Advances and Applications of Metal-Organic Frameworks (MOFs) in Emerging Technologies: A Comprehensive Review.

Metal-organic frameworks (MOFs) that are the wonder material of the 21st century consist of metal ions/clusters coordinated to organic ligands to form one- or more-dimensional porous structures with unprecedented chemical and structural tunability, exceptional thermal stability, ultrahigh porosity, and a large surface area, making them an ideal candidate for numerous potential applications. In this work, the recent progress in the design and synthetic approaches of MOFs and explore their potential applications in the fields of gas storage and separation, catalysis, magnetism, drug delivery, chemical/biosensing, supercapacitors, rechargeable batteries and self-powered wearable sensors based on piezoelectric and triboelectric nanogenerators are summarized. Lastly, this work identifies present challenges and outlines future opportunities in this field, which can provide valuable references.

A neutral rhenium-biimidazole complex for the selective recognition of fluoride ions.

The neutral rhenium(I)-biimidazole complex [Re(CO)3(biimH)(1,4-NVP)] (1) was designed and synthesized by a one-pot reaction of Re2(CO)10, 2,2'-biimidazole (biimH2) and 4-(1-naphthylvinyl)pyridine (1,4-NVP). The structure of 1 was characterized by various spectroscopic techniques including IR, 1H NMR, FAB-MS, and elemental analysis and further confirmed by a single-crystal X-ray diffraction analysis. The mononuclear complex 1, a relatively simple structure with an octahedral geometry, is comprised of facial-arranged carbonyl groups, one chelated biimH monoanion, and one 1,4-NVP. Complex 1 shows the lowest energy absorption band at around 357 nm and an emission band at 408 nm in THF. The luminescent characteristics of 1 combined with the hydrogen bonding ability of the partially coordinated monoionic biimidazole ligand permits the complex to selectively recognize fluoride ions (F-) in the presence of other halides through a dramatic luminescence enhancement. The recognition mechanism of 1 can be convincingly explained in terms of H-bond formation and proton abstraction upon the addition of F- ions by 1H and 19F NMR titration experiments. The electronic properties of 1 were further supported by time dependent density functional theory (TDDFT) computational studies.

Aggregation-induced emission enhancement (AIEE) of tetrarhenium(I) metallacycles and their application as luminescent sensors for nitroaromatics and antibiotics.

The self-assembly of tetrarhenium metallacycles [{Re(CO)3}2(µ-dhaq)(µ-N-N)]2 (3a, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene; 3b, N-N = 1,3-bis(1-octylbenzimidazol-2-yl)benzene), (H2-dhaq = 1,4-dihydroxy-9,10-anthraquinone) and [{Re(CO)3}2(µ-thaq)(µ-N-N)]2 (4, N-N = 1,3-bis(1-butylbenzimidazol-2-yl)benzene), (H2-thaq = 1,2,4-trihydroxy-9,10-anthraquinone) under solvothermal conditions is described. The metallacycles 3a,b and 4 underwent aggregation-induced emission enhancement (AIEE) in THF upon the incremental addition of water. TEM images revealed that metallacycle 3a in a 60% aqueous THF solution formed rectangular aggregates with a wide size distribution, while a 90% aqueous THF solution resulted in the formation of a mixture of nanorods and amorphous aggregates due to rapid and abrupt aggregation. UV-vis and emission spectral profiles supported the formation of nanoaggregates of metallacycles 3a,b and 4 upon the gradual addition of water to a THF solution containing metallacycles. Further studies indicated that these nanoaggregates were excellent probes for the sensitive and selective detection of nitro group containing picric acid (PA) derivatives as well as antibiotics.

A neutral mononuclear rhenium(I) complex with a rare in situ-generated triazolyl ligand for the luminescence "turn-on" detection of histidine.

