Fluorescence Emission Research Articles

Cuprophilic Interactions in Polymeric [Cu10O2(Mes)6]n.

The properties of cuprophilic compounds and the underlying fundamental principles responsible for the Cu(I)···Cu(I) interactions have been the subject of intense research as their diverse structural and physical attributes are being explored. In this light, we performed a new study of the compound [Cu10O2(Mes)6] reported by Haakansson et al. using state of the art experimental and theoretical analysis techniques. Doing this, we found the compound to be a polymer in the solid state, best written as [Cu10O2(Mes)6]n, with unsupported Cu(I)···Cu(I) contacts linking the monomers (2.776 Å). The monomeric unit also exhibits various cuprophilic contacts bridged by mesityl and/or oxo ligands. The compound was analyzed in its solid state, revealing luminescent properties resulting from two distinct fluorescent emissions, as well as in solution, in which its polymeric structure reversibly decomposes. A quantum theory of atoms in molecules (QTAIM) analysis based on density functional theory (DFT) calculations allows to characterize the various Cu(I)···Cu(I) contacts, in which only a few, and not necessarily the shortest, are associated with a bond critical point. Additionally, an energy decomposition analysis of the bonding between monomers indicates that it is dominated by dispersion forces in which the ligands play a dominant role, resulting in bonding energies significantly larger than found in previous DFT investigations based on less bulky models.

Two-dimensional metal-organic framework nanoleaf embedded with nitrogen-doped carbon dots for monitoring of picric acid

A novel preparation of 2D metal–organic framework (Zn-MOF, ZIF-8) nanoleaf (ZIF-L) embedded with nitrogen-doped carbon dots (NCDs) was applied successfully. The NCDs are synthesized through hydrothermal treatment of citric acid and ethylenediamine exhibiting excitation wavelength independence (λex-independence) of 6 nm and higher quantum yield reaches 84 %. The ZIF-L embedded with NCDs generates a 2D continuous framework of NCDs@ ZIF-L nanocomposite. The nanocomposite was fully characterized by FTIR, XRD, TEM, and N2 adsorption-desorption mechanism. The XRD data reveals no significant change in the crystallinity of ZIF-L upon the encapsulation of NCDs, but it enhances the fluorescence emission. The synergetic cooperation between ZIF-L and NCDs might free active sites that lead to higher adsorption capacity and thus enhance their application in chemical sensing. The NCDs@ZIF-L nanocomposite synergistically combines active-rich-electron nanospaces with a high surface area, both of which are particularly beneficial for the selective detection of hazardous picric acid (PA) because of reinforced hydrogen bonding interactions with the hydroxyl groups of PA aromatic rings. The NCDs@ZIF-L framework is utilized to monitor PA as a nitro explosive compound in aqueous media exhibiting a high sensing activity and selectivity to detect PA in diluted solutions with a low detection limit (LOD) reaching 0.139 µM. The nanocomposite was also utilized in real water samples spiked with different concentrations of PA in tap water, with R % reaching 91.3–102 % and RSD % less than 5 %, showing their applicability to detect PA under circumstances.

Efficient Deep-Blue Organic Light-Emitting Diodes Employing Doublet Sensitization.

Fast and efficient exciton utilization is a crucial solution and highly desirable for achieving high-performance blue organic light-emitting diodes (OLEDs). However, the rate and efficiency of exciton utilization in traditional OLEDs, which employ fully closed-shell materials as emitters, are inevitably limited by spin statistical limitations and transition prohibition. Herein, a new sensitization strategy, namely doublet-sensitized fluorescence (DSF), is proposed to realize high-performance deep-blue electroluminescence. In the DSF-OLED, a doublet-emitting cerium(III) complex, Ce-2, is utilized as sensitizer for multi-resonance thermally activated delayed fluorescence emitter ν-DABNA. Experimental results reveal that holes and electrons predominantly recombine on Ce-2 to form doublet excitons, which subsequently transfer energy to the singlet state of ν-DABNA via exceptionally fast (over 108s-1) and efficient (≈100%) Förster resonance energy transfer for deep-blue emission. Due to the circumvention of spin-flip in the DSF mechanism, near-unit exciton utilization efficiency and remarkably short exciton residence time of 1.36µs are achieved in the proof-of-concept deep-blue DSF-OLED, which achieves a Commission Internationale de l'Eclairage coordinate of (0.13, 0.14), a high external quantum efficiency of 30.0%, and small efficiency roll-off of 14.7% at a luminance of 1000cdm-2. The DSF device exhibits significantly improved operational stability compared with unsensitized reference device.

