable Logic in Metal-Organic Frameworks for Catalysis.

Abstract: Metal-organic frameworks (MOFs) have emerged as one of the most widely investigated materials in catalysis mainly due to their excellent component tunability, high surface area, adjustable pore size, and uniform active sites. However, the overwhelming number of MOF materials and complex structures has brought difficulties for researchers to select and construct suitable MOF-based catalysts. Herein, a programmable design strategy is presented based on metal ions/clusters, organic ligands, modifiers, functional materials, and post-treatment modules, which can be used to design the components, structures, and morphologies of MOF catalysts for different reactions. By establishing the corresponding relationship between these modules and functions, researchers can accurately and efficiently construct heterometallic MOFs, chiral MOFs, conductive MOFs, hierarchically porous MOFs, defective MOFs, MOF composites, and MOF-derivative catalysts. Further, this programmable design approach can also be used to regulate the physical/chemical microenvironments of pristine MOFs, MOF composites, and MOF-derivative materials for heterogeneous catalysis, electrocatalysis, and photocatalysis. Finally, the challenging issues and opportunities for the future research of MOF-based catalysts are discussed. Overall, the modular design concept of this review can be applied as a potent tool for exploring the structure-activity relationships and accelerating the on-demand design of multicomponent catalysts.

Chemical bonding analysis of excited states using the adaptive natural density partitioning method

Abstract: A novel approach to chemical bond analysis for excited states has been developed. Using an extended adaptive natural density partitioning method (AdNDP) as implemented in AdNDP 2.0 code, we obtained chemically intuitive bonding patterns for the excited states of H2O, B5+, and C2H4+ molecules. The deformation pathway in the excited states could be easily predicted based on the analysis of the chemical bond pattern. We expect that this new method of chemical bonding analysis would be very helpful for photochemistry, photoelectron spectroscopy, electron spectroscopy and other chemical applications that involved excited states.

Energy Transfer in Metal–Organic Frameworks for Fluorescence Sensing

Abstract: The development of materials with outstanding performance for sensitive and selective detection of multiple analytes is essential for the development of human health and society. Luminescent metal–organic frameworks (LMOFs) have controllable surface and pore sizes and excellent optical properties. Therefore, a variety of LMOF-based sensors with diverse detection functions can be easily designed and applied. Furthermore, the introduction of energy transfer (ET) into LMOFs (ET-LMOFs) could provide a richer design concept and a much more sensitive and accurate sensing performance. In this review, we focus on the recent five years of advances in ET-LMOF-based sensing materials, with an emphasis on photochemical and photophysical mechanisms. We discuss in detail possible energy transfer processes within a MOF structure or between MOFs and guest materials. Finally, the possible sensing applications of the ET-LMOF-based sensors are highlighted.

Nonplanar Butterfly‐Shaped π‐Expanded Pyrrolopyrroles

Abstract: Large aza-analogues of curved polycyclic aromatic hydrocarbons with a double-helicene structure present unique features for molecular photonics. We present the preparation and characterization of three such structures. The synthesis of these heterocyclic nanographenes involves only a few high-yield steps that use readily available starting materials. X-ray analysis revealed that each of these new dyes has three conformational isomers: one diastereoisomer in a meso form and two enantiomers in twisted forms [(P,P)] and [(M,M)]. The low energy barriers between the conformers, however, prevent their separation by using chiral HPLC, and the NMR spectra show only one set of signals for each of these curved compounds. Density functional theory (DFT) calculations quantify the small energy difference and the small energy barriers between the chiral and meso forms, which fully supports the experimental results. Their optical absorption lacks any sensitivity to the solvent environment, whereas their fluorescence features exhibit pronounced solvatochromism. This rarely observed solvatofluorochromism of centrosymmetric molecules without either electron-withdrawing groups or -donating substituents was probed by using time-resolved spectroscopy. These studies suggest that, similar to 9,9'-bianthryl, the nonpolar locally excited state shows negligible solvatochromism, whereas the charge-transfer state is sensitive to solvent polarity.

Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

Abstract: Coordination polymers are constructed from metal ions and bridging ligands, linking them into solid-state structures extending in one (1D), two (2D) or three dimensions (3D). Two- and three-dimensional coordination polymers with potential voids are often referred to as metal-organic frameworks (MOFs) or porous coordination polymers. Luminescence is an important property of coordination polymers, often playing a key role in their applications. Photophysical properties of the coordination polymers can be associated with intraligand, metal-centered, guest-centered, metal-to-ligand and ligand-to-metal electron transitions. In recent years, a rapid growth of publications devoted to luminescent or fluorescent coordination polymers can be observed. In this review the use of fluorescent ligands, namely, 4,4'-stilbenedicarboxylic acid, 1,3,4-oxadiazole, thiazole, 2,1,3-benzothiadiazole, terpyridine and carbazole derivatives, naphthalene diimides, 4,4',4''-nitrilotribenzoic acid, ruthenium(II) and iridium(III) complexes, boron-dipyrromethene (BODIPY) derivatives, porphyrins, for the construction of coordination polymers are surveyed. Applications of such coordination polymers based on their photophysical properties will be discussed. The review covers the literature published before April 2020.