Rhenium-Pyrazolyl-Based Figure-Eight- and Z-Shaped Metallocycles: Self-Assembly, Solid-State Structures, Dynamic Properties in Solution, and Competitive Ligand-Induced Supramolecular Transformations into Rhenium-Pyridyl/-Benzimidazolyl/-Phosphine-Based Metallocycles/Acyclic Complexes.

Rhenium(I)tricarbonyl core-based heteroleptic "figure-eight"- and Z-shaped metallocycles (1a-4a) of the general formula fac-[{(CO)3Re(µ-L)Re(CO)3}2(dppz)2] were self-assembled from Re2(CO)10, H2-L (H2-L = 5,8-dihydroxy-1,4-naphthaquinone (H2-dhnq) for 1a; 1,4-dihydroxy-9,10-anthraquinone (H2-dhaq) for 2a; 6,11-dihydroxy-5,12-naphthacenedione (H2-dhnd) for 3a; 2,2'-bisbenzimidazole (H2-bbim) for 4a), and bis(4-((pyrazolyl)methyl)phenylmethane) (dppz) via one-pot coordination-driven synthetic approach. The molecular structures of 1a and 4a were unambiguously confirmed by single-crystal X-ray diffraction (SC-XRD) methods. The metallocycles in the DMSO solution exist as an acyclic dinuclear-DMSO adduct of the general formula fac-[{(CO)3Re(µ-L)Re(CO)3}(DMSO)2] (1b, L = dhnq; 2b, L = dhaq; 3b, L = dhnd; 4b, L = bbim) and dppz, which are in dynamic equilibrium. The dynamic behavior of the rhenium-pyrazolyl bond in the solution state was effectively utilized to transform metallocycles 1a-4a into pyridyl/benzimidazolyl/phosphine donor-based heteroleptic metallocycles and acyclic dinuclear complexes (4-13). These include tetranuclear rectangles fac-[{(CO)3Re(µ-L)Re(CO)3}2(4,4'-bpy)2] (4 and 11, L = dhaq for 4 and bbim for 11), dinuclear metallocycles fac-[{(CO)3Re(µ-L)Re(CO)3}(dpbim)] (5-7 and 12; L = dhnq for 5, dhaq for 6, dhnd for 7, and bbim for 12), and dinuclear acyclic complexes fac-[{(CO)3Re(µ-L)Re(CO)3}(PTA)2] (8-10 and 13; L = dhnq for 8, dhaq for 9, dhnd for 10, and bbim for 13). These transformations were achieved through component-induced supramolecular reactions while treating with competitive ligands 4,4'-bipyridine (4,4'-bpy), bis(4-((1H-benzoimidazole-1-yl)methyl)phenyl)methane (dpbim), and 1,3,5-triaza-7-phosphaadamantane (PTA). The reaction mixture in the solution was analyzed using NMR and electrospray ionization mass spectrometry (ESI-MS) analysis. Additionally, crystal structures of 4, 6, and 13, which were obtained in the mixture of the solutions, were determined, providing unequivocal evidence for the occurrence of supramolecular transformation within the system. The results reveal that the size of the chelating ligand and the pyrazolyl donor angle of the ditopic ligand play crucial roles in determining the resulting solid-state metallacyclic architecture in these synthetic combinations. The dynamic behavior of the rhenium-pyrazolyl bond in the metallocycles can be utilized to transform into other metallocycles and acyclic complexes using suitable competing ligands via ligand-induced supramolecular transformations.

Trinuclear rhenium(I)-based metallocages as anticancer agents towards human cervical cancer cells.

The first examples of spherical-shaped trinuclear rhenium(I) organometallic cages displaying cytotoxic, antimetastatic, antiproliferative and DNA-damaging behavior towards a human cervical (HeLa) cancer cell line are reported. The compact design of the metallocages facilitates their interactions with biosystems leading to comparable efficiency to that of the commonly used anticancer drug cisplatin.