Enhancing Two-Photon Excited Fluorescence of Metal-Organic Framework Single Crystals through Modulation of Inorganic Nodes.

Regulation of the two-photon excited fluorescence (TPEF) emission intensity and wavelength of metal-organic framework (MOF) crystals with similar constitutions presents a significant challenge. In this study, two MOFs, Zn-BTPPA and Cd3-BTPPA, were constructed using tetrakis(1,1'-biphenyl-4-carboxylic acid)-1,4-benzenediamine (H4BTPPA) as the organic ligand and mononuclear Zn and trinuclear Cd3 inorganic nodes, respectively. The incorporation of H4BTPPA within the MOF structures enables effective TPEF emission in both Zn-BTPPA and Cd3-BTPPA. The TPEF results show that Zn-BTPPA and Cd3-BTPPA exhibited strong emissions at 523 and 463 nm, respectively, when excited with a 780 nm laser. Moreover, Zn-BTPPA and Cd3-BTPPA exhibited much higher two-photon absorption cross sections, approximately 4.9 and 5.2 times higher than that of the reported dinuclear MOF, Cd2-BTPPA, with a similar composition, respectively. With different inorganic nodes, the stacking of chromophores, π···π interactions, and ligand geometry were found to correlate with the enhanced TPEF in Cd3-BTPPA and the blue-shifted TPEF in Zn-BTPPA. This work serves as an inspiration for designing efficient TPEF MOF materials based on the structure-property relationship.

Construction of Concentration Quenching‐Resistant Multi‐Resonance TADF Emitters via Positional Isomerization for OLEDs

AbstractMultiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters are promising for high‐definition organic light‐emitting diodes (OLEDs) due to their high exciton utilization and color purity. However, strong interchromophore interactions cause most MR‐TADF emitters with planar structures to aggregate at high doping concentrations, leading to degraded efficiencies. Herein, using benzenesulfonyl‐functionalized dibenzothiophene sulfoximine with steric effects, three MR‐TADF emitters (2SBN, 3SBN, and 4SBN) are synthesized by coupling the classic DtBuCzB skeleton at different sites. Three emitters exhibit green or blue‐green emission with full width at half maximum (FWHM) values less than 29 nm and photoluminescence quantum yields exceeding 90%. OLEDs based on 2SBN, 3SBN, and 4SBN achieve high maximum external quantum efficiency (EQEmax) values of 30.1%, 27%, and 33.8%, respectively, at a 5 wt.% doping concentration. Notably, due to the distorted conformation of 4SBN and suppressed intermolecular interaction, the OLED remains high EQEmax of 28.9% at a doping concentration of 20 wt.%. These results demonstrate the feasibility of molecular design to modulate spatial conformations via positional isomerism to develop MR‐TADF emitters with reduced concentration quenching.

Dual‐Core Engineering for Efficient Deep‐Blue Multiple Resonance Thermally Activated Delayed Fluorescent Materials

AbstractDeveloping narrowband blue multiple resonance (MR) organic emitters with Commission Internationale de L'Eclairage (CIE) y coordinates <0.1 is essential for advanced display technologies. This study proposes a deep‐blue thermally activated delayed fluorescence (TADF) emitter, named 2BNO, which integrates two independent MR cores. Unlike many TADF materials with single‐bonded dual emitting cores, 2BNO utilizes a steric hindrance‐assisted fluorene bridge to achieve an orthorhombic molecular structure. The dual‐core MR‐TADF emitter shows enhanced light absorption and a high photoluminescence quantum yield. Notably, the emission of 2BNO is not significantly redshifted compared to single‐core compounds and maintains a narrow full width at half‐maximum (FWHM) of 24 nm with CIE coordinates of (0.147, 0.041) in 2Me‐THF solution, nearing the BT.2020 blue standard. Organic light‐emitting diodes (OLEDs) incorporating 2BNO as the emitter exhibit deep‐blue emission at 460 nm with a narrow FWHM of 29 nm and CIE coordinates of (0.14, 0.09). The dual emitting core design significantly improves device efficiency, achieving a high external quantum efficiency (EQE) of 19.8%. The dual‐core molecular design strategy in this work is demonstrated to be effective in promoting the efficiency of the TADF emitters while preserving deep‐blue color purity.

DNA/BSA Binding and Antimicrobial Properties of Biguanide-Cu(II) Complexes.