A rare in situ-generated mononuclear rhenium complex [Re(bpt)(CO)3(NH3)] (1, bpt = 3,5-bis(2-pyridyl)-1,2,4-triazolate) can be used as a "turn-on" luminescent probe for selectively sensing L-histidine against other amino acids. Compound 1 was prepared by reacting Re2(CO)10, 2-cyanopyridine and hydrazine with an in situ formed bpt ligand through cyclization via C-N and N-N couplings with its single-side chelating mode arrayed with respect to the Re center. Compound 1 was highly stable and showed a green light MLCT emission in DMF solution at 507 nm upon excitation at 360 nm. Interestingly, the emission from 1 could be quenched by the addition of metal ions such as Ni2+ and Cu2+ but the emission efficiently recovered with the introduction of histidine. However, histidine could only be selectively detected when a combination of compound 1 and Ni2+ was used. Therefore, the luminescence response of the Ni2+-modified compound 1 could be utilized as a "turn-on" probe for the selective detection of histidine. This work provides a simple method for developing new sensing platforms of a discrete metal complex based on rare in situ generation.

Hydrophobic Metal-Organic Frameworks and Derived Composites for Microelectronics Applications.

The extraordinary characteristic features of metal-organic frameworks (MOFs) make them applicable for use in a variety of fields but their conductivity in microelectronics over a wide relative humidity (RH) range has not been extensively explored. To achieve good performance, MOFs must be stable in water, i. e., under humid conditions. However, the design of ultrastable hydrophobic MOFs with high conductivity for use in microelectronics as conducting and dielectric materials remains a challenge. In this Review, we discuss applications of an emerging class of hydrophobic MOFs with respect to their use as active sensor coatings, tunable low-κ dielectrics and conductivity, which provide high-level roadmap for stimulating the next steps toward the development and implementation of hydrophobic MOFs for use in microelectronic devices. Several methodologies including the incorporation of long alkyl chain and fluorinated linkers, doping of redox-active 7,7,8,8-tetracyanoquinodimethane (TCNQ), the use of guest molecules, and conducting polymers or carbon materials in the pores or surface of MOFs have been utilized to produce hydrophobic MOFs. The contact angle of a water droplet and a coating can be used to evaluate the degree of hydrophobicity of the surface of a MOF. These unique advantages enable hydrophobic MOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Classic representative examples of each category are discussed in terms of coordination structures, types of hydrophobic design, and potential microelectronic applications. Lastly, a summary and outlook as concluding remarks in this field are presented. We envision that future research in the area of hydrophobic MOFs promise to provide important breakthroughs in microelectronics applications.

Advances of Inorganic Materials in the Detection and Therapeutic Uses against Coronaviruses.

Coronaviruses (CoVs) are enveloped viruses with particle-like characteristics and a diameter of 60-140 nm, positively charged, and single-stranded RNA genomes, which caused a major outbreak of human fatal pneumonia in the beginning of the 21st century. COVID-19 is currently considered a continuous potential pandemic threat across the globe. Therefore, considerable efforts have been made to develop innovative methods and technologies for suppressing the spread of viruses as well as inactivating the viruses but COVID-19 vaccines are still in the development phase. This perspective focuses on the sensing, detection and therapeutic applications of CoVs using inorganic- based nanomaterials, metal complexes, and metal-conjugates. Synthetic inorganic- based nanoparticles interact strongly with proteins of viruses due to their morphological similarities, and therefore, numerous antivirals have been tested for efficacy against different viruses in vitro through colorimetric and electrochemical assays. Metal complexes- based agents such as bismuth complexes form an attractive class of drugs with a number of therapeutic applications, including the inhibition and duplex-unwinding activity of SARS-CoV helicase by quantitative real-time PCR (Q-RT-PCR), phosphate release assay and radioassay studies. Metal-conjugates show major effects on inhibiting the 3Clike protease of SARS-CoV and the replication of RNA-dependent RNA polymerase (RdRp). We anticipate that these approaches will provide rapid and accurate antiviral strategies in the development of these innovative sensors for the detection, inhibition and antiviral activities of coronaviruses.

Selective anions mediated fluorescence "turn-on", aggregation induced emission (AIE) and lysozyme targeting properties of pyrene-naphthalene sulphonyl conjugate.