Self-Assembly of Rhenium(I) Double-Stranded Helicate and Mesocate from Flexible Ditopic Benzimidazolyl/Naphthanoimidazolyl N-Donor and Rigid Bis-Chelating Hydroxyphenylbenzimidazolyl N∩OH-Donor Ligands: Synthesis, Characterization, and Photophysical and B-DNA Docking Studies.

The self-assembly of three rheniumtricarbonyl core-based supramolecular coordination complexes (SCCs), fac-[Re(CO)3(µ-L)(µ-L')Re(CO)3] (1-3) was carried out using Re2(CO)10, rigid bis-chelating ligand (HO∩N-Ph-N∩OH (L1) (where HO∩N = 2-hydroxyphenylbenzimidazolyl), and flexible ditopic N-donor ligands (L2 = bis(3-((1H-benzoimidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L3 = bis(3-((1H-naphtho[2,3-d]imidazol-1-yl)methyl)-2,4,6-trimethylphenyl)methane, L4 = bis(4-(naphtho[2,3-d]imidazol-1-yl-methyl)phenyl)methane) via a one-pot solvothermal approach. In the solid state, the dinuclear SCCs adopt heteroleptic double-stranded helicate and meso-helicate architectures. The supramolecular structures of the complexes are retained in the solution based on the 1H NMR and electrospray ionization (ESI)-mass analysis. The spectral and photophysical properties of the complexes were studied both experimentally and using time-dependent density functional theory (TDDFT) calculations. All of the supramolecules exhibited emission in both solution and solid states. Theoretical studies were conducted to determine the chemical reactivity parameters, molecular electrostatic potential surface plots, natural population, and Hirshfeld analysis for complexes 1-3. Additionally, molecular docking studies were carried out for complexes 1-3 with B-DNA.

Transition-Metal-Free Dehydrogenation of Benzyl Alcohol for C-C and C-N Bond Formation for the Synthesis of Pyrazolo[3,4-b]pyridine and Pyrazoline Derivatives.

A series of cascade reactions that produce a range of functionalized aromatic heterocyclic compounds with pyrazole/pyrazoline cores have been developed. The method relies on a metal-free dehydrogenative process to produce in-situ benzaldehydes. The produced benzaldehyde was then allowed to react with some other substances, including acetophenone, pyrazole amine, and phenylhydrazine. The intermediate produced from these substrates underwent several chemical processes, including electrocyclization, the aza-Diels-Alder reaction, and the formation of intramolecular C-N bonds. These positive outcomes would open up the possibility of producing biologically active pyrazolo[3,4-b]pyridine and pyrazoline derivatives through a variety of possible reactions.

Synthesis and Optoelectronic Features of Rhodamine-Triazole Dyads as Metallochromic Probes for Copper-Selective Chemosensing.

Rhodamine-based chromic materials have attracted significant interest owing to their cation recognition ability with high sensitivity. However, rhodamine chromophores with controllable sensing selectivity towards transition metal species are only at the advent. Herein, three triazole-conjugated rhodamine dyads with different peripheral substituents were synthesized. The key triazole precursors required for the desired chemistry were prepared by adopting our recently developed CTAB catalyzed mechano-click chemistry. Molecular properties derived from photophysics, electrochemistry and surface morphology of the synthesized dyads were analyzed. Furthermore, frontier molecular orbitals, electronic structure and secondary quantum chemical parameters of dyads were also compared. Screening of dyads for their sensing ability towards an array of alkali, alkaline and transition metal ions exhibited a noticeable naked-eye detection of Cu2+ ions and was confirmed by spectrophotometric titration. The specific binding mode of dyads as probable with Cu2+ over other metal ions attributes to the chemoselectivity.

Self-assembly of a new class of rhenium(I)-based double stranded dinuclear monohelicates with their photophysical and electrochemical studies.