The biguanide Cu(II) complexes [Cu(L1-4)2](ClO4)2 were synthesized and spectroscopic/analytical techniques were used to clarify their structures. Single crystals of complex [Cu(L4)2](ClO4)2 was obtained and its definite structure was determined by single crystal X-ray diffraction study. The complexes [Cu(L1-4)2](ClO4)2 were screened for their FSds-DNA interactions by using UV-Vis absorption and fluorescence spectroscopies. The complexes [Cu(L2)2](ClO4)2 and [Cu(L3)2](ClO4)2 were shown to exhibit higher affinity for binding DNA. Examining the EB-DNA interaction, it is believed that the complexes interact with DNA through a groove binding mechanism. The interaction of complexes with BSA were observed through the quenching of the fluorescence emission. Complexes [Cu(L2)2](ClO4)2 and [Cu(L3)2](ClO4)2 show moderate binding affinity to BSA through a static mode. Additionally, the Cu(II) complexes were screened for their antibacterial activities against various bacterial strains. Complexes showed potential antimicrobial activity against Salmonella typhimurium, Bacillus cereus, Salmonella typhimurium and S. aureus.

Optical Methods for Optimizing Fluorescence Imaging Field of View and Image Quality in Surgical Guidance Procedures.

Cancer surgery is aimed at complete tumor resection and accurate lymph node detection. However, numerous blood vessels are distributed within the tumor, and the colors of the tumor, blood vessels, and lymph nodes are similar, making observations with the naked eye difficult. Therefore, tumors, blood vessels, and lymph nodes can be monitored via color classification using an operating microscope to induce fluorescence emission. However, as the beam width of the LED required to induce fluorescence emission is narrow and the power loss of the beam is significant at a certain working distance, there are limitations to inducing fluorescence emission, and light reflection occurs in the observation image, obstructing the view of the observation area. Therefore, the removal of reflected light is essential to avoid missing the diagnosis of the lesion under observation. This paper proposes the use of a beam mirror and polarizing filter to increase the beam width and beam intensity. The refraction and reflection effects of the beam were utilized using the beam mirror, and the rotation angle of the polarizing filter was adjusted to remove light reflection. Consequently, the minimum beam power using the beam mirror was 10.9 mW, the beam width was doubled to 40.2°, and more than 98% of light reflection was removed at 90° and 270°. With light reflection effectively eliminated, clear observation of lesions is possible. This method is expected to be used effectively in surgical, procedural, and diagnostic departments.

Enhanced Plasmonic Trapping and Fluorescent Emission of Nitrogen-Vacancy Nanodiamonds Using a High-Efficiency Nanofocusing Device.

Fluorescent nanodiamonds (FNDs) with nitrogen-vacancy centers are pivotal for advancing quantum photonics and imaging through deterministic quantum state manipulation. However, deterministic integration of quantum emitters into photonic devices remains a challenge due to the need for high coupling efficiency and Purcell enhancement. We report a deterministic FND-integrated nanofocusing device achieved by assembling FNDs at a plasmonic waveguide tip through plasmonic-enhanced optical trapping. This technique not only increases the emission rate by 58.6 times compared to isolated FNDs but also preferentially directs radiation into the waveguide at a rate 5.3 times higher than that into free space, achieving an exceptional figure-of-merit of ∼3000 for efficient energy transfer. Our findings represent a significant step toward deterministic integration in quantum imaging and communication, opening new avenues for quantum technology advancements.

Determination of Dipicolinic Acid through the Antenna Effect of Eu(III) Coordination Polymer.

Bacillus anthracis is a Gram-positive bacterium that can cause acute infection and anthracnose, which is a serious concern for human health. Determining Bacillus anthracis through its spore biomarker dipicolinic acid (DPA) is crucial, and there is a strong need for a method that is rapid, sensitive, and selective. Here, we created Eu(III)-coordination polymers (Eu-CPs) with surfaces that have abundant carboxyl and hydroxyl groups. This was achieved by using citric acid and europium nitrate hexahydrate as precursors in a straightforward one-pot hydrothermal process. These Eu-CPs were then successfully utilized for highly sensitive DPA determination. The fluorescence (FL) emission of Eu-CPs, which is typically weak due to the coordination of Eu(III) with water molecules, was significantly enhanced in the presence of DPA. This enhancement is attributed to the competitive binding between DPA's carboxyl or hydroxyl groups and water molecules. As a result, the absorbed energy of DPA, when excited by 280 nm ultraviolet light, is transferred to Eu-CPs through an antenna effect. This leads to the emission of the characteristic red fluorescence of Eu3+ at 618 nm. A strong linear relationship was observed between the enhanced FL intensity and DPA concentration in the range of 0.5-80 μM. This relationship allowed for a limit of detection (LOD) of 15.23 nM. Furthermore, the Eu-CPs we constructed can effectively monitor the release of DPA from Bacillus subtilis spores, thereby further demonstrating the potential significance of this strategy in the monitoring and management of anthrax risk. This highlights the novelty of this approach in practical applications, provides a valuable determination technique for Bacillus anthracis, and offers insights into the development cycle of microorganisms.