We have designed and synthesized a novel pyrene-naphthalene sulphonyl conjugate, 1-((1Z)-(4-((Z)-4-(pyrene-1-yl)methyleneamino)phenylsulfonyl)phenylimino)methyl)naphthalene-2-ol (PSN) through a facile two-step reactions. It was characterized by various spectral techniques. Fluorescence spectral studies showed that compound PSN featured fluorescence enhancement upon increasing the water content in THF. This can be attributed to the phenomena of aggregated induced emission (AIE), which is confirmed by SEM and AFM studies, due to the restriction of CHN isomerization of PSN. The anion sensing of PSN was examined with various anions. Among these anions, H2PO4- and F- ions were selectively sensing with a low detection limit of 3.52 × 10-7 M and 7.23 × 10-7 M, respectively, and an obvious color change from yellow to orange was observed by the naked eye. The mechanism of sensing involved the formation of hydrogen bonding interaction between O-H group of PSN and H2PO4-/ F- ions. The binding of PSN with LYZ was also examined by docking studies, which shows that H-bonding and hydrophobic interactions play crucial roles for the interaction of LYZ toward PSN.

Carbon Dot Nanoparticles Exert Inhibitory Effects on Human Platelets and Reduce Mortality in Mice with Acute Pulmonary Thromboembolism.

The inhibition of platelet activation is considered a potential therapeutic strategy for the treatment of arterial thrombotic diseases; therefore, maintaining platelets in their inactive state has garnered much attention. In recent years, nanoparticles have emerged as important players in modern medicine, but potential interactions between them and platelets remain to be extensively investigated. Herein, we synthesized a new type of carbon dot (CDOT) nanoparticle and investigated its potential as a new antiplatelet agent. This nanoparticle exerted a potent inhibitory effect in collagen-stimulated human platelet aggregation. Further, it did not induce cytotoxic effects, as evidenced in a lactate dehydrogenase assay, and inhibited collagen-activated protein kinase C (PKC) activation and Akt (protein kinase B), c-Jun N-terminal kinase (JNK), and p38 mitogen-activated protein kinase (MAPK) phosphorylation. The bleeding time, a major side-effect of using antiplatelet agents, was unaffected in CDOT-treated mice. Moreover, our CDOT could reduce mortality in mice with ADP-induced acute pulmonary thromboembolism. Overall, CDOT is effective against platelet activation in vitro via reduction of the phospholipase C/PKC cascade, consequently suppressing the activation of MAPK. Accordingly, this study affords the validation that CDOT has the potential to serve as a therapeutic agent for the treatment of arterial thromboembolic disorders.

Host-guest interaction studies of polycyclic aromatic hydrocarbons (PAHs) in alkoxy bridged binuclear rhenium (I) complexes.

The interaction of two neutral alkoxy bridged binuclear rhenium(I) complexes, 1 and 2 [{Re(CO)3(1,4-NVP)}2(µ2-OR)2] (1, R = C4H9; 2, R = C10H21; 1,4-NVP = 4-(1-naphthylvinyl)pyridine] with polycyclic aromatic hydrocarbons (PAH) is investigated. UV-vis absorption, emission, 1H NMR spectral titrations, TCSPC lifetime studies and DFT theoretical calculations were carried out to examine the binding responses of complexes 1 and 2 with various PAHs such as pyrene, naphthalene, anthracene and phenanthrene. The UV-Vis absorption spectra showed an increase in absorbance of the metal-to ligand charge-transfer (MLCT) and ligand centered (LC) bands upon addition of various PAH molecules to 1 and 2, whereas the emission behavior was found to show emission quenching, which might occur through energy transfer pathway. The binding constants (K) of complexes 1 and 2 for various PAHs are found to be in the order of 104 M-1 with a 1:1 binding mode, as determined from UV-vis absorption and emission spectral titration studies. 1H NMR spectral studies show that the chemical shifts of pyrene guest and the 1,4-NVP moiety of 2 are shifted up-field, whilst the alkoxy protons do not show any appreciable change in their chemical shifts. It is believed that the open cavities present in the Re(I) complexes may lead to the recognition of PAHs via CH···π interaction.

