Thoughts on the Rational Design of MOF-Guest Interactions for Future Intelligent Materials.

The MOF-guest relationship is broken down in elementary phases, descriptors, and parameters. These descriptors and parameters allow precise descriptions of processes, whether they occur at the point when the guest enters the MOF, during the stay, or at the point of exiting. Description of these three phases is possible according to the location of the guest inside the MOF, the activity between MOF and guest, whether stimuli can be used, and whether a selective action can be exercised.

Selective Chirality-Driven Photopolymerization of Diacetylene Crystals.

Crystal engineering of two diacetylene monomers was achieved by branching two chiral groups [R = PhC*MeNH(CO)CH] exhibiting an enantiopure configuration of ,-() and an achiral ,--isomer (). The X-ray structures of and reveal the presence of supramolecular arrangements driven by intermolecular H-bonding. A significant intermolecular closer proximity in than that in is depicted, ultimately resulting in a slow thermal (days) and swift (min) photochemical polymerization of to form , whereas is unreactive.

Singlet oxygen is an emissive ligand.

Unprecedented experimental evidence shows that gaseous singlet oxygen (O) acts as an emissive ligand following collisional photosensitization. This evidence was obtained by monitoring O phosphorescence intensity at ≈1275-1280 nm and the excited state lifetime of singlet oxygen generated by known tetraphenylporphyrin photosensitizers, while varying the atmospheric environment.

Important Counteranion Effect on Adsorption Efficacity of Hydrogen Sulfide by Silver(I)-Dithione Coordination Polymers.

Four new coordination polymers (CPs) have been prepared and evaluated for their efficacy in adsorbing hydrogen sulfide. The reactions of the structurally flexible assembling dithione ligand, , with different silver(I) salts lead to four new metal-organic coordination architectures (CPs , , , and ) exhibiting either one- or two-dimensional networks. CP , 2D-[(AgCl)], exhibits a linear series of rhomboid (S)Ag(μ-Cl)Ag(S) secondary building units (SBUs) where S is one of the thione functions of , altogether forming a 2D-network.

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF.

A new metal-organic framework (MOF; [ZnO()()()]; ) constructed on chromophoric ligands 5,5',10,10',15,15'-hexaethyltruxene-2,7,12-triacetate (), 9-fluorenone-2,7-dicarboxylate (), terephthalate (), and the ZnO node has been prepared and identified by powder X-ray diffraction. This luminescent MOF exhibits large mesoporous pores of 2.7 nm based on computer modeling using density functional theory (DFT) calculations.

Statistical Analysis of Copper(I) Iodide and Bis(Diphenylphosphino)alkane-Based Complexes and Coordination Polymers.

The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging.

Strong Host-Guest Dependence on the Emissive Properties of MOF-5 and [Zn(BTTB)(DMF)•(HO)].

3D-[ZnO(1,4-BDC)•(solvent)] (; BDC = benzodicarboxylate) and -[Zn(BTTB)(DMF)•(HO)] (; BTTB = 4,4',4″,4‴-benzene-1,2,4,5-tetrayltetrabenzoate) have been investigated by means of steady-state UV-visible and fluorescence and time-resolved emission spectroscopy, as a function of solvent and power of the excitation irradiation. The low-temperature X-ray structures (173 K) were permitted to locate solvent molecules (here HO) in the lattice. They were found distributed in the middle in the voids with no evidence of specific interactions (H-bond, coulombic, and dipole-dipole) with the framework.

Virus Management Using Metal-Organic Framework-Based Technologies.

The eradication and isolation of viruses are two concurrent approaches to protect ourselves from viral infections and diseases. The quite versatile porous materials called metal-organic frameworks (MOFs), have recently emerged as efficient nanosized tools to manage viruses, and several strategies to accomplish these tasks have been developed. This review describes these strategies employing nanoscale MOFs against SARS-CoV-2, HIV-1, tobacco mosaic virus, etc.

Metal-porphyrinic framework nanotechnologies in modern agricultural management.

Metal-porphyrinic frameworks are an important subclass of metal-organic frameworks (MOFs). These porous materials exhibit a large number of applications for sustainable development and related environmental considerations. Their attractive features include (1) as a free base or metalated with zinc(II) or iron(II or III), they are environmentally benign, and (2) they absorb visible light and are emissive and semi-conducting, making them convenient tools for sensing agrochemicals.

S-Heptazine N-ligand based luminescent coordination materials: synthesis, structural and luminescent studies of lanthanide-cyamelurate networks.

Various series of lanthanide metal-organic networks denoted Ln- (Ln = La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb), were synthesized under solvothermal conditions using potassium cyamelurate (K) and lanthanide nitrate salts. All obtained materials were fully characterized, and their crystal structures were solved by single-crystal X-ray diffraction. Four types of coordination modes were elucidated for the Ln- series with different Ln coordination geometries.

Chain Length Effect on the Structural and Emission Properties of the CuI/Bis((4-methoxyphenyl)thio)alkane Coordination Polymers.

A systematic chain length variation of the ligand -MeOCHS(CH)SCHOMe (1 ≤ ≤ 8) was performed to study its effect on the structures and photophysical properties of the coordination polymers (CP) when reacted with CuI. Indeed, direct correlations are noted between these features and . When is an odd number, the secondary building unit is systematically the common closed-cubane CuI cluster, rendering the material strongly luminescent (, emission quantum yield, Φ > 20%), and the CP is one-dimensional (1D).

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties.