Modulating Charge‐Transfer Excited States of Multiple Resonance Emitters via Intramolecular Covalent Bond Locking

AbstractAdvanced multiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters with high efficiency and color purity have emerged as a research focus in the development of ultra‐high‐definition displays. Herein, we disclose an approach to modulate the charge‐transfer excited states of MR emitters via intramolecular covalent bond locking. This strategy can promote the evolution of strong intramolecular charge‐transfer (ICT) states into weak ICT states, ultimately narrowing the full‐width at half‐maximum (FWHM) of emitters. To modulate the ICT intensity, two octagonal rings are introduced to yield molecule m‐DCzDAz‐BNCz. Compounds m‐CzDAz‐BNCz and m‐DCzDAz‐BNCz exhibit bright light‐green and green fluorescence in toluene, with emission maxima of 504 and 513 nm, and FWHMs of 28 and 34 nm, respectively. Sensitized organic light‐emitting diodes (OLEDs) employing emitters m‐CzDAz‐BNCz and m‐DCzDAz‐BNCz exhibit green emission with peaks of 508 and 520 nm, Commission Internationale de L'Eclairage (CIE) coordinates of (0.12, 0.65) and (0.19, 0.69), and maximum external quantum efficiencies (EQEs) of 30.2 % and 32.6 %, respectively.

Redox interference-free bimodal paraoxon sensing enabled by an aggregation-induced emission nanozyme catalytically hydrolyzing phosphoesters specifically

In view of the current serious situation of organophosphorus pesticides (OPs) residue contamination, developing rapid and accurate OPs sensors is a matter of urgency. Redox-nanozyme based colorimetric sensors have been widely researched and utilized in OPs residue determination, but overcoming the interference of external redox substances and the effect of single-signal modes on detection performance is still a challenge. Here we fabricated a Zr-based metal–organic framework (MOF) featuring specific phosphatase-like activity and strong aggregation-induced emission (AIE) fluorescence for redox interference-free bimodal pesticide sensing. In the MOF, the activity-tunable Zr4+ node offered high hydrolytic activity and affinity toward P–O containing substrates, and the rigid framework structure effectively enhanced the fluorescence emission of the ligand 1,1,2,2-tetra(4-carboxylphenyl)ethylene. The developed AIEzyme could efficiently catalyze the hydrolysis of paraoxon to yellow p-nitrophenol, which further reduced the intrinsic AIE fluorescence of AIEzyme through internal filtration effect. Thereby, a natural enzyme-free dual-mode colorimetric/fluorescence approach was established for paraoxon detection with no interference from redox substances, and a smartphone-assisted portable platform was further developed to enable the facile, rapid, and high-performance sensing of the pesticide in complex practical matrices.

The ATTO 565 Dye and Its Applications in Microscopy.

ATTO 565, a Rhodamine-type dye, has garnered significant attention due to its remarkable optical properties, such as a high fluorescence quantum yield, and the fact that it is a relatively stable structure and has low biotoxicity. ATTO 565 has found extensive applications in combination with microscopy technology. In this review, the chemical and optical properties of ATTO 565 are introduced, along with the principles behind them. The functionality of ATTO 565 in confocal microscopy, stimulated emission depletion (STED) microscopy, single-molecule tracking (SMT) techniques, two-photon excitation-stimulated emission depletion microscopy (TPE-STED) and fluorescence correlation spectroscopy (FCS) is discussed. These studies demonstrate that ATTO 565 plays a crucial role in areas such as biological imaging and single-molecule localization, thus warranting further in-depth investigations. Finally, we present some prospects and concepts for the future applications of ATTO 565 in the fields of biocompatibility and metal ion detection. This review does not include theoretical calculations for the ATTO 565 molecule.

W-Shaped π-Extended Double Undecabenzo[7]helicene.

