A Mechanistic Study of Metal Template Syntheses of Dibenzo-tetraaza(14)annulene Macrocyclic Complexes

Cutler, Ann R.; Dolphin, David

doi:10.1080/00958977608079884

Cited by 17 publications

(9 citation statements)

References 17 publications

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“…As shown in Scheme 1a, the reaction at 100 °C under an argon atmosphere of 1,2-phenylenediamine dihydrochloride (1) and 1,1,3,3-tetramethoxypropane (2) in the presence of triethylamine, with Ni(II) as a template, afforded the model compound NiTAA via the simultaneous formation of four imine bonds coordinated to Ni(II) atoms in 78% yield. 25,38 Note that the four-coordination mode without coordinated S1, SI).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Being synthetic analogues of naturally occurring porphyrins, tetraaza[14]annulenes are a class of well-known synthetic macrocycles. − The four nitrogen atoms of tetraaza[14]annulenes can be easily deprotonated to generate dianionic ligands that coordinate with metal ions to form metal tetraaza[14]annulenes. , Metal tetraaza[14]annulenes have been applied in catalase mimics, field effect transistors, catalysts, and dye-sensitized solar cells. − Marks et al reported that a partial oxidation of the ligand in Ni(II) tetraaza[14]annulene by iodine led to the formation of an electrically conductive metallo-macrocycle . However, metal tetraaza[14]annulenes have not been used so far to produce framework materials, although attaching this macrocycle to a framework material could be promising for many applications.…”

Section: Introductionmentioning

confidence: 99%

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Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework

Jiang

Joo

et al. 2019

J. Am. Chem. Soc.

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We report the synthesis and characterization of a two-dimensional (2D) conjugated Ni(II) tetraaza[14]annulene-linked metal organic framework (NiTAA-MOF) where NiTAA is a macrocyclic MN4 (M = metal, N = nitrogen) compound. The structure of NiTAA-MOF was elucidated by Fourier-transform infrared, X-ray photoemission, and X-ray diffraction spectroscopies, in combination with density functional theory (DFT) calculations. When chemically oxidized by iodine, the insulating bulk NiTAA-MOF (σ < 10–10 S/cm) exhibits an electrical conductivity of 0.01 S/cm at 300 K, demonstrating the vital role of ligand oxidation in the electrical conductivity of 2D MOFs. Magnetization measurements show that iodine-doped NiTAA-MOF is paramagnetic with weak antiferromagnetic coupling due to the presence of organic radicals of oxidized ligands and high-spin Ni(II) sites of the missing-linker defects. In addition to providing further insights into the origin of the induced electrical conductivity in 2D MOFs, both pristine and iodine-doped NiTAA-MOF synthesized in this work could find potential applications in areas such as catalase mimics, catalysis, energy storage, and dynamic nuclear polarization-nuclear magnetic resonance (DNP-NMR).

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework

Jiang

Joo

et al. 2019

J. Am. Chem. Soc.

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“…In addition to commonly explored porphyrins and phthalocyanines, also well known but less studied (in the context of carbon nanohybrid materials) are tetraazamacrocyclic compounds exhibiting rather similar optical and electronic properties, which belong to the family of tetraaza [14]annulenes including both free ligands and their transition metal complexes [17][18][19][20][21][22][23][24][25][26]. As considered per se, these compounds exhibit a wide spectrum of interesting and potentially useful properties [27][28][29], being able to act as DNA/RNA binding agents [30][31][32], catalase mimics [33], conducting materials [34][35][36][37][38][39], chiral receptors [40], gas sensors [41][42][43], and electrocatalysts [44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Interaction of a Ni(II) tetraazaannulene complex with elongated fullerenes as simple models for carbon nanotubes

Henao-Holguín

Basiuk

2015

J Mol Model

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Nickel(II) complex of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine (NiTMTAA), which can be employed for noncovalent functionalization of carbon nanotubes (CNTs), represents a more complex and interesting case in terms of structure of the resulting nanohybrids, as compared to the related materials functionalized with porphyrins and phthalocyanines. Due to its saddle shape, the NiTMTAA molecule adsorbed can adopt different, energetically non-equivalent orientations with respect to CNT, depending on whether CH3 or C6H4 groups contact the latter. The main goal of the present work was to provide information on the interactions of NiTMTAA with simple single-walled CNT (SWNT) models accessible for dispersion-corrected DFT calculations. For reasons of comparison, we employed three such functionals: M06-2X and LC-BLYP as implemented in Gaussian 09 package, and PBE-G as implemented in Materials Studio 6.0. In order to roughly estimate the effect of nanotube chirality on the interaction strenght, we considered two short closed-end SWNT models (also referred to as 'elongated fullerenes'), one armchair and one zigzag, derived from C60 and C80 hemispheres. In addition, we calculated similar complexes with C60, as well as I h and D 5h isomers of C80. The results were analyzed in terms of optimized geometries, formation energies, HOMO-LUMO gap energies, and intermolecular separations. Graphical Abstract Interaction of Ni(II) tetraazaannulene complex with elongated fullerenes.

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“…For example, [Ni( L301)] can be obtained according to Scheme 2-18 in two ways. The second is considered to be more effective as, on heating an aqueous solution of o-phda, 1,1,3,3-tetramethoxypropane and nickel( 11) acetate (2:2: l), the analytically pure macrocyclic product is isolated in a more than 85% yield [335]. The second is considered to be more effective as, on heating an aqueous solution of o-phda, 1,1,3,3-tetramethoxypropane and nickel( 11) acetate (2:2: l), the analytically pure macrocyclic product is isolated in a more than 85% yield [335].…”

Section: 7mentioning

confidence: 99%

“…The first involves using the 1,5benzdiazepinium salt (HL298)PF6, which in the presence of nickel( 11) acetate in boiling aqueous methanol or dimethylformamide gives [Ni( L301)] in 20% yield [335]. In the absence of the nickel ions, a sediment of undefined composition not containing H2L301 is formed [335]. In the absence of the nickel ions, a sediment of undefined composition not containing H2L301 is formed [335].…”

Section: 7mentioning

confidence: 99%

Template synthesis of polyazamacrocyclic compounds

Gérbéléu

Arion

Burgess

1999

Template Synthesis of Macrocyclic Compounds

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Compounds containing nitrogen in their cyclic backbone are one of the most representative groups of macrocyclic systems, and are very often synthesised by template reactions. The ligsons participating in the construction of ligand products must have certain groups or positions in moleculeswhich are sometimes concealed, revealing themselves when coordinated and activated by the template.Building up polyazamacrocyclic systems on the appropriate matrices is carried out by the interaction of compounds containing amine or imine groups with aldehydes, ketones, organic halogen derivatives, substituted malonic esters and ligsons containing unsaturated C-C bonds. The process may also be performed by interaction of the appropriate blocks, containing both functional groups necessary for obtaining the final product. Among such template reactions the most frequent is the formation of azomethine construction bonds, then C-N and C-C and in some cases, N=N chelatogene bonds.

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A Mechanistic Study of Metal Template Syntheses of Dibenzo-tetraaza(14)annulene Macrocyclic Complexes

Cited by 17 publications

References 17 publications

Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework

Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework

Interaction of a Ni(II) tetraazaannulene complex with elongated fullerenes as simple models for carbon nanotubes

Template synthesis of polyazamacrocyclic compounds

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