A new class of double stranded dinuclear monohelicates, fac-[{Re(CO)3-(µ-L)-Re(CO)3}Ln] (1-4), were self-assembled from Re2(CO)10, a rigid bischelating donor (H2-L: 1,4-dihydroxybenzoquinone (H2-dhbq) for 1 and 3; 2,5-pyrazine dicarboxylic acid (H2-pydc) for 2 and 4) and a flexible bis(monodentate) pyrazolyl N donor Ln (L1 = bis(4-((pyrazolyl)methyl)phenyl)methane for 1 and 2; L2 = bis(4-((pyrazolyl)methyl)phenyl)methanone for 3 and 4) in mesitylene. Metallomacrocycle 1 was confirmed by single crystal X-ray crystallography. Although these helicates contain two organic ligand strands, only one strand is arranged in a helical fashion, which is an unprecedented form in the helicate architecture. The molecular structures of 1-4 as helicates and mesocates were optimized using DFT methods. The dynamic interconversion of the metallomacrocycles in solution was studied by 1H NMR studies. The photophysical properties of 1-4 were studied experimentally and the nature of electronic transitions was determined by TD-DFT analysis. Quinonoid motif-based complexes 1 and 3 displayed strong visible light absorption. The redox properties of 1-4 were studied using cyclic voltammetry.

Dimethyl Sulfoxide-Assisted, Iodine- and Ascorbic Acid-Catalyzed One-Pot Synthetic Approach for Constructing Highly Substituted Pyrazolo[1,5-a]quinoline Thioether Derivatives.

A dimethyl sulfoxide-assisted and iodine/ascorbic acid-catalyzed simple approach to pyrazolo[1,5-a]quinoline thioether derivatives 22 is described. The compounds were identified using 1H NMR, 13C NMR, high-resolution mass spectrometry, and single-crystal X-ray diffractometry. The pyrazolo[1,5-a]quinoline thioether was synthesized in a stepwise fashion through aryl sulfenylation and benzannulation strategies. The generated heteroaryl thioether compounds 23 were exposed to the benzannulation path to produce pyrazolo[1,5-a]quinoline thioether 22. The benzannulation reaction proceeds by way of diazotization of the pyrazole amine derivative 23, radical generation by the removal of nitrogen, and eventually trapping of the aryl radical with the support of phenylacetylene 19. A catalytic amount of ascorbic acid aided the benzannulation reaction. There were several other control studies conducted, including trapping reactions with isopropenyl acetate, tetramethylpiperidine N-oxyl reactions, and reactions without phenylacetylene. Since a change in the substitution has previously demonstrated substantial bioactivity, the core structure of pyrazole was evaluated for functional group tolerance. A reasonable mechanism is then proposed, accompanied by the support of control experiments and scope. A Suzuki reaction was used to create an aryl/heteroaryl compound 35 from one of the synthesized compounds 22b. In the controlled oxidation reaction paths, molecule 22a was selectively transformed into the corresponding sulfoxide 32 and sulfone 33.

Rhenium(I)-Based Neutral Coordination Cages with a Spherical Cavity for Selective Recognition of Fluoride.

Neutral heteroleptic trinuclear coordination cages containing a preorganized well-defined small spherical endocavity, which is made up of electron-deficient bowl frameworks, three coordination-induced neutral polar C-H donors, and a phenyl motif, were self-assembled via a one-pot approach; the endocavity accommodates fluoride selectively in the presence of other halides.

Rhenium(I)-Based Heteroleptic Pentagonal Toroid-Shaped Metallocavitands: Self-Assembly and Molecular Recognition Studies.