The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[CuI()], , which is formed when ArS(CH)SAr (, Ar = 4-CHOMe) reacts with 2 equiv of CuI in EtCN. In MeCN, ([CuI()(MeCN)], consisting of an alternating [-CuI--CuI--] chain where the CuI cubane units bear two metal-bound MeCN molecules, is formed.

New phosphorescent iridium(III) dipyrrinato complexes: synthesis, emission properties and their deep red to near-infrared OLEDs.

A series of heteroleptic Ir(iii) complexes composed of two cyclometalated C^N ligands and one dipyrrinato ligand used as an ancillary ligand are synthesized and characterized. With the introduction of a fluorine atom, phenyl ring or diphenylamino group into both C^N ligands and by keeping the ancillary ligand unchanged, these Ir(iii) dipyrrinato phosphors do not show an obvious shift in their emission bands. They exhibit emissions extending well into the near-infrared region with an intense band located at around 685 nm in both photo- and electroluminescence spectra, and the deep red to near-infrared organic light emitting diodes (OLEDs) based on them afforded a maximum external quantum efficiency of 2.

Porphyrin-Containing MOFs and COFs as Heterogeneous Photosensitizers for Singlet Oxygen-Based Antimicrobial Nanodevices.

Visible-light irradiation of porphyrin and metalloporphyrin dyes in the presence of molecular oxygen can result in the photocatalytic generation of singlet oxygen (O). This type II reactive oxygen species (ROS) finds many applications where the dye, also called the photosensitizer, is dissolved (i.e.

Recent Advances in Nanoscale Metal-Organic Frameworks Towards Cancer Cell Cytotoxicity: An Overview.

Abstract: The fight against cancer has always been a prevalent research topic. Nanomaterials have the ability to directly penetrate cancer cells and potentially achieve minimally invasive, precise and efficient tumor annihilation. As such, nanoscale metal organic frameworks (nMOFs) are becoming increasingly attractive as potential therapeutic agents in the medical field due to their high structural variability, good biocompatibility, ease of surface functionalization as well as their porous morphologies with tunable cavity sizes.

The TDDFT Excitation Energies of the BODIPYs; The DFT and TDDFT Challenge Continues.

The derivatives of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) are pivotal ingredients for a large number of functional, stimuli-responsive materials and therapeutic molecules based on their photophysical properties, and there is a urgent need to understand and predict their optical traits prior to investing a large amount of resources in preparing them. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations were performed to calculate the excitation energies of the lowest-energy singlet excited state of a large series of common BODIPY derivatives employing various functional aiming at the best possible combination providing the least deviations from the experimental values. Using the common "fudge" correction, a series of combinations was investigated, and a methodology is proposed offering equal or better performances than what is reported in the literature.

A Platinum(II) Organometallic Building Block for the Design of Emissive Copper(I) and Silver(I) Coordination Polymers.

The tritopic organometallic ligand -MeSCHC≡CPt(PMe)(C≡N) () was prepared from -PtCl(PMe) and -ethynyl(methyl thioether)benzene. Its versatility was shown with the formation of [CuX()] coordination polymers (CPs) with CuX salts in MeCN (X = I (), CN (), SCN ()). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy.

From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH)SBz; = 1-9).

With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH)SBz ( = 1-9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCHBz () affording respectively the one-dimensional (1D) CPs {Cu(μ-I)Cu}(μ-)] () and {Cu(μ-Br)Cu}(μ-)] (), which incorporate Cu(μ-X)Cu rhomboids as secondary building units (SBUs).

Unusual triplet-triplet annihilation in a 3D copper(i) chloride coordination polymer.

A new coordination polymer (CP) defined as [CuCl(EtS(CH)SEt)] (CP2) was prepared by reacting EtS(CH)SEt with CuCl in acetonitrile in a 1 : 2 stoichiometric ratio. The X-ray structure reveals formation of non-porous 3D material composed of parallel 2D-[CuClS] layers of Cl-bridged Cu(μ-Cl) rhomboids assembled by EtS(CH)SEt ligands. A weak triplet emission (Φ < 0.

A 9.16% Power Conversion Efficiency Organic Solar Cell with a Porphyrin Conjugated Polymer Using a Nonfullerene Acceptor.

A new low-molecular-weight porphyrin-based polymer, , with pyridine-capped diketopyrrolopyrrole (DPP) has been synthesized, and its optical and electrochemical properties were investigated. The polymer is prepared with a low content of homocoupling units and gives a widely spread absorption from 400 to 900 nm with a narrow optical band gap of 1.46 eV.

Characterization and Minimization of Glaser Competitive Homocoupling in Sonogashira Porphyrin-Based Polycondensation.

A porphyrin-containing polymer exhibiting various degrees of Glaser-Hay coupling is reported. Sonogashira polycondensation of zinc(II) (5,15-bis[3,4,5-tri(2-butyloctyl)phenyl]-10,20-bis(ethynyl)porphyrinate) with N, N'-bis( p-iodobenzene)-2,3,5,6-tetrafluorobenzoquinone-1,4-diimine (fQI) is found to be prone to homocoupling, a problem underestimated in the literature. H NMR and photophysical analysis are used to assess the ratio of Glaser versus Sonogashira couplings.

Control of Structures and Emission Properties of (CuI) 2-Methyldithiane Coordination Polymers.

A structurally unique and strongly luminescent nonporous 3D coordination polymer (CP) [CuI(methyldithiane)] , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates an unprecedented CuI cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350, and 400 K to study the temperature dependence of the Cu···Cu distances.