A chiral W-shaped fully π-extended double [7]helicene (ED7H) has been synthesized and fully characterized. It displays fluorescence emission (λem = 636 nm) with a quantum yield (Φf) of 0.10. In comparison to its X-shaped and monomict π-extended [7]helicene analogues, enantiopure W-shaped ED7H exhibited superior chiral optical characteristics, including distinct circular dichroism signals from 400 to 650 nm, a good dissymmetric emission factor |glum| of 4 × 10-3, and a circularly polarized luminescence brightness value BCPL of 42 M-1 cm-1.

2,3 : 6,7‐Naphthalene Bis(dicarboximide) Cyclophane: A Photofunctional Host for Ambient Delayed Fluorescence in Solution

AbstractHarvesting triplet excitons of heavy atom‐free purely organic chromophores under aerated conditions is challenging due to the quenching of long‐lived triplet states by molecular oxygen and vibrational dissipation. Herein, we show a supramolecular approach of triplet harvesting via mitigating quenching pathways of a triplet harvester. Specifically, we used a host–guest system based on 2,3 : 6,7‐naphthalene bis(dicarboximide)‐derived cyclophane (NBICy) and carbazole derivative (EtCz). Complexation studies and single‐crystal X‐ray analysis showed the formation of a rigid host–guest complex (K≈104 M−1 in CCl4), resulting in triplet‐exciton stabilization under aerated conditions via mitigating vibrational interference and oxygen quenching. Photophysical studies elucidate the delayed fluorescence emission from the charge‐transfer state (1CT) with a quantum yield (QY) of 6–8 % under ambient conditions which increased up to 36 % in an inert atmosphere.

Carbonized Polymer Dots: Influence of the Carbon Nanoparticle Structure on Cell Biocompatibility.

Carbonized polymer dots (CPDs) were obtained by using microwave irradiation under the same conditions. However, different carbogenic precursors were used, such as aromatic diamine molecules, ortho-phenylenediamine (o-OPDA), and 3,4-diaminobenzoic acid (3,4-DABA). Both carbon nanoparticles showed different structural results based on Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and atomic force microscopy analyses. However, there are similar spectroscopic (UV-visible and fluorescence emission) profiles. The photophysical results, like quantum yield (QY) and fluorescence lifetime, were not identical; CPDs-OPDA has a higher QY and fluorescence lifetime than CPDs-3,4-DABA. CPDs-3,4-DABA presents a more hydrophobic character than CPDs-OPDA and has a more negative superficial charge. Cell viability studies in both standard and tumor lines demonstrated higher cytotoxicity from CPDs-OPDA than that from CPDs-3,4-DABA. The oxidative stress identified in cells treated with CPDs-OPDA was based on reactive oxygen species and associated with nitric oxide production. CPDs-3,4-DABA showed more DPHH inhibition than CPDs-OPDA, indicating the antioxidant activity of CPDs.

Reversible pH-switchable NIR-II nano-photosensitizer for precise imaging and photodynamic therapy of tumors

Photodynamic therapy (PDT) has attracted widespread attention from researchers as an emerging cancer treatment method. There have been many reports on various types of NIR-II photosensitizers for imaging and treatment of tumor sites. However, there are few reports on the development of NIR-II organic small molecule photosensitizers that have intelligent response to the tumor microenvironment, precise imaging, real-time treatment, and high biocompatibility. In this work, we developed a series of NIR-II photosensitizers (RBTs) with near-infrared excitation, good photostability, and large Stokes shift. Among them, RBT-Br exhibited higher reactive oxygen species (ROS) generation efficiency due to the introduction of halogen heavy atoms to enhance intersystem crossing (ISC). It is noteworthy that RBT-Br can generate singlet oxygen (1O2) and superoxide anion radicals (•O2−) simultaneously under 730 nm laser. Subsequently, we used molecular engineering technology to construct three pH-responsive NIR-II photosensitizers (RBT-pHs) by utilizing the closure of the lactam ring, among which RBT-pH-1 (pKa = 6.78) is able to be directionally activated under the stimulation of tumor micro-acid environment, with its fluorescence emission window reaching 933 nm. Subsequently, RBT-pH-1 NPs encapsulated in DSPE-mPEG5k were applied for PDT treatment of mouse tumors. The results showed that RBT-pH-1 NPs were activated by the acidic tumor microenvironment and generated ROS under laser excitation, exhibiting precise tumor imaging and significant tumor growth inhibition. We look forward to these multifunctional NIR-II organic small molecule photosensitizers providing a more efficient approach for clinical treatment of tumors. Statement of significanceA reversible pH-switchable NIR-II nano-photosensitizer RBT-pH-1 NPs (pKa = 6.76) is developed for precise imaging and PDT therapy of mouse tumors, which can be effectively used for targeted enrichment and activation of tumor micro-acid environments. The results show that this NIR-II photosensitizer generates ROS through tumor micro-acid environment stimulation and laser triggering, showing precise tumor imaging guidance and significant tumor growth inhibition.