A family of neutral, heteroleptic, dinuclear M2LL'-type pentagonal toroid-shaped metallomacrocycles (1-8) were synthesized using flexible ditopic N donors (Ln = L1-L2), rigid bis-chelating ligands (H2-L' = H2-E), and Re2(CO)10 in a one-pot solvothermal self-assembly approach. The ligands and the metallomacrocycles were characterized using ATR-IR, electrospray ionization mass spectrometry, nuclear magnetic resonance, ultraviolet-visible, and emission spectroscopy methods. The molecular structures of 1, 2, 4, 6, and 7 were confirmed by an X-ray diffraction study and are similar to those of calix[5]arene. The cyclic inner cavities of the metallomacrocycles accommodate toluene/mesitylene/acetone/chlorobenzene as guest molecules that are stabilized by cumulative C-H···π and π···π interactions with the cyclic framework of metallomacrocycle. The photophysical properties of the ligands and the metallomacrocycles were studied. The host-guest recognition properties of metallocavitands 1, 2, 7, and 8 as a model host with phenol and nitrobenzene derivatives as guest molecules were studied by emission spectroscopy methods.

fac-Re(CO)3-based neutral heteroleptic tetrahedrons.

Four new flexible ditopic nitrogen donors possessing a xylene spacer and 2-phenylbenzimidazolyl or its derivatives as a coordinating unit and one rigid bis-chelating ligand consisting of two 2-hydroxyphenylbenzimidazolyl motifs and a central phenylene spacer were synthesized and further used with Re2(CO)10 for making a new family of neutral, heteroleptic tetrahedral-shaped supramolecular coordination complexes via a one-pot approach. The new ligands and the complexes were characterized using various analytical and spectroscopic methods. The molecular structures of the complexes were determined using single crystal X-ray diffraction analysis, which reveal that four rhenium cores are arranged in the vertices, and four ligands are at the edges of the tetrahedron.

Phosphine oxide-based tricarbonylrhenium(i) complexes from phosphine/phosphine oxide and dihydroxybenzoquinones.

Neutral phosphine oxide (P[double bond, length as m-dash]O) donor-based organometallic complexes [{Re(CO)3O[double bond, length as m-dash]PCy3}{µ-DHBQ}{Re(CO)3O[double bond, length as m-dash]PCy3}] (1), [{Re(CO)3O[double bond, length as m-dash]PPh3}{µ-DHBQ}{Re(CO)3O[double bond, length as m-dash]PPh3}] (2), [{Re(CO)3O[double bond, length as m-dash]PCy3}{µ-THQ}{Re(CO)3O[double bond, length as m-dash]PCy3}] (3), [{Re(CO)3O[double bond, length as m-dash]PPh3}{µ-THQ}{Re(CO)3O[double bond, length as m-dash]PPh3}] (4), [{Re(CO)3O[double bond, length as m-dash]PCy3}{µ-CA}{Re(CO)3O[double bond, length as m-dash]PCy3}] (5), and [{Re(CO)3O[double bond, length as m-dash]PPh3}{µ-CA}{Re(CO)3O[double bond, length as m-dash]PPh3}] (6) were assembled from phosphine/phosphine oxide, a dihydroxybenzoquinone donor and Re2(CO)10via a one-pot solvothermal approach. The soft phosphine donor was transformed into a hard phosphine oxide donor during the formation of 1, 3, 4, 5, and 6. The complexes 1-6 were air and moisture stable and were soluble in polar organic solvents. The complexes were characterized by elemental analysis, FT-IR, and NMR spectroscopic methods. The molecular structures of 1, 2, 4, and 6 were analyzed by single-crystal X-ray diffraction analysis. The UV-Visible absorption studies indicated that 1-6 in THF display strong visible light absorption in the range of ∼350-700 nm.

Sulfate Donor Based Dinuclear Heteroleptic Triple-Stranded Helicates from Sulfite and Ditopic Nitrogen Donor Ligands and Their Transformation to Dinuclear Homoleptic Double-Stranded Mesocates.