Lipid-Wrapped Upconversion Nanoconstruct/Photosensitizer Complex for Near-Infrared Light-Mediated Photodynamic Therapy.

Photodynamic therapy (PDT) is a noninvasive medical technology that has been applied in cancer treatment where it is accessible by direct or endoscope-assisted light irradiation. To lower phototoxicity and increase tissue penetration depth of light, great effort has been focused on developing new sensitizers that can utilize red or near-infrared (NIR) light for the past decades. Lanthanide-doped upconversion nanoparticles (UCNPs) have a unique property to transduce NIR excitation light to UV-vis emission efficiently. This property allows some low-cost, low-toxicity, commercially available visible light sensitizers, which originally are not suitable for deep tissue PDT, to be activated by NIR light and have been reported extensively in the past few years. However, some issues still remain in the UCNP-assisted PDT platform such as colloidal stability, photosensitizer loading efficiency, and accessibility for targeting ligand installation, despite some advances in this direction. In this study, we designed a facile phospholipid-coated UCNP method to generate a highly colloidally stable nanoplatform that can effectively load a series of visible light sensitizers in the lipid layers. The loading stability and singlet oxygen generation efficiency of this sensitizer-loaded lipid-coated UCNP platform were investigated. We also have demonstrated the enhanced cellular uptake efficiency and tumor cell selectivity of this lipid-coated UCNP platform by changing the lipid dopant. On the basis of the evidence of our results, the lipid-complexed UCNP nanoparticles could serve as an effective photosensitizer carrier for NIR light-mediated PDT.

Translational Medicine in Pulmonary-Renal Crosstalk: Therapeutic Targeting of p-Cresyl Sulfate Triggered Nonspecific ROS and Chemoattractants in Dyspneic Patients with Uremic Lung Injury.

Molecular mechanisms and pathological features of p-Cresyl sulfate (PCS)-induced uremic lung injury (ULI) in chronic kidney disease (CKD) remain unclear. We analyzed pleural effusions (PE) from CKD and non-CKD patients for uremic toxins, reactive oxygen species (ROS), and chemotactic cytokines. Correlations between PE biomarkers and serum creatinine were also studied. Cell viability and inflammatory signaling pathways were investigated in PCS-treated human alveolar cell model. To mimic human diseases, CKD-ULI mouse model was developed with quantitative comparison of immunostaining and morphometric approach. PE from CKD patients enhance expressions of uremic toxins, hydroxyl radicals, and IL-5/IL-6/IL-8/IL-10/IL-13/ENA-78/GRO α/MDC/thrombopoietin/VEGF. PE concentrations of ENA-78/VEGF/IL-8/MDC/PCS/indoxyl sulphate correlate with serum creatinine concentrations. In vitro, PCS promotes alveolar cell death, cPLA2/COX-2/aquaporin-4 expression, and NADPH oxidase/mitochondria activation-related ROS. Intracellular ROS is abrogated by non-specific ROS scavenger N-acetyl cysteine (NAC), inhibitors of NADPH oxidase and mitochondria-targeted superoxide scavenger. However, only NAC protects against PCS-induced cell death. In vivo, expressions of cPLA2/COX2/8-OHdG, resident alveolar macrophages, recruited leukocytes, alveolar space, interstitial edema and capillary leakage increase in lung tissues of CKD-ULI mice, and NAC pretreatment ameliorates alveolar⁻capillary injury. PCS causes alveolar⁻capillary injury through triggering intracellular ROS, downstream prostaglandin pathways, cell death, and activating leukocytes to release multiplex chemoattractants and extracellular ROS. Thus PCS and nonspecific ROS serve as potential therapeutic targets.

Aggregation-induced emission enhancement of anthracene-derived Schiff base compounds and their application as a sensor for bovine serum albumin and optical cell imaging.