Role of Pyridine Nitrogen Position on the Moisture Sensitivity of Organic Emitters.

Moisture-sensitive fluorescent emitters are a class of smart materials that can change their emission behavior upon exposure to water. In this study, we have synthesized two highly fluorescent organic emitters, 4BPy-PTA and 2BPy-PTA, and showed how moisture sensitivity can be enhanced by molecular design modification. Owing to the different nitrogen atom positions in the acceptor units, the emitters show different degrees of moisture sensitivity. Upon moisture exposure, both emitters change their emission color from greenish-yellow to blue, but a larger shift was witnessed in 4BPy-PTA (81 nm) than in 2BPy-PTA (68 nm). Moisture exposure enhances the photoluminescence quantum yield (PLQY) of 4BPy-PTA from 37 to 48%, whereas it suppresses the PLQY of 2BPy-PTA from 59 to 15%. A shorter moisture sensing time, large emission color shift, and enhanced PLQY make 4BPy-PTA a better moisture-sensitive material than 2BPy-PTA. Interestingly, the emission colors of the emitters can be completely regained by heating and partially by applying mechanical force to the moisture-exposed solids. In addition, these emitters also show mechanochromic luminescence behavior with a completely reversible emission color switch between blue and green.

A new three-dimensional barium(II) coordination polymer constructed from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structure, Hirshfeld surface analysis and properties.

A new three-dimensional (3D) coordination polymer, namely, poly[diaqua[μ5-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato]barium(II)], [Ba(C14H6N2O8)(H2O)2]n, (I), has been synthesized by the microwave-irradiated reaction of Ba(NO3)2 with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetatic acid, H2L}. The title compound was structurally characterized by single-crystal X-ray diffraction analysis and powder X-ray diffraction analysis, as well as IR spectroscopy. In the crystal structure of (I), the BaII ion is nine-coordinated by six carboxylate O atoms from five symmetry-related L2- dianions and one imide O atom, as well as two water O atoms. The coordination geometry of the central BaII ion can be described as a spherical capped square antiprism. One carboxylate group of the ligand serves as a μ3-bridge linking the BaII cations into a one-dimensional polynuclear secondary building unit (SBU). Another carboxylate group of the ligand acts as a μ2-bridge connecting the 1D SBUs, thereby forming a two-dimensional (2D) SBU. The resulting 2D SBUs are extended into a 3D framework via the pyromellitic diimide moiety of the ligand as a spacer. The 3D Ba framework can be simplified as a 5-connected hexagonal boron nitride net (bnn) topology. The intermolecular interactions in the 3D framework were further investigated by Hirshfeld surface analysis and the results show that the prominent interactions are H...O (45.1%), Ba...O (11.1%) and C...H (11.1%), as well as H...H (11.1%) contacts. The thermal stability, photoluminescence properties and UV-Vis absorption spectra of (I) were also investigated. The coordination polymer exhibits a fluorescence emission with a quantum yield of 0.071 and high thermal stability.

2D coordination polymers of cadmium(II) and zinc(II) derived from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size.

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[diaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O''']cadmium(II)], [Cd(C14H6N2O8)(H2O)2]n (1), and poly[[tetraaqua[μ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O'''][μ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']dizinc(II)] dihydrate], {[Zn(C14H6N2O8(H2O)2]·H2O}n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH3COO)2·2H2O and Zn(CH3COO)2·2H2O, respectively, with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetic acid, H2L}. In the crystal structure of 1, the CdII ion is six-coordinated by four carboxylate O atoms from four symmetry-related L2- dianions and two coordinated water molecules, furnishing an octahedral coordination geometry. The bridging L2- dianion links four symmetry-related CdII cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the ZnII ion is five-coordinated by three carboxylate O atoms from three different L2- dianions and two coordination water molecules, furnishing a trigonal bipyramidal coordination geometry. Two crystallographically independent ligands serve as μ4- and μ2-bridges, respectively, to connect the ZnII ions, thereby forming a 2D layer with a 3,3-connected hcb topology. Crystal structure analysis reveals the presence of n→π* interactions between two carbonyl groups of the pyromellitic diimide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission compared with free H2L. The framework of 2 decomposes from 720 K, indicating its high thermal stability. A comparative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.