Sulfate donor based supramolecular coordination complexes [{ fac-Re(CO)3}(µ-SO4)(L n)2{ fac-Re(CO)3}] (1-3) were obtained using ditopic N donors (L n; n = 1-3), NaHSO3, and Re2(CO)10 in a one-pot, multicomponent, coordination-driven self-assembly approach, in which SO32- becomes oxidized to SO42- during the reaction and acts as a building framework. Complexes 1-3 were characterized using IR, ESI-TOF-MS, and 1H NMR spectroscopy. The structures of complexes 1-3 were confirmed using single-crystal X-ray diffraction analysis. The transformation of the dinuclear heteroleptic triple-stranded helicate to the dinuclear homoleptic double-stranded mesocate [{Re(CO)3Cl}2(L n)2] (L n = L1, L2, L3; 4a-6a) was achieved by the addition of BaCl2. The direct treatment of Re(CO)5X (X = Cl, Br) with L1/L2/L3 yielded the dinuclear homoleptic double-stranded helicates [{Re(CO)3X}2 (L n)2] (4b-6b and 7-9).

Rhenium(i) based irregular pentagonal-shaped metallacavitands.

Neutral ditopic flexible N-donor ligands (Ln = bis(4-(naphtho[2,3-d]imidazol-1-ylmethyl)phenyl)methane, L1 bis(4-(benzimidazol-1-ylmethyl)phenyl)methane, L2 or bis(4-(2-nonylbenzimidazol-1-ylmethyl)phenyl)methane, L3) possessing a bis(4-methylphenyl)methane spacer with two imidazolyl donor units were designed and synthesized. The ligands were utilized to develop metallacavitands analogous to irregular pentagonal-shaped metallacavitands with larger cavities. The metallacavitands 1-4 were assembled from Re2(CO)10, a rigid bis-chelating donor (1,4-dihydroxy-9,10-anthraquinone or chloranilic acid) and Lnvia a solvothermal approach. The ligands and the metallacavitands were characterized by analytical and spectroscopic methods. The molecular structures of 1 and 4 were further confirmed by single crystal X-ray diffraction analysis which revealed that a toluene molecule resides in the hydrophobic cavity. Ln and 1-4 are emissive in DMSO at room temperature. The internal cavity of the metallacavitand acts as a host for aromatic guest molecules. The host-guest interaction properties of 1 with anthracene, naphthalene, nitrobenzene, 2-nitrotoluene, 4-nitrotoluene and 2,4-dinitrotoluene were studied by an emission spectroscopic method.

Crystal structure of the cis and trans polymorphs of bis-[µ-2-(1,3-benzo-thia-zol-2-yl)phenolato]-κ3N,O:O;κ3O:N,O-bis-[fac-tri-carbonyl-rhenium(I)].

The title dinuclear complex, [Re2(C13H8NOS)2(CO)6], crystallizes in two polymorphs where the 2-(1,3-benzo-thia-zol-2-yl)phenolate ligands and two carbonyl groups are trans- (I) or cis-arranged (II) with respect to the [Re2O2(CO)4] core. Polymorphs I and II exhibit a crystallographically imposed centre of symmetry and a twofold rotation axis, respectively. The structures may be described as being formed by two octa-hedrally distorted metal-coordinating units fused through µ-oxido bridges, leading to edge-sharing dimers. The crystal packing is governed by C-H⋯O hydrogen-bonding inter-actions, forming chains parallel to the c axis in I and a three-dimensional network in II.

Spheroid Metallacycles and Metallocavitands with Calixarene- and/or Cleft-Shaped Receptors on the Surface.

Flexible hexatopic ligands, 1,2,3,4,5,6-hexakis(1H-naphtho[2,3-d]imidazol-1-ylmethyl)benzene (L(2)) and 1,2,3,4,5,6-hexakis(4,5-diphenylimidazol-1-ylmethyl)benzene (L(3)), containing six neutral naphthanoimidazolyl and 4,5-diphenylimidazolyl N donors were synthesized and used to assemble M6L6L'-type [M = Re(CO)3, L = anionic angular rigid NN donors, and L' = flexible hexatopic N donors] spheroid metallacycles. These molecules with a diameter of ∼17 Šwere obtained from Re2(CO)10, H-L (imidazole, benzimidazole, and naphthanoimidazole), and L' [1,2,3,4,5,6-hexakis(benzimidazol-1-ylmethyl)benzene (L(1)), L(2), and L(3)] in a one-step process. Ligands L(2) and L(3) were characterized by elemental analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and (1)H NMR spectroscopy. Metallacycles 1-5 were characterized by elemental analysis, ESI-TOF-MS, Fourier transform infrared spectroscopy, and single-crystal X-ray diffraction analysis. Molecules 1, 2, and 4 can be considered as metallocavitands and contain multiple solvent-accessible receptors, i.e., two metallocalix[3]arene units and six/four calix[4]arene-/cleft-shaped receptors, on the surface. Guests such as acetone molecules could be accommodated in the calix[4]arene/cleft-shaped receptor of the metallocavitands.