Three anthracene-based Schiff base complexes, R1-R3 (R1 = (E)-N´-((anthracen-10-yl)methylene)benzohydrazide; R2 = (E)-1-((anthracen-10-yl)methylene)-4-phenylsemicarbazide; and R3 = (E)-1-((anthracen-10-yl)methylene)-4-phenylthiosemicarbazide) were synthesized from 9-anthracenecarboxaldehyde, benzohydrazide, 4-phenylsemicarbazide and 4-phenylthiosemi-carbazide respectively, and characterized by various spectral techniques. The absorption spectral characteristics of R1-R3 were bathochromically tuned to the visible region by extending the π conjugation. These target compounds were weakly fluorescent in tetrahydrofuran (THF) solution because of rapid isomerization of the C=N double bond in the excited state. However, the aqueous dispersion of R1-R3 in the THF/water mixture by the gradual addition of water up to 90% resulted in an increase in the fluorescence intensity mainly due to aggregation-induced emission enhancement (AIEE) properties. The formation of nanoaggregates of R1-R3 were confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The compounds R1-R3 are ideal probes for the fluorescence sensing of bovine serum albumin (BSA) and breast cancer cells by optical cell imaging.

Simple Preparation of Porous Carbon-Supported Ruthenium: Propitious Catalytic Activity in the Reduction of Ferrocyanate(III) and a Cationic Dye.

The present study involves the synthesis, characterization, and catalytic application of ruthenium nanoparticles (Ru NPs) supported on plastic-derived carbons (PDCs) synthesized from plastic wastes (soft drink bottles) as an alternative carbon source. PDCs have been further activated with CO2 and characterized by various analytical techniques. The catalytic activity of Ru@PDC for the reduction of potassium hexacyanoferrate(III), (K3[Fe(CN)6]), and new fuchsin (NF) dye by NaBH4 was performed under mild conditions. The PDCs had spherical morphology with an average size of 0.5 µm, and the Ru NP (5 ± 0.2 nm) loading (4.01 wt %) into the PDC provided high catalytic performance for catalytic reduction of ferrocyanate(III) and NF dye. This catalyst can be recycled more than six times with only a minor loss of its catalytic activity. In addition, the stability and reusability of the Ru@PDC catalyst are also discussed.

Development of luminescent sensors based on transition metal complexes for the detection of nitroexplosives.

The detection of chemical explosives is a major area of research interest and is essential for the military as well as homeland security to counter the catastrophic effects of global terrorism. In recent years, tremendous effort has been devoted to the development of luminescent materials for the detection of explosives in the vapor, solution, and solid states with a high degree of selectivity and sensitivity and a rapid response time. Apart from the wide range of organic fluorescent chemosensors, transition metal complexes play a prominent role in the sensing of nitroaromatic explosives owing to their rich photophysical characteristics. This review briefly summarizes the salient features of the design and preparation of transition metal (Zn(ii), Ir(iii), Pd(ii), Pt(ii), Re(i) and Ru(ii)) complexes/metallacycles/metallosupramolecules with emphasis on their photophysical properties, sensing behavior, mechanism of action, and the driving forces for detecting explosives and future prospects and challenges. Most of the probes that have been reported to date act as "turn-off" luminescent sensors because their emission (intensity, lifetime, and quantum yield) is eventually quenched upon sensing with nitroaromatic compounds (NACs) through photo-induced electron or energy transfer. These unique properties of transition metal complexes in response to explosives open up new vistas for the development of real world applications such as on-site detection, in-field security, forensic research, etc.

An Integrated System to Remotely Trigger Intracellular Signal Transduction by Upconversion Nanoparticle-mediated Kinase Photoactivation.

