Synthesis, X-ray Structure, and Self-Assembly of Functionalized Bis(2,2‘:6‘,2‘ ‘-terpyridinyl)arenes

meta-Bis(terpyridinyl)phenol has been synthesized from O-benzyl-3,5-di(formyl)phenol in three steps. Its alkylation afforded a series of bisterpyridinylarenes, which can be self-assembled to afford the corresponding hexametallomacrocycles possessing Fe(II), Zn(II), or Ru(II) connectivity

Synthesis, X-ray Structure, and Self-Assembly of Functionalized Bis(2,2‘:6‘,2‘ ‘-terpyridinyl)arenes

meta-Bis(terpyridinyl)phenol has been synthesized from O-benzyl-3,5-di(formyl)phenol in three steps. Its alkylation afforded a series of bisterpyridinylarenes, which can be self-assembled to afford the corresponding hexametallomacrocycles possessing Fe(II), Zn(II), or Ru(II) connectivity

Synthesis, X-ray Structure, and Self-Assembly of Functionalized Bis(2,2‘:6‘,2‘ ‘-terpyridinyl)arenes

meta-Bis(terpyridinyl)phenol has been synthesized from O-benzyl-3,5-di(formyl)phenol in three steps. Its alkylation afforded a series of bisterpyridinylarenes, which can be self-assembled to afford the corresponding hexametallomacrocycles possessing Fe(II), Zn(II), or Ru(II) connectivity

Convenient Synthesis of 1 → 3 <i>C</i>-Branched Dendrons

A facile, efficient synthesis of 1 → 3 C-branched polyamide dendrons is described. Treatment of acryloyl chloride with 1 → 3 C-branched amines, e.g., di-tert-butyl 4-[2-(tert-butoxycarbonyl)ethyl]-4-aminoheptanedioate, gave the corresponding acrylamides in high yields, which upon reaction with nitromethane generated the homologated nitroalkane-polyesters. Finally, nitroalkane alkylation with 2 equiv of the acrylamides, followed by nitro group reduction, afforded the desired amino-polyesters

Novel Twofold Interpenetrating Channel Framework Based on Metal Tetramer Subunits

Tetrameric, metal-based subunits, [Ni4(d-ala)2(l-ala)2] (d-ala = d-alanine anion, l-ala = l-alanine anion), designed as nodes to construct coordination frameworks, allowed the synthesis of a new twofold interpenetrating channel architecture {[Ni4(d-ala)2(l-ala)2(1,2-bpe)4]·17H2O}n [1,2-bpe = 1,2-bis(4-pyridyl)ethylene]. Characterization included thermogravimetric analyses, IR spectroscopy, X-ray powder diffraction, and single crystal X-ray diffraction. Triangular and rectangular short circuits were formed by the tetrameric nodes and 1,2-bpe linkers that consisted of a triangular prism, and they were further assembled into a twofold interpenetrating parallelepiped motif. The hierarchical construction, based on tetramer nodes and the 1,2-bpe linkers in the channel framework, was investigated

Novel Twofold Interpenetrating Channel Framework Based on Metal Tetramer Subunits

Tetrameric, metal-based subunits, [Ni4(d-ala)2(l-ala)2] (d-ala = d-alanine anion, l-ala = l-alanine anion), designed as nodes to construct coordination frameworks, allowed the synthesis of a new twofold interpenetrating channel architecture {[Ni4(d-ala)2(l-ala)2(1,2-bpe)4]·17H2O}n [1,2-bpe = 1,2-bis(4-pyridyl)ethylene]. Characterization included thermogravimetric analyses, IR spectroscopy, X-ray powder diffraction, and single crystal X-ray diffraction. Triangular and rectangular short circuits were formed by the tetrameric nodes and 1,2-bpe linkers that consisted of a triangular prism, and they were further assembled into a twofold interpenetrating parallelepiped motif. The hierarchical construction, based on tetramer nodes and the 1,2-bpe linkers in the channel framework, was investigated

Gradient Tandem Mass Spectrometry Interfaced with Ion Mobility Separation for the Characterization of Supramolecular Architectures

Traveling wave ion mobility mass spectrometry (TWIM MS) was combined with gradient tandem mass spectrometry (gMS2) to deconvolute and characterize superimposed ions with different charges and shapes formed by electrospray ionization (ESI) of self-assembled, hexameric metallomacrocycles composed of terpyridine-based ligands and CdII ions. ESI conditions were optimized to obtain intact hexameric cation assemblies in a low charge state (2+), in order to minimize overlapping fragments of the same mass-to-charge ratio. With TWIM MS, intact hexameric ions could be separated from remaining fragments and aggregates. Collisional activation of these hexameric ions at varying collision energies (gMS2), followed by TWIM separation, was then performed to resolve macrocyclic from linear hexameric species. Because of the different stabilities of these architectures, gMS2 changes their relative amounts, which can be monitored individually after subsequent ion mobility separation. On the basis of this unique strategy, hexameric cyclic and linear isomers have been successfully resolved and identified. Complementary structural information was gained by the gMS2 fragmentation pattern of the metallosupramolecules, acquired by collisionally activated dissociation after TWIM dispersion. TWIM MS interfaced with gMS2 should be particularly valuable for the characterization of a variety of supramolecular polymers, which often contain isomeric architectures that yield overlapping fragments and aggregates upon ESI MS analysis

Synthesis and Single-Crystal X-ray Characterization of 4,4‘ ‘-Functionalized 4‘-(4-Bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines

To expand the utility of bis(terpyridine) metal connectivity, the selective symmetrical and unsymmetrical 4,4‘ ‘-functionalization (−CN, −Me, −CO2Me) of 4‘-(4-bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines was achieved using the Kröhnke synthesis. The final substituted 2,2‘:6‘,2‘ ‘-terpyridines along with their corresponding intermediates, 4a−c, were recrystallized and characterized by 1H NMR and 13C NMR as well as X-ray crystallography; COSY correlations were also conducted to permit definitive proton assignment

Novel Twofold Interpenetrating Channel Framework Based on Metal Tetramer Subunits

Tetrameric, metal-based subunits, [Ni4(d-ala)2(l-ala)2] (d-ala = d-alanine anion, l-ala = l-alanine anion), designed as nodes to construct coordination frameworks, allowed the synthesis of a new twofold interpenetrating channel architecture {[Ni4(d-ala)2(l-ala)2(1,2-bpe)4]·17H2O}n [1,2-bpe = 1,2-bis(4-pyridyl)ethylene]. Characterization included thermogravimetric analyses, IR spectroscopy, X-ray powder diffraction, and single crystal X-ray diffraction. Triangular and rectangular short circuits were formed by the tetrameric nodes and 1,2-bpe linkers that consisted of a triangular prism, and they were further assembled into a twofold interpenetrating parallelepiped motif. The hierarchical construction, based on tetramer nodes and the 1,2-bpe linkers in the channel framework, was investigated

Synthesis and Single-Crystal X-ray Characterization of 4,4‘ ‘-Functionalized 4‘-(4-Bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines

To expand the utility of bis(terpyridine) metal connectivity, the selective symmetrical and unsymmetrical 4,4‘ ‘-functionalization (−CN, −Me, −CO2Me) of 4‘-(4-bromophenyl)-2,2‘:6‘,2‘ ‘-terpyridines was achieved using the Kröhnke synthesis. The final substituted 2,2‘:6‘,2‘ ‘-terpyridines along with their corresponding intermediates, 4a−c, were recrystallized and characterized by 1H NMR and 13C NMR as well as X-ray crystallography; COSY correlations were also conducted to permit definitive proton assignment