Rhenium(I)-Based Monocyclic and Bicyclic Phosphine Oxide-Coordinated Supramolecular Complexes.

Neutral, flexible ditopic phosphine (P-P) or phosphine oxide (O=P-P=O) donors, rigid anionic bis-chelating oxygen donors, and Re2(CO)10 were used to assemble ten phosphine oxide (P=O)-donor-based neutral monocyclic M2LL'-, bicyclic M4L2L″-, and bicyclic M4LL'2-type supramolecular coordination complexes (SCCs). A soft ditopic phosphine donor was transformed into a hard ditopic phosphine oxide donor, during the formation of the cyclic complexes 1-3, 5-6, and 9-10. Complexes 4, 7, and 8 were obtained using a hard P=O donor ligand. These SCCs were characterized using elemental analysis, FTIR, NMR, and single-crystal X-ray diffraction analysis. The absorption properties of 1-8 were studied using absorption UV-vis spectroscopic methods, and the results were analyzed using theoretical calculations. The results revealed that the neutral P=O donor significantly influenced the photophysical properties by enhancing the absorption coefficient in the visible region.

Rhenium(I)-based Double-heterostranded Helicates.

Rhenium(I)-based supramolecular coordination complexes were obtained using Re2(CO)10, (2-hydroxyphenyl)benzimidazole-derived bis-chelating N∩O donors and a benzimidazolyl-derived ditopic monodentate N-donor possessing Troger's base spacer in a one-pot approach.

Rhenium(I)-based bridgeless double metallocalix[4]arenes.

Bridgeless double metallocalix[4]arenes possessing two orthogonally arranged dinuclear cavitands were obtained from a Re2(CO)10, rigid bis-chelating OO donor (H2-L), and a flexible bis-ditopic NN donor (L') by a one-pot approach.

Spheroid metallocavitands with eight calixarene-shaped receptors on the surface.

Spheroid metallocavitands [((Re(CO)3L)3)2L'] with a diameter of ~17 Å, possessing eight solvent-accessible calixarene-shaped receptors on the surface, were obtained from a Re2(CO)10, rigid NN donors (H-L), and flexible hexatopic N donors (L') in a one-step process.

Luminescent dirhenium(I)-double-heterostranded helicate and mesocate.

The semirigid ligands 1,4-bis(2-(2-hydroxyphenyl)benzimidazol-1-ylmethyl)benzene (H2-pBC) and 1,3-bis(2-(2-hydroxyphenyl)benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (H2-mBC), containing two hydroxyphenylbenzimidazolyl units as bis-chelating (or bis(bidentate)) N∩OH donor, were synthesized and were used to assemble neutral, luminescent heteroleptic, unsaturated double-hetero-stranded, rhenium(I)-based helicate (1) and mesocate (2) with the flexible bis(monodentate) nitrogen donor (1,4-bis(benzimidazol-1-ylmethyl)benzene/1,3-bis(benzimidazol-1-ylmethyl)benzene), and Re2(CO)10. The photophysical properties of the complexes were studied. Both complexes 1 and 2 exhibit dual emissions in both solution and solid state. In solution, these complexes show both fluorescence and phosphorescence. Complex 1 undergoes a predominantly ligand-centered oxidation, resulting in the generation of phenoxyl radicals.