Upconversion nanoparticle (UCNP)-mediated photoactivation is a new approach to remotely control bioeffectors with much less phototoxicity and with deeper tissue penetration. However, the existing instrumentation on the market is not readily compatible with upconversion application. Therefore, modifying the commercially available instrument is essential for this research. In this paper, we first illustrate the modifications of a conventional fluorimeter and fluorescence microscope to make them compatible for photon upconversion experiments. We then describe the synthesis of a near-infrared (NIR)-triggered caged protein kinase A catalytic subunit (PKA) immobilized on a UCNP complex. Parameters for microinjection and NIR photoactivation procedures are also reported. After the caged PKA-UCNP is microinjected into REF52 fibroblast cells, the NIR irradiation, which is significantly superior to conventional UV irradiation, efficiently triggers the PKA signal transduction pathway in living cells. In addition, positive and negative control experiments confirm that the PKA-induced pathway leading to the disintegration of stress fibers is specifically triggered by NIR irradiation. Thus, the use of protein-modified UCNP provides an innovative approach to remotely control light-modulated cellular experiments, in which direct exposure to UV light must be avoided.

Well-dispersed rhenium nanoparticles on three-dimensional carbon nanostructures: Efficient catalysts for the reduction of aromatic nitro compounds.

Rhenium nanoparticles (ReNPs) supported on ordered mesoporous carbon (OMC) as a catalyst (Re/OMC) through a solvent-evaporation induced self-assembly (ELSA) method were prepared. The synthesized heterogonous catalyst was fully characterized using X-ray diffraction, field emission transmission electron microscopy, N2 sorption, metal dispersion, thermogravimetric analysis, Raman, Fourier-transform infrared, and X-ray photon spectroscopies. In addition, the catalyst was applied to reduce the aromatic nitro compounds (ANCs) for the first time in aqueous media and the reactions were monitored by following the intensity changes in the UV-vis absorption spectra with respect to time. This method provides the advantages of obtaining a high rate constant (k), green reaction conditions, simple methodology, easy separation and easy workup procedures. Moreover, the catalyst can be easily recovered by centrifugation, recycled several times and reused without any loss of activity. The higher activity of this catalyst was attributed to higher dispersion and smaller particle size of ReNPs as observed from FE-TEM and XRD results.

Construction of a Near-Infrared-Activatable Enzyme Platform To Remotely Trigger Intracellular Signal Transduction Using an Upconversion Nanoparticle.

Photoactivatable (caged) bioeffectors provide a way to remotely trigger or disable biochemical pathways in living organisms at a desired time and location with a pulse of light (uncaging), but the phototoxicity of ultraviolet (UV) often limits its application. In this study, we have demonstrated the near-infrared (NIR) photoactivatable enzyme platform using protein kinase A (PKA), an important enzyme in cell biology. We successfully photoactivated PKA using NIR to phosphorylate its substrate, and this induced a downstream cellular response in living cells with high spatiotemporal resolution. In addition, this system allows NIR to selectively activate the caged enzyme immobilized on the nanoparticle surface without activating other caged proteins in the cytosol. This NIR-responsive enzyme-nanoparticle system provides an innovative approach to remote-control proteins and enzymes, which can be used by researchers who need to avoid direct UV irradiation or use UV as a secondary channel to turn on a bioeffector.

Alkoxy bridged binuclear rhenium (I) complexes as a potential sensor for ß-amyloid aggregation.

Alkoxy bridged binuclear rhenium(I) complexes are used as a probe for the selective and sensitive detection of aggregation of ß-amyloid fibrils that are consorted with Alzheimer's disease (AD). The strong binding of the complexes is affirmed by the fluorescence enhancement and calculated binding constant value in the order of 10(5)M(-1) is obtained from the Scatchard plots. The binding of ß-amyloid can be attributed to π-π stacking interaction of naphthalene moiety present in rhenium(I) complexes, and it is supported by docking studies. The selectivity is quite high towards other proteins and the formation of fibrils can be observed in the range of 30-40 nm through the AFM and TEM techniques.

Aggregation-induced emission enhancement in alkoxy-bridged binuclear rhenium(I) complexes: application as sensor for explosives and interaction with microheterogeneous media.

The aggregation-induced emission enhancement (AIEE) characteristics of the two alkoxy-bridged binuclear Re(I) complexes [{Re(CO)3(1,4-NVP)}2(µ2-OR)2] (1, R = C4H9; 2, C10H21) bearing a long alkyl chain with 4-(1-naphthylvinyl)pyridine (1,4-NVP) ligand are illustrated. These complexes in CH2Cl2 (good solvent) are weakly luminescent, but their intensity increased enormously by almost 500 times by the addition of poor solvent (CH3CN) due to aggregation. By tracking this process via UV-vis absorption and emission spectral and TEM techniques, the enhanced emission is attributed to the formation of nanoaggregates. The nanoaggregate of complex 2 is used as a sensor for nitroaromatic compounds. Furthermore, the study of the photophysical properties of these binuclear Re(I) complexes in cationic, cetyltrimethylammonium bromide (CTAB), anionic, sodium dodecyl sulfate (SDS), and nonionic, p-tert-octylphenoxypolyoxyethanol (TritonX-100, TX-100), micelles as well as in CTAB-hexane-water and AOT-isooctane-water reverse micelles using steady-state and time-resolved spectroscopy and TEM analysis reveals that the nanoaggregates became small and compact size.

One-step orthogonal-bonding approach to the self-assembly of neutral rhenium-based metallacycles: synthesis, structures, photophysics, and sensing applications.

Self-assembled metallacycles offer structural diversity and interesting properties based on their unique frameworks and host-guest chemistry. As a result, the design and synthesis of these materials has attracted significant research interest. This Account describes our comprehensive investigations of an effective orthogonal-bonding approach for the self-assembly of neutral Re-based metallacycles. We discuss the various types of assemblies that can be created based on the nuclearity of the luminophore, including bimetallic materials, rectangles, cages, and calixarenes. This approach permits the preparation of a rectangular molecule, rather than two molecular squares, in excellent yields. We extended this strategy to the high yield synthesis of a series of Re-based metallacycles with different shapes. With the rich spectroscopic and luminescence properties, Re(I) metallacycles provide an excellent platform for studies of host-guest interactions. When possible, we also present potential applications of the luminescent Re-based metallosupramolecular assemblies. The orthogonal-bonding approach involves the simultaneous introduction of two ligands: a bis-chelating ligand to coordinate to two equatorial sites of two fac-(CO)(3)Re cores and a monotopic or ditopic nitrogen-donor ligand to the remaining orthogonal axial site. Furthermore, by the appropriate choice of the predesigned organic ligands with various backbones and connectivity information and fac-Re(CO)(3) metal centers, we could also design other novel functional metallacycles including rotors, gondolas, cages, triangles, and metallacalixarenes in high yields. The incorporation of flexible ligands into the Re(I) metallacycles allows us to introduce various conformation states and novel structures. As a result, these structures acquire new functions, such as adaptive recognition properties. For example, we assembled Re(I)-based metallacyclic rotors via a one-step process. These rotors, which contain a para-phenylene unit that rapidly rotates within the metallacycles, are prototypes of a neutral altitudinal rotor. Most of the metallacycles are luminescent. The ability to chemically modify the organic ligands offers opportunities to create structural diversity and to tune the photophysical properties of these Re(I) metallacycles efficiently. Several strategies for increasing emission quantum yields and excited-state lifetimes and tuning the colors in Re(I) metallacycles are available. The cyclometalated ligands in Re(I) metallacycles improve excited state lifetimes and quantum yields, and these C-H bond-activated metallacycles are considerably more emissive than their non-C-H bond-activated analogues. The introduction of crown-ether-like recognition sites into neutral gondola-shaped metallacycles that selectively recognize metal ions also enhanced emission. Rhenium-based rectangular boxes, synthesized via a simple one-step route, contain a large and tunable hydrophobic inner cavity, which selectively recognizes benzene molecules. Such structures were the best host for benzene reported to date. In addition, we designed and synthesized novel neutral metallacalixarenes with tunable size, cavity, color, and functionality. These structures are efficient hosts for the recognition of planar aromatic guests.